JP2005048252A - Carbon film-coated article having lubricity and releasing property, and surface treatment method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problems that, though an improvement in various film deposition conditions has been tried as the means for improving nonuniformity in film thickness and adhesion, the obtained article is the limited one owing to the complication of a pretreatment stage, thermal influence on the working, the limitation of the base material to be used, the limitation of carbon film thickness or the like, also, the article could not endure use over a long period since there has been limitation on the content of fluorine in a carbon film. <P>SOLUTION: In the carbon film-coated article having both lubricity and releasing properties and the surface treatment method therefor, using a plasma base ion implantation-film deposition method, in a vacuum, gaseous fluorine or hydrocarbonaceous gas containing at least one or more atoms is introduced, and high frequency electric power is fed to generate plasma, high frequency pulse voltage is applied to the object to be treated therein, ions containing carbon or fluorine are implanted into the surface of the object to be treated, and simultaneously, a fluorine-containing carbon film is formed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a surface treatment technique for ion implantation / film formation in plasma and a technique for manufacturing a carbon film-coated article containing fluorine for the purpose of imparting lubricity and releasability to metal, ceramics, plastic molded articles and the like. Is.

Conventionally, a method of forming a diamond-like carbon layer (hereinafter referred to as a carbon film) has been proposed in order to impart slipperiness to the surface of a metal material or the surface of a ceramic material. A method of forming a carbon film by a plasma CVD method using raw materials such as methane gas and acetylene gas on the surface of a member that slides with a machine part or a contact member has already been put into practical use, such as a video tape capstan roller, a small bearing, Excellent performance such as hot / cold switching valve.

As described in Japanese Patent Application No. 10-189695, Japanese Patent Application No. 11-172130, etc., in the plasma CVD method, the plasma generation method, the applied voltage, the gas composition, etc. are devised to enable the low temperature processing as much as possible. By developing an apparatus, a method of forming a carbon film on the surface of a ceramic or plastic molded product has been proposed, and further, it has been proposed to use it for an O-ring for a camera, a wiper rubber for an automobile, or the like. However, these plasma CVD methods are methods in which the introduced gas is turned into plasma at high frequency, and activated carbon elemental carbon is chemically reacted and deposited on the surface of the component. The bond strength may be weak and adhesion may be poor.

In particular, in order to process a heat-sensitive material such as a plastic material or rubber, it is necessary to generate a soft plasma by modulating a high frequency in order to reduce (weaken) the plasma density. In order to attract carbon ions in the plasma, it is common to apply a bias voltage of several tens of volts to several hundreds of volts, but at such a voltage, the carbon is only attached to the surface layer portion of the substrate. For this reason, it is impossible to perform ion implantation to the inside of the substrate (several tens of nm or more). Therefore, in the plasma CVD method, in order to improve the adhesion to the base material, silicon as a base treatment layer, silicon oxide, silicon nitride, silicon carbide, titanium tetrachloride, pentaethoxytitanium, tetraisoproxytitanium, etc. are used. It is necessary to improve the adhesion to the substrate by introducing an intermediate layer of a compound of silicon or titanium and carbon.

Also, in PVD method (physical vapor deposition method) that forms a film by sputtering a carbon solid target, a carbon film is formed by heating the substrate temperature of metal or ceramic at 300 to 500 ° C. in order to improve adhesion. In addition, it was necessary to form a film by depositing silicon or chromium material, which is compatible with carbon, as a base treatment. Further, in order to attract carbon ions in plasma, it is common to apply a DC or AC bias voltage of several tens of volts to several hundreds of volts. This voltage is used as film forming energy, It is not possible to greatly improve the adhesion.

Furthermore, it is necessary to provide a device with a special reaction mechanism in order to uniformly apply the base, and a rotation mechanism is indispensable in order to ensure the uniformity of the film thickness. It could only deal with products with a certain shape.

  On the other hand, as a method for imparting releasability and slipperiness to the material surface, a method of coating a tetrafluoroethylene resin and its copolymer material and a method of forming a carbon film using a gas mixed with a fluorine-based gas have been proposed. ing. However, lubricating fluorides coated with tetrafluoroethylene resin and copolymer materials thereof have problems of low hardness, difficulty in maintaining stable performance over a long period of time, easy wear, and peeling of the film.

In addition, a method of forming a carbon film by mixing a fluorinated gas such as carbon tetrafluoride gas or dicarbon difluoride gas simultaneously with methane gas or ethylene gas by a conventional plasma CVD method is as described above. In addition to low adhesion, the film is formed with low energy, so that a carbon film is easily formed in an orderly manner, and the carbon film is hard and brittle. In addition, there is a problem that it is difficult to forcibly enter fluorine even if the fluorine content in the carbon film is increased.

In the above-described technique, since a DC bias voltage is applied, the semiconductor and the insulating molded product are easily charged, and a phenomenon of dielectric breakdown due to charge-up charge sometimes appears. For this reason, there has been a demand for a process capable of forming a uniform carbon film without being bound by the product shape and the material of the base material and without adding a complicated rotation mechanism.
JP 2000-96233 A

Accordingly, the main object of the present invention is to provide a coating method and a coated article for various metal materials, ceramic materials, and plastic molded articles having a complex shape with irregularities on a carbon film having excellent adhesion and having both lubricity and releasability. There is to do.
The present invention is not limited to the conventional combination of ion implantation technology and plasma film formation technology by applying a pulse bias as a surface modification technology that has both lubricity and releasability on the surface of metal, ceramics, plastic molding materials, etc. An object of the present invention is to provide a novel carbon film-coated article focusing on the interfacial phenomenon caused by ion implantation with a base material and the structure of the film composition formed into a film with good adhesion and low cost.

Conventional diamond-like carbon (diamond-like carbon film) has high hardness, excellent wear resistance, electrical insulation, hydrophilicity, etc., and the built-in hydrogen content depends on the film formation method and raw materials used However, carbon films with various hardnesses were obtained.
There are plasma CVD methods, sputtering methods, ion plating methods, plasma-based ion implantation / film-forming methods, etc. as film-forming methods, but the present invention applies plasma-based ion implantation / film-forming methods to various metal materials, ceramic materials, and plastic molding. It is provided as a surface modification technique that combines lubricity and releasability on the surface of materials and the like.

  Another object of the present invention is to release an active element called fluorine by reacting with carbon in an optimum ratio even for various metal materials, ceramic materials, and plastic molded products having uneven complex shapes. The object is to provide a product having both lubricity and releasability without containing fluorine.

