TW548338B - An apparatus for forming a carbon film to an inner surface of a plastic bottle and a method for manufacturing a plastic bottle with an inner surface coated a carbon film - Google Patents

Abstract

An apparatus for forming a carbon film to the inner surface of a plastic bottle, which includes: a cylindrical external electrode with a bottom, having a size of surrounding the circumference of the plastic bottle when the plastic bottle is inserted, an internal electrode inserted almost across the whole length along the longitudinal direction in the plastic bottle of the external electrode, a gas exhausting means for exhausting the gas inside the external electrode, a high-frequency power source connected to the internal electrode and applying high-frequency electric power to the internal electrode, a bias supply connected to the external electrode and applying bias voltage to the external electrode; the internal electrode is a cylindrical with a bottom and constructed to act as a passage for introducing the medium gas provided from a gas supply means, and on the bottom, or on the side surface between the range from the bottom to 25% of the length inserted into the plastic bottle, through holes for blowing out the medium gas are provided.

Description

548338 A7 B7 V. Description of the Invention (Technical Field of the Invention) The present invention relates to a device for forming a coating on a plastic container and a method for manufacturing a plastic container covered with a carbon film. The prior art was made by coating a carbon film on a plastic container. A method using a high-frequency plasma is disclosed in Japanese Patent Application Laid-Open No. 8-53116 and Japanese Patent Application No. 2788412 (Japanese Patent Application No. 8-53117). Japanese Patent Application No. 3176558 (Japanese Patent Application No. 9-272567) ), There is a method for coating a carbon film with a high-frequency plasma as a method for applying the same. In Patent No. 3072269 (Japanese Patent Application Laid-Open No. 10-226884), a method for coating a surface of a container having a special shape is disclosed in the patent. No. 3115252 (Japanese Patent Application Laid-Open No. 10-258825) and the like are disclosed as a method for mass production of a plurality of containers at the same time. In addition, there are documents disclosed as technologies for coating a plastic container with a carbon film. "K. Takemoto, et al, Proceedings of ADC / FCT '99, p285", "E. Shimamura et al, 10th years IAPRI World Conference 1997, p251" The above-mentioned Patent No. 2788412 (Japanese Patent Application Laid-Open No. 8-53117), which is a basic invention of carbon film coating of a plastic container by slurry CVD, is described with reference to Fig. 7. Fig. 7 uses a high-frequency electric power described in this publication. A cross-sectional view of a device for forming a coating on a plastic container of slurry CVD. An external electrode 101 is set on a shelf 102 by, for example, a sealing plate 103 made of polytetrafluoroethylene. The external electrode 101 is a plastic container to be stored. For example, it has an internal shape approximately along the outer shape of the bottle B. The external electrode 101 and the neck preferably follow the shape of a screw cap for the bottle cap. The external electrode 101 includes a cylindrical body 101a and a body mounted on the 101a. Upper cover part-6- This paper size applies to China National Standard (CNS) A4 (210X297 mm) binding

548338 A7 B7 V. Description of the invention (2) 101b, and also a vacuum container. The gas exhaust pipe 104 is connected to the lower portion of the external electrode 101 through the frame 102 and the sealing plate 103. The internal electrode 105 is inserted into a bottle B housed in the external electrode 101. This internal electrode 105 has a hollow structure and has a large number of gas blow-out holes 106 formed in the surface. A gas supply pipe 107 for supplying a CVD medium gas passes through the shelf 102 and the sealing plate 103 and is connected to the lower end of the internal electrode 105. The CVD medium gas is supplied into the internal electrode 105 through the supply pipe 107, and is supplied into the bottle B through the gas blowing hole 106. The RF input terminal 108 is connected to the lower portion of the external electrode 101 through the shelf 102 and the sealing plate 103. The RF input terminal 108 is electrically insulated from the rack 102 in terms of electrical characteristics. In addition, a lower end of the RF input terminal 108 is connected to a high-frequency power source 110 through a matching unit 109. The external electrode 101 and the high-frequency power for plasma generation are applied from the high-frequency power source 110 through the matching unit 109 and the RF input terminal 108. A method for coating a bottle with a carbon film will be described with the thus constructed device. First, the bottle B is inserted into the main body 101a of the external electrode 101, and the bottle B is housed in the external electrode 101 by being attached to the main body 101a. The gas in the external electrode 101 is exhausted through the gas exhaust pipe 104. At this time, the gas in the space inside and outside the bottle B which has been accommodated in the external electrode 101 is exhausted. After reaching the specified vacuum degree (representative value: 1 (T2 ~ 1 (T5 Torr)), the medium gas is supplied to the internal electrode 105 through the gas supply pipe 107, for example, at a flow rate of 10 to 50 ml / min, and then through the internal electrode 105 The gas blowing hole 106 is blown out into the bottle B. Furthermore, for example, using benzene, the size of the paper is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm)

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Line 548338 A7 B7 V. Description of the invention (3) Benzene, xylene, cyclohexane and other aliphatic hydrocarbons, aromatic hydrocarbons, oxygen-containing hydrocarbons, nitrogen-containing hydrocarbons, etc. The medium gas. The pressure in the bottle B is set to, for example, 2 X 10_1 to 1 X 1 (Γ2 Torr) according to the balance between the gas supply amount and the gas discharge amount.

The high-frequency power source 110 applies high-frequency power of 50 to 1000 W to the external electrode 101 through the matching unit 109 and the RF input terminal 108. The application of the external electrode 101 to which such high-frequency power is applied generates a plasma between the external electrode 101 and the internal electrode 105. At this time, because the bottle B is stored inside the external electrode 101 with almost no gap, a plasma is generated in the bottle B. The medium gas is dissociated or re-ionized by the plasma to generate a film type for forming a carbon film, which is deposited on the inner surface of the bottle B to form a carbon film. After forming the carbon film to a predetermined film thickness, stop applying high-frequency power, stop the supply of the medium gas, and exhaust the residual gas, and supply nitrogen, Greek gas, or air into the external electrode 101, and then reduce the space to Atmospheric pressure. After that, the bottle B is removed from the external electrode 101. Furthermore, it takes 2 to 3 seconds to form a carbon film with a thickness of 30 nm by this method. The coating method using such a high-frequency plasma has the following problems. (1) The medium gas is supplied into the plastic container (for example, bottle B) from the majority of the gas blowing holes 106 that are open along the axial direction of the internal electrode 105, and is then exhausted from the mouth of the plastic container. Because of this, the gas flow path in the plastic container is the space between the internal electrode and the external electrode. Although the space near the mouth of the plastic container becomes more conductive and promotes the flow of gas from the blowout hole, the container is farther from the mouth. Gas flow from the gas blow-out hole near the bottom is delayed. Its -8- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm)

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As a consequence, the medium gas near the bottom of the container is exposed to the plasma for a longer period of time than the gas near the mouth of the container, due to the possibility that the gas binding molecules become too large 2 and become powdery. The powdery substance 'does not cover the Gufen surface as a thin film, but becomes a foreign substance deposited on it. The generation of such foreign matter is inappropriate at the following points. , A). Even if most of the powdery substances are piled up, because there is a gap between those powdery substances, there is no gas barrier effect like a carbon film. b) · Internal container of substances that may be mixed into the beverage. (2) The control points of the self-bias value generated by the external electrode are inappropriate as follows. a) The self-bias value depends on the high-frequency power value applied to the external electrode. Because the coating speed is not limited, it must be consistent with the high-frequency power value that is most suitable for the film quality, and it will sacrifice the performance of either side. b) The self-bias value varies depending on the shape of the external electrode, internal electrode, or both. Because the self-bias value that is most suitable for the film quality is not limited to be consistent with the inherent bias value that depends on the shape of the inner and outer pens, you must choose which side takes precedence. If the electrode shape is given priority, it becomes difficult to form a carbon film having a gas barrier property to be found. DISCLOSURE OF THE INVENTION The present invention aims to provide a device for forming a coating on the inside of a plastic container. The purpose is to improve the coating speed of the carbon film, the lifting surface, and the film quality at the same time. Electricity. And covered with a fine, hard carbon film. In addition, the present invention also provides a method for manufacturing a plastic container covered with a carbon film, which has a good -9- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 548338