  The present invention uses plasma-based ion implantation / film formation to generate RF plasma by an external antenna or plasma by self-bias voltage around metal, ceramics, and plastic molded articles (base materials). Applying a negative pulse voltage of 100 V to several tens of kV to inject carbon-containing ions into the surface of the molded product to form a carbon gradient layer, and introducing fluorine-containing gas into the fluorine-containing carbon The purpose of realizing the solution of the above-mentioned problems is achieved by forming a film. Specifically, surface modification of various types of molded products is performed 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. To do. Insulating molded products such as ceramics, rubber, and plastic are provided with electrodes for applying voltage on the back or center, and power is supplied to the high-frequency plasma source in a specific atmosphere (gas type, degree of vacuum). When a negative high voltage pulse voltage is applied around the injection target (ceramics, rubber, plastic molding), the electrons in the plasma are rejected and ions are generated around the injection target. A sheath is formed. This 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 to the implant from all directions and accelerated, aiming at the implant. The element to be ion-implanted.

  In the present invention, ions can be implanted into insulators such as ceramics and plastic molded products. Conventionally, since positive ions are implanted by applying a DC bias voltage, there is a case where a molded product is charged and causes a breakdown due to a 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 substrate when the pulse voltage is absent, and the charge charged on the substrate is released into the plasma, eliminating the charge-up. The In addition, by optimizing the pulse frequency and application time for each shape, it is possible to prevent dielectric breakdown and to prevent film non-uniformity and film formation speed from decreasing due to charge-up.

Parameters affecting the characteristics of plasma-based ion implantation and deposition include the frequency of the high-frequency plasma source, plasma amplification voltage, repetition frequency, number of pulses, etc., and parameters on the high-voltage induced pulse power supply side include applied voltage and current current. The number of repetitive pulses, the pulse width, the delay time, etc., and the gas flow rate, gas pressure, etc. of the plasma generation raw material have an effect. By controlling these, an ion sheath is formed along the contour of the injection target, and only ions are injected into various metals, ceramics, and plastic moldings that are the injection target, thereby improving lubricity and mold release. The present invention provides a method and a coated article for coating a carbon film having properties on the surface of various materials.

  The hydrocarbon gas used here is a gas mainly composed of at least one selected from hydrocarbon compounds consisting of methane, acetylene, benzene, toluene, cyclohexanone, chlorobenzene, etc., and introduced into the vacuum chamber. Then, it is preferable to generate a carbon atom or a molecular ion by applying a high frequency voltage to turn the gas into a plasma, and accelerating the ion to perform ion implantation.

The main component is at least one selected from fluorine-containing compounds such as fluorine-containing gas, carbon difluoride, carbon tetrafluoride, carbon hexafluoride, sulfur hexafluoride and tetrafluorocarbon. It is preferable that gas is introduced into the vacuum chamber and a high frequency voltage is applied to make the gas into plasma to generate fluorine atoms or molecular ions, which are accelerated and ion-implanted.

  As a method for selecting hydrocarbon-based gas and fluorine-based gas, what is the ratio of carbon atoms and fluorine atoms to be implanted into the substrate? Further, it is preferable to determine the gas species and the mixing ratio depending on the percentage of fluorine atoms contained in the carbon film. The atoms generated from the additive gas are also effective as carbon ions or molecular ions combined with hydrogen, fluorine, chlorine, etc. depending on the plasma generation conditions. In methane, acetylene, benzene, and toluene gases, it is known that the degree of carbon ion implantation and the state of carbon film formation vary greatly depending on aliphatic and aromatic systems, and carbon difluoride and tetrafluoride. By adding carbon, carbon hexafluoride, sulfur hexafluoride, tetradecafluorocarbon, etc., the types of metal materials, ceramic materials, plastic materials and plasmas mainly composed of at least one selected from these gas materials It is desirable to select the optimum gas system according to the production conditions.

  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, plasma decomposition of the gas is not sufficient and the deposition rate does not increase, and if it is higher than 2.45 GHz, the stability of plasma generation and the cost of the apparatus increase. is there. This is because if the high-frequency output is 10 W or less, the plasma density is low, and even if ion implantation can be performed, film formation cannot 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 the conventional mass separation type ion implantation, it is possible to inject only carbon ions after being excited by an electric field using a commercially available gas such as methane or acetylene. However, in the plasma method, a negative high voltage is applied to various substrates in a pulsed manner, and molecular ions bonded to carbon are also simultaneously implanted as impurities. The inventors of the present application have found that the following high-frequency pulse application conditions are suitable as a result of various investigations of favorable plasma conditions that can sufficiently inject carbon ions even in the presence of these extra ions.

As the high-frequency pulse applied voltage, it is necessary to optimize the frequency, pulse width, and applied voltage. The reason for this is that if the frequency is 500 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 10 kHz 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 −0.5 to 50 kV from the viewpoint of imparting lubricity and releasability to the substrate. When it is −0.5 kV or less, the ion implantation depth into the substrate is shallow, the inclined structure between the substrate and the carbon film cannot be obtained, and it does not contribute to the improvement of the adhesion, and the high voltage is −50 kV or more. Increasing the inclination structure between the base material and the carbon film, but the high frequency pulse power supply has increased in size, resulting in a significant increase in equipment cost. In the case of insulators, plastic molded products due to discharge and heat generation on the base material surface The generation of strain becomes remarkable, and 50 kV or more is not preferable.

  The time for ion implantation onto the surfaces of various substrates is not limited, but is preferably 5 to 30 minutes. More preferably, it is a short-time treatment from the viewpoint of productivity. However, in the case of plastic molded products, the surface layer becomes brittle by injecting the carbon element, and the adhesion may be lowered. There is a need to.

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 ions of 10 ¹⁷ ions / cm ² . On the other hand, in plasma-based ion implantation, a current flows into the molded product from the periphery at a time, so that a current of several A to several tens of A flows, thereby enabling a carbon ion implantation process in a short time. 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.

However, if ions are implanted into the insulator for a long time, electric charges are accumulated on the insulating surface, and discharge occurs due to a charge-up phenomenon, resulting in non-uniform film thickness. In such a case, it is preferable to uniformly cover the periphery of the insulator with a conductive material such as a metal wire mesh and to devise measures for releasing electric charges. For example, a metal mesh made of stainless steel with a few mesh roughness is uniformly arranged at a position about 1 cm away from the surface of the plastic molded product, and this wire mesh is connected to a negative pulse application electrode with a predetermined resistance interposed therebetween, so that the charge can be increased. Can be prevented. Since the size, distance, resistor size, etc. of the metal mesh are influenced by the shape of the molded product, the pulse application voltage, the frequency, etc., it is necessary to select from the respective ion implantation conditions.