Film quality, uniform film thickness. According to the present invention, there is provided a plastic container coated with a carbon film inside, and a method for manufacturing the plastic container, which is an object to be treated, is inserted with a bottomed cylindrical external electrode having a size that surrounds its outer periphery, An internal electrode inserted in a plastic container in the external electrode in approximately the entire length in the length direction, and an internal electrode inserted in the plastic container in the external electrode in approximately the entire length in the length direction, and in order to exclude the above-mentioned external electrode Means for removing gas from a gas; and a device for forming a carbon film in a plastic container, which is a high-frequency power source having a high-frequency power source connected to the internal power source and applying high-frequency power to an internal electrode thereof, and is connected to The external electrode is a bias power source that applies a bias voltage to the external electrode. The internal electrode has a structure with a bottomed cylindrical shape and an introduction flow path that also introduces a medium gas supplied from a supply method. Or from the bottom to the side area within 25% of the length of the plastic container inserted into the plastic container, Vector gas blown penetration perforation. According to the present invention, in a method for manufacturing a plastic container covered with a carbon film on the inside including the following steps, a step 'which is to surround the outer periphery of a plastic container to be processed and insert it into a cylindrical external electrode with a bottom (B) Type X sequence 'It will have a bottomed tube shape and have a -10-

548338 Description of the five inventions (A7 B7) The inner #electrode of the structure of the road is inserted into the plastic container approximately the entire length of the plastic container in the length direction. (C) The process is used to insert the The gas of gas: The same day of exhaust by gas means, the medium gas is supplied by the gas supply means at the internal electrode, and the medium gas is blown out of the plastic container by the internal electrode, (d) a kind of process, which consists of partial A pressure power source applies a bias voltage to the external pole, and applies high-frequency power to the internal frequency source to the internal electrode, and generates a plasma around the internal electrode to dissociate the medium gas. A method for manufacturing a plastic container covered with a carbon film, wherein the medium gas is passed from the bottom or bottom of the internal electrode through a side area within a range of 25% of the length inserted into the plastic container, or Both of them are provided with through holes for blowing out the medium gas, and are supplied into the plastic container, and pass through the mouth and the internal electrode of the plastic container. The gap is evacuated, and the above-mentioned plasma gas is dissociated by the above-mentioned plasma in this circulation process. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic perspective view showing a device for forming a carbon film on the inside of a plastic container according to a first embodiment of the present invention. 2A, 2B, and 2C are diagrams showing internal electrodes incorporated in the carbon film forming apparatus of Fig. 1. Figs. 3A, 3B, and 3C are diagrams showing internal electrodes used in Comparative Example 1. -11 · Applicable to China National Standard (CNS) A4 specification (210X297 mm)