The method of forming a fluorine-containing carbon film at the same time that a high-frequency pulse voltage is applied to the object to be processed of the present invention and carbon or fluorine-containing ions are implanted into the surface of the object to be processed can be applied to various substrates. However, it has become clear that it is particularly suitable for surface modification of non-ferrous metals such as aluminum, titanium, magnesium and alloys thereof among metal materials. Until now, various attempts have been made to form carbon films on non-ferrous metals by plasma CVD and PVD methods, but the base material is soft and the oxide layer on the surface layer impairs the adhesion of the carbon film. However, when a film thickness of several tens to 100 μm was formed, the film peeled off and could not be put into practical use.

In the carbon ion implantation method of the present invention, ions are implanted with energy sufficient to break through the surface oxide layer, so that it is possible to easily form a carbon gradient structure, while increasing the surface hardness of the non-ferrous metal while increasing the surface hardness of the carbon film. Since it is possible to form the film while suppressing the elastic modulus of the carbon film, the residual stress in the carbon film is low, and adhesion can be easily obtained. For this reason, it is possible to easily obtain a carbon film in the range of 3.0 to 100 μm with a hard substrate with a large plate thickness, and a surface that forms a thin carbon film of 0.1 to 3 μm with a flexible substrate such as a metal foil Suitable for reforming.

It is also very useful to obtain a carbon film-coated article on a ceramic substrate such as glass, alumina, zirconia, or quartz. Adding a large amount of carbon or fluorine to a ceramic material is impossible in a normal process, but an arbitrary amount can be implanted by an ion implantation method. As with non-ferrous metals, it is possible to easily form a carbon gradient structure by implantation, and in this process it is possible to form a film while suppressing the elastic modulus of the carbon film, so that the residual stress in the carbon film is reduced. Low adhesion is easy to obtain. For this reason, it is possible to easily obtain a carbon film of 3.0 to 100 μm, which is suitable for surface modification of ceramics.

Furthermore, the carbon film-coated article is suitable for flexible molded products such as rubber and plastic. In the present invention, it is composed of plastic molded products such as polyolefin materials, polyolefin elastomers, polyester elastomers, polyurethane elastomers, silicone elastomers, etc., and this surface is covered with a carbon film having both lubricity and releasability, so that an unprecedented product can be obtained. provide. In the present invention, the adhesion can be improved by ion implantation of carbon or fluorine into a resin or rubber for which adhesion is difficult to obtain by a conventional method to form an inclined structure.

There are various types of rubber and plastic materials. In the present invention, a flexible elastomer material is more suitable than a hard plastic molded product such as an epoxy resin, a phenol resin acrylic resin, or a polystyrene resin. Although it was possible to obtain adhesion to a hard plastic material to such an extent that it would not be peeled off by conventional methods, the flexible material peeled off the carbon film due to fine cracks when bent, but the process of the present invention was flexible. By forming a thin carbon film with a thickness of 0.1 to 1.0 μm on the base material, a product having an excellent appearance without peeling even after bending is provided.

The carbon film-coated article of the present invention is an article such as the above-mentioned metal, ceramics, plastic molded article, etc., and carbon is ion-implanted by 50 nm or more from the surface of the non-treated product, and a hard carbon film layer is formed on the surface layer part by at least 0.1 to 3 μm. The main feature is that it is filmed. In the conventional plasma CVD method, PVD method, etc., in order to attract carbon ions in the plasma, it is common to apply a DC voltage or an AC bias voltage of several tens to several hundreds V. Carbon atoms were not ion-implanted by more than 10 nm from the surface of the object, and it did not contribute to improving the adhesion to the substrate.

As a result of evaluating various changes in high-frequency pulse voltage, pulse width, frequency, loading time, processing temperature, etc., the fact that deeper carbon atoms are implanted from the surface of the workpiece contributes to improved adhesion. I found it. As a result of the experiment, 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 ratio to the adhesiveness decreases. The reason for this is considered that the residual stress of the carbon film to be formed cannot be relaxed in the tens of atomic layers from the surface layer, and several hundreds of atomic layers are necessary.

When carbon atoms are implanted deeper than the surface layer, and a hard carbon film layer formed on the surface is formed at least 0.1 to 100 μm, the carbon film that has both lubricity and releasability has a greater effect. To do. Conventional plasma CVD methods, PVD methods, etc. have generally formed a 0.1-2.0 μm carbon film due to residual stress generated at the substrate interface. As a result, the residual stress generated at the interface of the substrate was reduced, and a carbon film having a thickness of 3.0 μm or more was easily formed. According to experiments, it was found that, for example, a carbon film having a thickness of 50 to 100 μm can be formed on a flexible aluminum substrate, and can be applied as a sliding member having a high function and a long life.

  Furthermore, it was also found that the carbon ion implantation effect on rubber and plastic molded articles is useful for reducing water vapor and various gas permeability. A carbon ion implantation layer of 50 nm or more is formed from the surface layer of the object to be processed, and a carbon film is formed on the surface layer that is several tens at% or more higher than the original carbon element concentration. A rubber / plastic molded product can be obtained. The gas permeability of rubber and plastic materials is affected by the gas solubility in the base material and the intermolecular distance, etc., but the ion-implanted molded product reduces the intermolecular distance, and the dense carbon film absorbs the gas. This is probably because it does not penetrate.

On the other hand, the carbon film-coated article of the present invention can be provided with a carbon film having both lubricity and releasability by containing 5 to 30 at% fluorine atoms in the carbon film. The carbon film formed according to the present invention preferably contains 5 to 30 at% of fluorine element. Attempts to add fluorine to the carbon film have been made for a long time, but it has been found that it is more effective to form a film in combination with a plasma-based ion implantation method. Fluorine is a very active element and forms various compounds with high reactivity. However, it is difficult to use the compound in a stable state over a long period of time because it is easily decomposed by water and heat.

Since the conventional film formation by the plasma CVD method is performed with relatively low energy, the C—C bond occurs preferentially, and the fluorine content in the carbon film is often several percent or less. Alternatively, after forming a carbon film, a fluorinated gas is allowed to flow to cause a fluorination reaction, so that there are many carbon films containing fluorine of several tens of at% only on the surface layer. This is because a carbon film formed by thermal plasma tends to be hard and brittle due to orderly film growth. It is said that the carbon film is a mixture of sp3 structure derived from the diamond structure and sp2 structure derived from the graphite structure, and it is known that many sp3 structures are likely to be formed by the carbon film formation by the plasma CVD method. Yes. When fluorine is added to this structure, it becomes an unstable mixture of sp3 / sp2 structure, and since it is hard and brittle, it has poor wear resistance.

On the other hand, in the plasma-based ion implantation method, the carbon film is formed while controlling with the pulse bias voltage without applying the DC bias voltage, so the ratio of the sp3 / sp2 structure is controlled and the ratio of fluorine addition is easy. I found it controllable. Although it is known that hydrogen is mixed in the carbon film, it is possible to add fluorine while suppressing the mixing of hydrogen, and the amount thereof also decreases the friction coefficient with a fluorine content of 5 to 30 at%. As a result, the optimum carbon film can be formed by the pulse method. This is because the pulse voltage has an effect of disturbing the order of film growth in film formation by the pulse method.