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548338 A7 ______B7 V. Description of the Invention (7) Figures 4A, 4B, and 4C are diagrams showing the internal electrodes of the second embodiment of the present invention. Fig. 5 is a schematic diagram showing a power supply unit connected to an internal electrode according to a third embodiment of the present invention. Fig. 6 is a circuit diagram showing a matching device connected to a bias power source according to a third embodiment of the present invention. Fig. 7 is a sectional view showing a device for forming a carbon film into a conventional plastic container. Fig. 8 is a graph showing a relationship between a gas pressure x a bias voltage and a coating speed. Figure 9 is a graph of the relationship between the JT gas pressure X bias voltage and the Raman spectrum D / G ratio in Table 7. Fig. 10 is a graph showing the relationship between gas pressure X bias power and coating speed. Fig. 11 is a graph showing the relationship between the gas pressure X bias power and the Raman spectrum D / G ratio. Best Mode for Carrying Out the Invention The present invention will be described in detail below with reference to the drawings. (First Embodiment) FIG. 1 is a schematic perspective view of a device for forming a carbon film on a plastic container according to a first embodiment of the present invention. FIG. 2A is a front view of an internal electrode incorporated in the device. FIG. 2B FIG. 2A is a cross-sectional view taken along line B_B in FIG. 2A, and FIG. 2C is a view C in FIG. 2A. The bottomed cylindrical external electrode for bias application shown in FIG. 1 has a larger inner diameter than the outer diameter of a plastic container (such as a PET bottle) B forming a carbon coating film, Inside there is a space the size of a B bottle. -12- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) '-(Has a bottomed cylindrical internal electrode 2 with the The length that can be inserted in almost the entire length in the longitudinal direction. The internal electrode 2 also has an introduction flow path for blowing out the medium gas in the above-mentioned bottle B and is connected to a gas supply means (not shown). The internal electrode 2 is, for example, As shown in Figures 2A to 2C, the bottomed cylinder is open at one end. The internal electrode 2 is, for example, provided with a 丨 mm diameter hole 3 at the bottom and inserted from the bottom to the above-mentioned bottle. The side area within the range of 25% of the length in B (for example, from the bottom, the side area where 5/0 of the length of the inside of the above-mentioned bottle B is inserted) is provided with 8 holes. The diameter and number of holes are not limited to this. If the internal electrode 2 is perforated in a side area exceeding 25% of the length inserted from the bottom of the special bottle B, a carbon film coated with a uniform thickness inside the plastic container becomes The diameter of the internal electrode 2 is The diameter across the mouth of the bottle; the length is the length that can be inserted in the entire length of the bottle B in principle. As a guideline for the length, I hope that the ratio of the total length of the bottle B will be approximately (1-0 / (2! 〇). Here, 0 is the diameter of the Pott bottle, l is the full length of the Pott bottle, and L> (D / 2). The internal electrode 2 is made of a heat-resistant metal such as tungsten or stainless steel. It is made of materials, but it can be made of aluminum. The external electrode 1 has an internal gas system which is exhausted by an exhaust means (not shown). The exhaust means is connected to the external electrode 1 by, for example, 丨) = An exhaust pipe and a vacuum tube, or 2) a vacuum container that houses the external electrode worker, an exhaust tube and a vacuum tube connected to the vacuum container. The shape of the vacuum container is arbitrary. Each of the above external electrodes is -13- 548338 A7 B7 V. Description of the invention (9) It is not necessary to store it in an empty container, or to store most external electrodes in a vacuum container. The high-frequency power source 4 'is connected to the internal electrode 2 via a matching device 5 and a power supply unit 6. The bias power source 7 is connected to the external electrode through a matching unit 8. The bias power source 7 may be a DC power source, an AC power source, or a combination of these. Next, the manufacturing method of a plastic container covered with a carbon film is described with reference to Figs. 1 and 2A using the device of Fig. 2C. After constructing a device in which a special bottle B is installed as shown in FIG. 1, the device is housed in a vacuum container (not shown), and the gas in the vacuum container is exhausted through an exhaust pipe and a vacuum pump (not shown). 2A is supplied to the one end of the internal electrode 2 shown in FIG. 2C by a gas supply means (not shown) from the above-mentioned medium through the internal electrode 2 through the bottom and The gas blowout hole 3 from the bottom to the side area in the range of 25% to the length inserted into the above-mentioned bottle B is discharged in the inside of the bottle B as shown by the arrow, and then flows to the% portion of the bottle B go with. Next, grasp the balance between the gas supply amount and the gas exhaust amount, and set it at a predetermined gas pressure. Then, a bias voltage is applied from the bias power source 7 to the bottomed cylindrical external electrode 丨 through the regulating container 8. Thereafter, or at the same time, the high-frequency power is applied to the above-mentioned internal electrode 2 through the matching device 5 and the power supply unit 6 from the Nannan power source 4. At this time, as shown in FIG. 丨, a plasma 9 is generated around the internal electrode 2 and the generated plasma 9 is pulled to the above external electrode where the bias voltage is applied, that is, pulled to the The bott bottle stored in the inside is called B side. With this plasma 9, the medium gas is dissociated to generate • 14- This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 public love) 548338 A7 B7

V. Description of the invention (1Q product film is deposited in the Pate bottle B inside the above-mentioned external electrode applied by the bias voltage, and a Pate coated with a carbon film is manufactured by forming a coating film (carbon film) Bottle. After forming a predetermined film thickness, stop the application of each power, stop the supply of medium gas and residual gas exhaust, supply nitrogen, Greek gas, or air, etc., and then restore the space to atmospheric pressure. After that, exchange the pouch Move to the coating operation of the next bottle. As the above medium gas, it is basically a hydrocarbon compound. For example, it is possible to use chains such as formazan, acetamidine, acetamidine, diamine, pentamidine, hexane, etc Burning class; Ethylene dipropene, butene, pentamidine, succinic diluent, etc .; Blocks, such as ethyl block, winter, meteoline, xylene, phenylhydrazone, allyl, etc. ,% Propane, cyclohexane and other cycloalkanes; cyclopentane, ethyl alcohol and other cycloolefins, methanol, ethyl alcohol and other oxygen-containing hydrocarbons; methyl ammonia, aminoethane, aniline and other substances Nitrogen, hydrocarbons, etc. Others-carbon oxide, carbon dioxide, etc. can also make use of The above high and high frequencies are generally defined as 30 ~ 300MHz, but it is not limited to this. In addition, the application of these powers can be continuous or intermittent (fluctuation). One or more According to the i-th embodiment, by applying high-frequency power i to the internal electrode 2 from the high-frequency power source 4, the electric table is generated around the internal electrode 2. In addition, by using a bottomed cylindrical external electrode 1 By applying a bias voltage from the bias power source 7, the plasma can be carried into a plastic container (such as a bottle). As a result, a) # using high-frequency and high-frequency power, because of the low gas pressure in particular Compared with high-frequency and high-frequency power, a higher electron density can be obtained, so the frequency of collision with the medium gas increases, which can increase the density of the film-forming species. -15- 548338