  In the present invention, carbon ion implantation is indispensable, but fluorine ion implantation is not always necessary. After carbon implantation, it is effective to form a carbon film using the above-described hydrocarbon-based and fluorine-based gases. In the present invention, high-voltage plasma-based carbon ion implantation is performed, and then the residual stress in the carbon film is relaxed by applying a low pulse bias voltage to form a carbon film that is fluorinated at an arbitrary ratio. Becomes easy, and it becomes possible to form a film having good adhesion.

  In the carbon film of the present invention, a metal, ceramic, or plastic molded product is attached to a negative voltage application sample stage and integrated with a high voltage feedthrough. High-frequency (RF) power is applied between the feedthrough and the chamber, electrons are reciprocated by changes in the electric field between them, and collisions with gas molecules are repeated to ionize hydrocarbon and fluorine gas molecules, resulting in high-density plasma. Form. Ions, radicals, and electrons coexist in the plasma, so if a high voltage pulse voltage is applied, the ions in the plasma can be injected into a rubber or plastic molded product sample. Ions of several tens of volts) are deposited on the surface, and at this time, carbon elements are bonded by radical polymerization to form a film. Using this superposed plasma ion implantation / deposition apparatus, ion implantation / deposition or a combination of ion implantation and deposition can be performed by controlling RF power and high-voltage pulse power.

  The physical properties of the carbon film vary depending on the type of gas used, the gas pressure, the applied voltage, etc., but a carbon film having excellent adhesion to the substrate, high hardness and a large film thickness is preferred. In the plasma-based ion implantation / deposition apparatus, it is preferable to form a film by a process of at least three steps. After cleaning the substrate surface, ion implantation is performed at a high voltage, and then methane, acetylene, etc. It is preferable to form a carbon film by introducing a gas, and subsequently form the carbon film with an energy of a lower voltage (several kV). This is because when the carbon film is formed with high energy, the structure of the carbon film is disturbed, and it is difficult not only to obtain a hard and high-grade film but also to obtain a film forming speed. In particular, it is preferable to form a film with a lower energy as the surface layer portion is obtained because a high quality carbon film can be obtained. As described above, it has been found that the three steps of high energy ion implantation, medium energy carbon film formation, and low energy carbon film formation are useful for relaxing residual stress in the carbon film and advantageous for forming a thick film.

  As described above, according to the method of the present invention, first, carbon ion implantation is performed from a hydrocarbon-based gas plasma to a metal, ceramic, or plastic molded article using a plasma-based ion implantation / film formation method. A carbon film-coated article excellent in lubricity, water repellency, and releasability by forming a carbon film while introducing a gas or a hydrocarbon-based gas containing at least one fluorine atom, and a surface treatment method thereof It turned out that it can provide.

  Further, the carbon film-coated article of the present invention has high surface hardness due to carbon ion implantation, increases lubricity, water repellency / release properties, and has a solvent resistance other than rubber packing materials, polymer molded containers, etc. The same applies to industrial rubber and polymer molded products such as commonly used plastic bearings and sliding members. Furthermore, the carbon ion plus fluorine-containing carbon film formation technology of the present invention is an industrial ceramic material or metal material molded product such as an improved surface hardness other than the metal material or ceramic material of the present invention, and improved functionality of lubricity and releasability. The same can be applied to the above.

Embodiments of the present invention will be described below.
First, a schematic configuration of a plasma-based ion implantation / deposition apparatus used in the surface treatment method for various substrates of the present invention will be described with reference to FIG. This apparatus comprises a vacuum chamber 3 in which an installation base 2 for metal, ceramics and plastic molded products 1 is built. The installation table 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. This apparatus is also provided with a high-frequency plasma source 6 for introducing a predetermined hydrocarbon-based gas and a fluorine-based gas through the introduction port 5 to form a hydrocarbon / fluorine gas-based gas plasma. A metal plasma source 7 for ion-implanting metal elements is also provided to improve the adhesion of the carbon film.

  The apparatus further includes a high voltage negative pulse power source 8 and a radio frequency (RF) power source 9 for applying a high voltage negative charge to various molded articles 1. The high voltage negative pulse power supply 8 generates a negative charge having a predetermined energy, and applies a negative charge pulse to the various molded articles 1 through the high voltage feedthrough 10. This feedthrough is connected to an installation table, and the installation table is an insulator 11 and is in an electrically floating state. Further, when the carbon film is formed, power can be supplied from the high-voltage feedthrough 10 through the superimposing device 11 that superimposes the high voltage pulse and the high frequency to form the supply gas into a plasma. A shield cover 13 is attached to the high voltage feedthrough 10 to protect the feedthrough 10.

  On the sample setting table 2 of this apparatus, a metal, ceramic, and plastic molded product (a) having a diameter of 70 mm and a thickness of 2 mm as shown in FIG. 2 and various molded products (b) having a diameter of 10 mm and a thickness of 1 mm are set. (A) Physical and chemical characteristics were evaluated for the sample, and composition analysis was made possible for the (b) sample. When a negative charge pulse is applied to these metal, ceramic, and plastic molded articles, carbon ions or ions such as CHx, CFx, and C2Fx in the plasma are attracted to the mold material, and carbon ions or fluorine ions are implanted. Since ions are implanted by applying a negative charge pulse to metal, ceramics, and plastic molded products, an electric field is generated along the shape of the molded product even if the molded product is not a flat plate but a three-dimensional product with irregularities. Carbon ions collide almost at right angles to. Therefore, even if the insulating rubber / plastic molded product has irregularities, carbon ions can be implanted into the entire surface of the rubber / plastic molded product. Although hydrogen ions are also implanted together with carbon or fluorine ions, it is known that hydrogen in the base material diffuses and degass after injection, and the physical properties of the base material are greatly affected. It is not considered.

  After carbon ion implantation, a carbon film can be formed in the same apparatus. Carbon ion implantation is performed at a voltage of several kV or more, preferably 10 kV or more. However, the carbon film is formed by hydrocarbon gas such as methane, acetylene, benzene, toluene, argon / fluorine mixed gas, tetrafluoride. Film formation is performed while applying a voltage of 10 kV or less by mixing a fluorine-based gas composed of carbon, hexafluorodicarbon, sulfur hexafluoride, tetrafluorocarbon, etc. at an arbitrary ratio. The reason for this is that when a carbon film is formed at a high energy, the film structure of the carbon film is disturbed by the collision energy of ions, and it is difficult not only to obtain a hard and advanced film, but also to obtain a film formation speed. . In particular, it is preferable to form a film with lower energy as the surface layer portion is obtained because a high-quality carbon film-coated article can be obtained. It is preferable to use a film forming technique in which the voltage is gradually lowered from the high voltage side to the low voltage side by automatic control during film formation.

Carbon film is formed from hydrocarbon gases such as methane, acetylene, benzene, toluene, and argon / fluorine mixed gas, carbon tetrafluoride, carbon hexafluoride dicarbon, sulfur hexafluoride and tetrafluorocarbon 10 The fluorine-containing gas is mixed at an arbitrary ratio to form a film, and the fluorine content in the carbon film varies depending on the type of gas used, the gas flow rate, the applied voltage, and the like. As the proportion of the fluorine-based gas to be mixed increases, the fluorine content in the carbon film increases, but it is not necessarily proportional. Usually, the fluorine content in the carbon film can be contained only at a ratio lower than the mixing ratio. This reason is related to the stability of the CF bond, which is considered to be unstable as CF → CF ₂ → CF ₃ , and the bonded F is considered to be decomposed again. Theoretically, C: F can be 1: 1, that is, 50 at%. However, as a result of research, it is difficult to obtain a stable carbon film even if it contains 30 at% or more of fluorine. Is preferably 5 to 30 at%.

Mixing of fluorine-based gas consisting of argon / fluorine mixed gas, carbon tetrafluoride, dicarbon hexafluoride, sulfur hexafluoride, tetrafluorocarbon 10 and so on during carbon film deposition is performed from the time of carbon ion implantation. However, it is preferable to mix gradually after a while after the start of the carbon film formation. In order to obtain the lubricity and releasability of the carbon film, the film is formed while mixing a fluorine-based gas at an arbitrary ratio and applying a voltage of 10 kV or less. This is because when the carbon film is formed with high energy, the structure of the carbon film is disturbed, and it is difficult not only to obtain a hard and high-grade film but also to obtain a film forming speed. In particular, it is preferable to form a film with a lower energy as the surface layer portion is obtained because a high quality carbon film coated article can be obtained.

This will be described below based on examples.

  Using a plasma-based ion implantation / deposition system as shown in FIG. 1, a rubber / polymer molding disk with an outer dimension of φ70 × 2 mm and a φ10 × 1 mm test plate for analytical evaluation as shown in FIGS. Then, plasma was generated under the following conditions, and carbon ion implantation + carbon film was formed and evaluated.

Material used: Aluminum alloy (Nippon Light Metal AC4CH)
Gas type: Methane gas / acetylene / argon / fluorine 5% gas mixture ratio: Methane gas 100 / acetylene 90-50 / argon / fluorine 10-50
Pressure during injection and film formation: 0.5 Pa to 1.0 Pa
Injection energy: 10keV, 20keV, 30keV
Deposition energy: 10 keV → 2 keV
Injection time: 10, 20, 30 minutes Carbon film deposition time: 180 minutes Applied frequency: 1000 Hz and 2000 Hz

  Under each of the above conditions, carbon ion implantation was initially performed with only methane gas at each voltage, and then the carbon film was formed using an acetylene / argon / fluorine mixed gas while lowering the voltage. Since the pressure fluctuates when the gas mixture ratio changes, the pressure range at that time is shown, and the arrow of film formation energy indicates that the experiment was performed while reducing the voltage within the film formation time. The distribution of the implanted carbon element in the depth direction was evaluated with an Auger analyzer (AES), and the carbon implantation depth and amount (Atomic Concentration (%)) were determined. Further, the hardness and adhesion of the aluminum substrate surface were measured with a dynamic hardness meter and a scratch adhesion evaluation tester, and the friction coefficient was measured with a steel ball in a friction test by a ball and disk method. Although the measured film thickness of the carbon film differs depending on the film forming conditions, a carbon film of 2 to 4 μm was formed. Furthermore, as a general method for evaluating the releasability on the surface of the aluminum substrate, the contact angle with water was evaluated with a contact angle measuring device using a distilled water appropriate method. As a typical example of the AES analysis, carbon injection distributions at injection energies of 10 keV, 20 keV, and 30 keV under conditions of an injection time of 30 minutes and 1000 Hz are shown in FIG. Regarding the hardness, adhesion, coefficient of friction, and contact angle, changes in the above conditions are shown in FIG. 4 in comparison with an untreated aluminum substrate.

  The horizontal axis in FIG. 3 indicates the depth direction of the aluminum material, the origin indicates the carbon film material, and the vertical axis indicates the ratio of the carbon element in the material. In the analysis, the carbon film was analyzed after thinning by argon sputtering in advance. As can be seen from FIG. 3, the carbon layer, which is the main component of the carbon film, is formed on the aluminum surface up to about 300 nm, and the vicinity of 310 nm is seen as the outermost layer portion of aluminum. From this, it can be seen that the carbon injection layer is a carbon layer having a high concentration from 360 nm to around 450 nm. As a result, it can be seen that the higher the implantation energy, the deeper the carbon penetration depth, and the ion implantation into the interior. It can be seen that the carbon implantation depth is about 10 nm at 10 keV, 90 nm at 20 keV, and 120 nm at 30 keV. This shows that the higher the applied voltage before forming the carbon film, the deeper the carbon enters the aluminum material, indicating a tilted structure.

  On the other hand, as shown in FIG. 4, the dynamic hardness, scratch adhesion and friction coefficient of the aluminum surface are very soft for untreated aluminum, but all show a hardness of 900 or more by forming a carbon film. It can be seen that the adhesion strength is 15 N or more even though the substrate is soft. Moreover, although the aluminum base material showed a very high friction coefficient, all showed the low friction coefficient of 0.23 or less by the carbon film. Looking at the relationship between the ion implantation energy and the implantation time, it was found that the higher the energy and the longer the time, the higher the hardness and the lower the friction coefficient, but the influence of the F mixing ratio greatly contributed. The F mixing ratio did not coincide with the F content in the carbon film, and the fluorine content in the film was determined separately by photoelectron spectroscopy.

  Furthermore, as a result of measuring the contact angle of distilled water to the aluminum surface, as shown in FIG. 4, untreated aluminum is hydrophilic, but the fluorine-containing carbon film shows a contact angle of almost 90 degrees or more and the water repellent surface is It turns out that it is obtained. The contact angle increases as the F mixing ratio increases. Examination of the relationship between the ion implantation energy and the implantation time did not significantly affect the implantation time, and it was found that the lower the implantation energy, the higher the water repellency. From this, it is clear that a new material surface excellent in lubricity and water repellency can be formed by performing moderate carbon ion implantation and forming an F-containing carbon film on the surface compared with an untreated aluminum alloy. It is.