b) If the bias potential is reduced, the bias potential of the plasma potential can be adjusted, so the ion energy incident on the plastic container can be adjusted. c) Because the ionic reach is proportional to the electron density, it is the same as the above. The adjustment of the potential difference can be used to control the ion flux incident on the plastic container. Therefore, the coating speed of the carbon film to the inner surface of the plastic container can be increased, and the control of the coating speed and the quality of the carbon film can be achieved. In addition, the plastic is supplied by passing a medium gas through the bottom or from the bottom to a side area within a range of 25% of the length inserted into the plastic container, or through both of them, and through-holes are provided for blowing out the medium gas. A container (such as a bottle) forcibly generates a gas flow from the bottom of the container to the mouth. Therefore, it is possible to prevent stagnation of gas from being made in the plastic container. As a result, the quality of the film with less contamination is very good, and it is possible to produce a plastic container covered with a uniform carbon film on the inside. (Embodiment Example 1) As shown in Figs. 2A to 2C, as the internal electrode, i.e. a gas blowout hole with a diameter of 1 mm was passed through the bottom of a stainless steel single-sided tube with a diameter of 1/2 and a length of 200 mm, and used A structure is a side area in a range from the bottom to 5% of the length inserted into the plastic trough. Eight gas blow-out holes of the same diameter are respectively drilled at the same circumferential position. The internal electrode was inserted into a bott bottle housed in a bottomed cylindrical external electrode as shown in FIG. 1. The external electrode was placed in a vacuum container, and C ^ H2 gas as a medium was passed at a gas flow rate of 20 seem. Under the conditions of a gas pressure of 0.1 Torr in a vacuum container, a high frequency of 100 MHz supplied by a high-frequency power supply, and a high frequency of 13 MHz biased by a bias power supply, under the above-mentioned Baote-16- The dimensions apply to the Chinese National Standard (CNS) A4 specification (210X297 mm) 548338 A7 _______B7 V. Description of the invention (12) The bottle is covered with a carbon film. (Comparative Example 1) FIG. 3A is a front view of an internal electrode used in the comparative example 1. FIG. 3A is a cross-sectional view taken along the line B and B of FIG. 3A, and FIG. 3C is a c view of FIG. As shown in FIG. 3A to FIG. 3C, as the internal electrode: a gas blowout with a diameter of 1 mm was passed through the bottom of a stainless steel single-sided tube with a diameter of 1/2 inch and a length of 200 mm, except that a structure was used. It is a side area in the range from the bottom to 35% of the length inserted into the plastic container. 32 gas blow-out holes of the same diameter are arranged in parallel at the same circumferential position. In the same manner as in Example 1, a carbon film was coated on the inside of the bottle. The coating speed in Example 1 and Comparative Example 1 were investigated, and the thickness of the carbon film was uniform, and the presence or absence of powder particles incorporated into the carbon film was investigated. The results are shown in Table 1 below. In addition, the “coating speed is based on a non-coated pour bottle as a reference sample.” The film thickness was calculated from the interference spectrum apex (highest) wavelength and valley (lowest capture) wavelength of the light transmittance of the coated sample. The inflection rate of the coating was 2. The calculated film thickness was divided by the coating time to obtain the speed. As a measuring device, a self-recording spectrophotometer manufactured by Hitachi was used. • 17- This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) 548338 A7 B7 V. Description of the invention (Table 1 Comparative example 1 Implementation example 1 Bottom; Bottom, 1 rod-shaped internal electrode hole configuration 1 8 sides, 4 sides, 8 sides, 1 side knot coating speed (average side of the bottle) (nm / s) 1.9 3.0 Fruit film thickness uniformity + 61% + 2% (side of the bottle) ) -31% -3% Whether there are powders or not. It is clear from the above Table 1 that, as in Example 1, a gas blow-out hole with a diameter of 1 mm is provided at the bottom, and the internal electrode uses a structure, which is In the side area within the range from the bottom to 5% of the length inserted into the plastic container, eight gas blowing holes of the same diameter are perforated at the same circumferential position, and the medium gas is removed from each of the internal electrodes. The gas blow-out hole is supplied into the bottle, which not only improves the coating and greatly improves the uniformity of the film thickness compared to Comparative Example 1. (Second Embodiment) FIG. 4A is a front view of the internal electrode, and FIG. Front view of the internal electrodes installed in