  Using a plasma-based ion implantation / deposition system as shown in FIG. 1, a rubber / polymer molding disk with an outer dimension of φ70 × 2 mm and a φ10 × 1 mm test plate for analytical evaluation as shown in FIGS. Then, plasma was generated under the following conditions, and carbon ion implantation + carbon film was formed and evaluated.

Material used: Alumina material (A-476, manufactured by Kyocera Corporation)
Gas type used: Methane gas / acetylene / carbon tetrafluoride gas mixture ratio: Methane gas 100 / acetylene 90-50 / carbon tetrafluoride 10-50
Pressure during injection and film formation: 0.5 Pa to 1.0 Pa
Injection energy: 10keV, 20keV, 30keV
Deposition energy: 10 keV → 2 keV
Injection time: 10, 20, 30 minutes Carbon film deposition time: 180 minutes Applied frequency: 1000 Hz and 2000 Hz

  Under each of the above conditions, carbon ion implantation is initially performed with only methane gas at each voltage, and then the carbon film is formed using an acetylene / carbon tetrafluoride gas mixed gas while lowering the voltage. It was. Since the pressure fluctuates when the gas mixture ratio changes, the pressure range at that time is shown, and the arrow of film formation energy indicates that the experiment was performed while reducing the voltage within the film formation time. The distribution of the implanted carbon element in the depth direction was evaluated with an Auger analyzer (AES), and the carbon implantation depth and amount (Atomic Concentration (%)) were determined. Further, the hardness and adhesion of the alumina substrate surface were measured with a dynamic hardness meter and a scratch adhesion evaluation tester, and the friction coefficient was measured with a steel ball in a friction test by a ball and disk method. Although the measured film thickness of the carbon film varies depending on the film formation conditions, a carbon film of 1.5 to 3 μm was formed. Further, the contact angle with water was evaluated by a contact angle measuring device using a distilled water appropriate method as an index of releasability on the surface of the alumina substrate. As a typical example of AES analysis, carbon injection distributions at injection energies of 10 keV, 20 keV, and 30 keV under conditions of an injection time of 30 minutes and 1000 Hz are shown in FIG. Regarding the hardness, adhesion, coefficient of friction, and contact angle, changes in the above conditions are shown in FIG. 6 in comparison with the untreated alumina substrate.

  The horizontal axis of FIG. 5 indicates the depth direction of the alumina material, the origin indicates the carbon film material, and the vertical axis indicates the ratio of the carbon element in the material. In the analysis, the carbon film was analyzed after thinning by argon sputtering in advance. As can be seen from FIG. 5, the carbon layer, which is the main component of the carbon film, is formed up to about 300 nm on the alumina surface, and the vicinity of 280 nm is seen as the outermost layer portion of alumina. From this, it can be seen that the carbon injection layer is a carbon layer having a high concentration from 380 nm to 550 nm. As a result, it can be seen that the higher the implantation energy, the deeper the carbon penetration depth, and the ion implantation into the interior. It can be seen that the carbon implantation depth is about 10 nm at 10 keV, 180 nm at 20 keV, and 250 nm at 30 keV. This shows that the higher the applied voltage before the carbon film is formed, the deeper the carbon enters the alumina material, indicating a tilted structure.

  On the other hand, as shown in FIG. 6, the dynamic hardness, scratch adhesion and friction coefficient of the alumina surface show a tendency that the hardness of the untreated alumina is slightly lowered by forming a carbon film because the substrate itself is hard. However, it can be seen that the scratch adhesion shows an adhesion of 20 N or more because the substrate is hard. The friction coefficient of the alumina base material was high, but the carbon film showed a low friction coefficient of 0.23 or less. Looking at the relationship between the ion implantation energy and the implantation time, it was found that the higher the energy and the longer the time, the higher the hardness and the lower the friction coefficient, but the greater the influence of the F mixing ratio. The F mixing ratio did not coincide with the F content in the carbon film, and the fluorine content in the film was determined separately by photoelectron spectroscopy.

  Further, as a result of measuring the contact angle of distilled water to the alumina surface, as shown in FIG. 6, untreated alumina is hydrophilic, but the fluorine-containing carbon film shows a contact angle of almost 90 degrees or more, and the water repellent surface is It turns out that it is obtained. The contact angle increases as the F mixing ratio increases. Examination of the relationship between the ion implantation energy and the implantation time did not significantly affect the implantation time, and it was found that the lower the implantation energy, the higher the water repellency. From this, it is clear that a new material surface excellent in lubricity and water repellency can be formed by performing moderate carbon ion implantation and forming an F-containing carbon film on the surface compared with untreated alumina. is there.

  Next, by changing the materials used, using a rubber / polymer molding disk with an outer dimension of φ70 × 2 mm as shown in FIGS. 2A and 2B and a φ10 × 1 mm test plate for analytical evaluation, the same as in Experimental Example 1 Plasma was generated and carbon ion implantation + carbon film was formed and evaluated.

Materials used: Nitrile rubber (Nippol DN201 manufactured by ZEON)
Gas type used: Methane gas / toluene / carbon tetrafluoride gas mixture ratio: Methane gas 100 / toluene 90-50 / carbon tetrafluoride 10-50
Pressure during injection and film formation: 0.5 Pa to 1.0 Pa
Injection energy: 10keV, 20keV, 30keV
Deposition energy: 10 keV → 2 keV
Injection time: 10, 20, 30 minutes Carbon film deposition time: 60 minutes Applied frequency: 1000 Hz and 3000 Hz

  Under each of the above conditions, carbon ion implantation is first performed using only methane gas at each voltage, and then the nitrile rubber molded product is ion-implanted. Thereafter, the carbon film is formed using a toluene / carbon tetrafluoride mixed gas while lowering the voltage. Went. Since the pressure fluctuates when the gas mixture ratio changes, the pressure range at that time is shown, and the arrow of film formation energy indicates that the experiment was performed while reducing the voltage within the film formation time. The distribution of the implanted carbon element in the depth direction was evaluated with an Auger analyzer (AES), and the carbon implantation depth and amount (Atomic Concentration (%)) were determined. Further, the hardness of the nitrile rubber surface and the adhesion of the carbon film were measured using a dynamic hardness meter and a scratch adhesion evaluation tester, and the friction coefficient was measured using a steel ball in a friction test by a ball and disk method. Further, as an index of releasability on the nitrile rubber surface, the contact angle with water was evaluated by a contact angle measuring device using a distilled water appropriate method. As a typical example of the AES analysis, the carbon injection distribution at an injection energy of 10 keV, 20 keV, and 30 keV under the conditions of an injection time of 30 minutes and 2000 Hz is shown in FIG. Regarding the hardness, adhesion, coefficient of friction, and contact angle, changes in the above conditions are shown in FIG. 8 in comparison with untreated nitrile rubber.

  The horizontal axis of FIG. 7 indicates the depth direction of the nitrile rubber material, the origin indicates the carbon film material, and the vertical axis indicates the ratio of the carbon element in the material. As can be seen from FIG. 7, on the surface of the nitrile rubber, a carbon layer, which is a carbon film component, is formed up to around 300 nm, and around 320 nm is seen as the outermost layer portion of the nitrile rubber. It can also be seen that the base concentration is high because nitrile rubber contains a considerable amount of carbon. From this, it can be seen that the carbon injection layer is a carbon layer having a high concentration from 550 nm to about 800 nm. As a result, it is found that the higher the implantation energy, the deeper the carbon penetration depth, and the higher the concentration of the carbon than the base. It can be seen that the carbon implantation depth is 10 keV to about 130 nm, 20 keV is 380 nm, and 30 keV is about 550 nm. This shows that the higher the applied voltage before the carbon film is formed, the deeper the carbon enters the nitrile rubber material, indicating an inclined structure.

  On the other hand, as shown in FIG. 8, the nitrile rubber surface has a dynamic hardness and a friction coefficient of untreated nitrile rubber, which are very soft. However, by forming a carbon film, each shows a hardness of 600 or more. Also showed a friction coefficient of 0.27 or less. Looking at the relationship between the ion implantation energy and the implantation time, it was found that the higher the energy and the longer the time, the higher the hardness and the lower the friction coefficient, but the influence of the F mixing ratio greatly contributed. The F mixing ratio did not coincide with the F content in the carbon film, and the fluorine content in the film was determined separately by photoelectron spectroscopy.

  Furthermore, as a result of measuring the contact angle of water on the surface of the nitrile rubber, as shown in FIG. 8, the untreated nitrile rubber is hydrophilic, but the contact angle is increased by carbon film formation, and a water-repellent surface is obtained. I understand. It was found that the contact angle tends to increase as the F mixing ratio increases. Examining the relationship between the ion implantation energy and the implantation time does not significantly affect the relationship, and it is understood that the F mixing ratio needs to be optimized. From this, it is clear that a new material surface that is lubricious and water-repellent can be formed by performing moderate carbon ion implantation and forming an F-containing carbon film on the surface compared to untreated nitrile rubber. is there.

  Next, by changing the materials used, using a rubber / polymer molding disk with an outer dimension of φ70 × 2 mm as shown in FIGS. 2A and 2B and a φ10 × 1 mm test plate for analytical evaluation, the same as in Experimental Example 1 Plasma was generated and carbon ion implantation + carbon film was formed and evaluated.

Material used: Polypropylene resin (Nobrene H501 manufactured by Sumitomo Chemical)
Gas type used: Methane gas / acetylene gas / carbon tetrafluoride gas mixture ratio: methane gas 100 / acetylene 90-50 / carbon tetrafluoride 10-50
Pressure during injection and film formation: 0.5 Pa to 1.0 Pa
Injection energy: 10keV, 20keV, 30keV
Deposition energy: 10 keV → 2 keV
Injection time: 10, 20, 30 minutes Carbon film formation time: 90 minutes Applied frequency: 1000 Hz

  Under each of the above conditions, carbon ion implantation is first performed with only methane gas at each voltage to the polypropylene resin molded product, and then the carbon film is formed using an acetylene / carbon tetrafluoride mixed gas while lowering the voltage. went. Since the pressure fluctuates when the gas mixture ratio changes, the pressure range at that time is shown, and the arrow of film formation energy indicates that the experiment was performed while reducing the voltage within the film formation time. The distribution of the implanted carbon element in the depth direction was evaluated with an Auger analyzer (AES), and the carbon implantation depth and amount (Atomic Concentration (%)) were determined. Further, the hardness and adhesion of the polypropylene resin surface were measured using a dynamic hardness meter and a scratch adhesion evaluation tester, and the friction coefficient was measured using a steel ball in a ball and disk friction test. Furthermore, the contact angle with water on the surface of the polypropylene resin was evaluated with a contact angle measuring device using a distilled water appropriate method. As a typical example of AES analysis, carbon injection distributions at injection energies of 10 keV, 20 keV, and 30 keV under conditions of an injection time of 30 minutes and 1000 Hz are shown in FIG. Regarding the hardness, adhesion, coefficient of friction, and contact angle, changes in the above conditions are shown in FIG. 10 in comparison with untreated polypropylene resin.

  The horizontal axis in FIG. 9 indicates the depth direction of the polypropylene resin material. Since this sample has a carbon film thickness as thick as 2 μm, it was measured in advance by argon sputtering, the origin indicates the middle part of the carbon film material, and the vertical axis indicates the ratio of the carbon element in the material. As can be seen from FIG. 9, the carbon layer of the carbon film component remains on the surface of the polypropylene resin, and the vicinity of 220 nm can be seen as the outermost layer portion of the nitrile rubber. From this, it can be seen that the carbon injection layer is a carbon layer having a high concentration from 450 nm to 800 nm. It can be seen that polypropylene resin originally has few carbon components, and the higher the injection energy, the deeper the carbon penetration depth, and the higher the concentration inside. It can be seen that the carbon implantation depth is about 10 nm at 10 keV, about 400 nm at 20 keV, and 600 nm at 30 keV. This indicates that the higher the applied voltage before the carbon film is formed, the deeper the carbon enters the polypropylene resin material, indicating an inclined structure.

  On the other hand, as shown in FIG. 10, the dynamic hardness of the polypropylene resin surface is soft in the untreated polypropylene resin, but all of them show a hardness of 1000 or more by forming a carbon film, and the adhesion of the film is 15 N or more. Adhesion was shown, and the carbon film did not peel even when bent, giving good adhesion. The coefficient of friction decreased from that of the untreated sample, and both showed a coefficient of friction of 0.23 or less. Looking at the relationship between the ion implantation energy and the implantation time, it seems that the ion implantation for a long time has a slightly higher hardness and a lower friction coefficient, but the influence of the F mixing ratio contributes greatly as in the rubber material. understood. The F mixing ratio did not coincide with the F content in the carbon film, and the fluorine content in the film was determined separately by photoelectron spectroscopy.

  Furthermore, as a result of measuring the contact angle of water on the surface of the polypropylene resin, as shown in FIG. 10, the untreated polypropylene resin is slightly hydrophobic. It turns out that it is obtained. It was also found that the contact angle increases as the F mixing ratio increases. Looking at the relationship between the ion implantation energy and the implantation time, it can be seen that the contact angle is largely independent of energy and is affected by the deposition conditions of the carbon film. Compared with untreated polypropylene resin, the sample of the present invention performs moderate carbon ion implantation and forms a F-containing carbon film on its surface, thereby forming a new material surface that is lubricious and excellent in water repellency. It is clear to do.

  Next, the relationship between the plasma generation fluorine gas mixing ratio at the time of carbon film formation and the fluorine content in the formed carbon film is analyzed using a photoelectron spectrometer (XPS), and the F content is determined. Identified. The gas types used were acetylene gas / argon / fluorine mixed gas, carbon tetrafluoride or hexafluorodicarbon gas, 90:10, 80:20, 70:30, 60:40, 50:50, 40: respectively. A gas obtained by introducing a gas mixed at a ratio of 60 into a vacuum chamber and forming a carbon film of about 1 μm was used. As a result, as shown in FIG. 9, it can be seen that the F content in the carbon film increases proportionally as the mixing ratio of the fluorine-based gas increases. However, even when 50% or more of the fluorine-based gas is mixed, the F content tends to be suppressed to 30% or less. It was found that when the mixed gas was less than 50%, the F content entering the carbon film was approximately ½ or less and varied depending on the fluorine gas type.

Examining the relationship between the surface physical characteristics of FIGS. 4, 6, 8, and 10 and the fluorine content of FIG. 11, the hydrocarbon-based gas after carbon ion implantation into the metal, ceramic, and plastic molded articles of the present invention By forming a carbon film by mixing a fluorine-based gas, it becomes clear that the carbon film contains 5 to 30% of fluorine, thereby maintaining lubricity while maintaining high hardness and adhesion. It is clear that a novel carbon film-coated article having excellent water repellency, that is, releasability can be obtained.

Although not described in the experimental examples, the rubber and plastic molded sheets obtained in FIGS. 8 and 10 are flexible and the carbon film on the surface does not peel off even when a 180-degree bending test is performed. Only fine cracks occurred. In addition, as in the experimental example, the carbon film was applied at 1 kV without applying a 10-30 keV voltage. After the bending test, the carbon film partially peeled off, and the coefficient of friction increased, resulting in an untreated rubber / plastic molded product. It was equivalent. From this, it became clear that pulse ion implantation of carbon is indispensable as a pretreatment for forming a carbon film.

It is a block diagram of the plasma base ion implantation and film-forming apparatus used for the metal mold | die processing method of this invention. The shape of the press mold used for the experiment and the test sample is shown. It is a graph which shows the relationship between the carbon ion implantation to an aluminum alloy + carbon implantation depth by the Auger analysis after carbon film formation, and carbon concentration. This is a result of measuring physical changes such as hardness, adhesion, friction coefficient, contact angle after carbon ion implantation into an aluminum alloy + carbon film formation. It is a graph which shows the relationship between the carbon injection depth by the Auger analysis after carbon ion implantation + carbon film formation to an alumina base material, and carbon concentration. It is the result of measuring physical changes such as carbon ion implantation into an alumina base material + carbon film formation, hardness, adhesion, friction coefficient, contact angle, and the like. It is a graph which shows the relationship between the carbon implantation depth by the Auger analysis after carbon ion implantation + carbon film formation to a nitrile rubber, and carbon concentration. It is the result of measuring physical changes such as carbon ion implantation into nitrile rubber + carbon film formation, hardness, adhesion, friction coefficient, contact angle. It is a graph which shows the relationship between the carbon implantation depth by the Auger analysis after carbon ion implantation + carbon film formation to a polypropylene resin, and carbon concentration. It is the result of measuring physical changes such as hardness, adhesion, coefficient of friction, and contact angle after carbon ion implantation and carbon film formation into polypropylene resin. It is the result evaluated by the XPS analysis of the relationship between the fluorine-based gas mixing ratio during the carbon film formation and the fluorine content in the carbon film.

Explanation of symbols

1 Mold material
2 Installation stand
3 Vacuum chamber
4 Exhaust device
5 Hydrocarbon gas inlet
6 RF plasma source
7 Metal plasma source
8 High voltage negative pulse power supply
9 RF power supply
10 Feedthrough for high voltage
11 Insulator
12 Superimposing device
13 Shield cover

Claims (9)

In a vacuum, fluorine gas or a hydrocarbon-based gas containing at least one atom or more of fluorine is introduced to generate plasma by supplying high-frequency power, and a high-frequency pulse voltage is applied to the object to be processed so that carbon Alternatively, fluorine and ions containing these two elements are injected into the surface of the object to be processed, and at the same time, a fluorine-containing carbon film is formed, and a carbon film-coated article having both lubricity and releasability and its surface treatment Method. As a fluorine gas or a gas containing at least one atom or more of fluorine, at least one kind selected from argon / fluorine mixed gas, carbon tetrafluoride, carbon hexafluoride dicarbon, sulfur hexafluoride, tetrafluorocarbon, etc. 2. The lubricity and separation property according to claim 1, wherein a gas obtained by mixing an arbitrary amount of the above gas and at least one gas selected from methane, ethane, acetylene, benzene, cyclohexane and the like in an arbitrary ratio is supplied. Carbon film-coated article having moldability and surface treatment method thereof. 2. The lubrication according to claim 1, wherein the high frequency power for generating the gas plasma is a frequency ranging from 0.2 MHz to 2.45 GHz, an output ranging from 10 W to 20 kW, and a pulse width of 1.0 μsec or more. Film-coated article having surface property and releasability and surface treatment method thereof. The high-frequency pulse applied voltage is characterized in that the frequency is in the range of 500 Hz to 10 kHz, the pulse width is in the range of 1.0 to 1000 μsec, and the applied voltage is in the range of −0.5 kV to −50 kV. 2. The carbon film-coated article having lubricity and releasability according to 1, and a surface treatment method thereof. 2. The carbon film-coated article having lubricity and releasability and a surface treatment method thereof according to claim 1, wherein the carbon film-coated article is made of a non-ferrous metal such as aluminum, titanium, magnesium and alloys thereof. 2. The carbon film-coated article having lubricity and releasability and a surface treatment method thereof according to claim 1, wherein the carbon film-coated article is made of ceramics such as glass, alumina, zirconia, and quartz. 2. The carbon film-coated article having lubricity and releasability according to claim 1, wherein the carbon film-coated article comprises a plastic molded article such as a polyolefin material, a polyolefin elastomer, a polyester elastomer, a polyurethane elastomer, and a silicone elastomer. Its surface treatment method. The carbon film-coated article is an article according to claim 5, 6 or 7, characterized in that it has a carbon gradient layer of 50 nm or more from its surface by carbon ion implantation, and has a carbon film layer of at least 0.1 to 100 μm on the surface layer portion. 2. The carbon film-coated article having lubricity and releasability according to claim 1 and a surface treatment method thereof. The carbon film-coated article according to claim 8, wherein the carbon film formed on the surface thereof contains 5 to 30 at% fluorine, and the carbon having lubricity and releasability according to claim 1 Film-coated article and surface treatment method thereof.