the device, Figure 4B 4A is a cross-sectional view taken along line B-B of FIG. 4A, and FIG. 4C is a view C of FIG. 4A. The internal electrode 2 has an electrical insulator (for example, 4 ceramics with an outer diameter of 4 mm and an inner diameter of 3 mm) provided inside. : Tube) 10. The electrical insulator 10 is not limited to this material as long as it does not hinder the flow of the medium gas. -18- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 548338 A7 _ · _B7 V. Description of the invention (14) According to the second embodiment, if a plasma is generated around the internal electrode 2 described in the first embodiment, an electrical insulator is used. 10 Physically blocking the space of the internal electrode 2 can prevent the generation of plasma in the internal electrode 2. That is, there are the following points that are not suitable: once the plasma is generated in the internal electrode 2, it is originally in the interior. The generation efficiency of the plasma to be generated by the electrode 2 is reduced, and it is covered in unnecessary places, and the function of the device is degraded, etc. By doing so, the electrical insulator 10 that secures electrical properties is interposed in the internal electrode 2 as a medium. Gas flow One side installation can physically block the space in the internal electrode 2 and exclude the space where plasma is generated. Therefore, it is possible to improve the efficiency of plasma generation and prevent coating from being unnecessary. (Third Embodiment) Figure 5 is a schematic diagram of a power supply unit connected to an internal electrode according to a third embodiment of the present invention. The internal power supply unit 6 connected to the internal electrode 2 has a tube structure and a medium gas flows therein. This power supply unit 6 , Is connected to the gas supply pipe 12 through an insulating pipe u. This insulating tube u is an electrical insulating material using the above-mentioned gas supply tube 12 and the electric source supply unit 6. The high-frequency and high-frequency power supply 4 is connected to a power supply unit 6 via a matching device 5 as described above. The ground shield 13 is arranged around the power supply section 6 described above. The ground shield 3 is tubular, conductive, and grounded, and its inner diameter is slightly larger than the outer diameter of the power supply section 6 described above. However, its outer diameter is not specified. In the power supply unit 6 constructed as described above, the flow of the medium gas is passed from the gas supply pipe 12 through the insulating pipe u to one end of the internal electrode 2 and passes through this -19-5 ^ paper size suitable for household materials (CNS) A4 specification (21GX 297 mm)-548338 A7 B7 V. Description of the invention (inside the internal electrode 2, the gas blow-out hole 3 is discharged into the pour bottle (not shown), and the gas is exhausted to a vacuum container (not shown) The function of the power supply unit 6 shown in FIG. 5 is explained in this way. The principle of the ground shield 13 is to make the distance between the power supply unit 6 and the ground part extremely narrower than that of the plasma sheath. Plasma cannot be generated in its space. The electric mass is maintained by the existence of an ionic layer between the electrode and the plasma. The thickness of the ionic layer is generally from several times to 10 times the Debye length of the plasma. The worship length is expressed by the following formula (1): A〇W = 6.90x {-^ [(1) However, · Debye length,

Te: electron temperature,

Ne: electron density. Therefore, the Debye length is obtained from the predicted electron temperature and electron density of the plasma. The value of 10 times is taken as the length of the ion layer, and the distance between the ground shield 13 and the power supply unit 6 is regarded as not exceeding ions. Layer length (eg 丨 mm [diameter part 2 mm]). The length of the Debye is in "Plasma Basic Engineering", written by Deng Jingxin, and detailed by Uchida Old Crane Farm. Furthermore, when the ground shield 13 is not provided, if power is applied to the power supply unit 6, the electric field rises between the external electrode or the vacuum container (both are grounded). Depending on the conditions at that time (electricity, gas pressure) , The distance between the supply department and the external electrode or the vacuum container, etc.) Plasma may be generated. The function of the ground shield is to prevent unnecessary electricity from being generated around the power supply unit 6. Once the unnecessary plasma is generated, it should have been generated around the internal electrode. • 20- This paper ruler is based on the National Standard (CNS) A4 specification (2 outline 29? Public reply) 548338 A7 _.__ B7 V. Description of the invention (~ ~) The formation efficiency of the plasma is reduced, it is covered in unnecessary places, and its function as a coating device is degraded. In addition, according to the third embodiment, as shown in Fig. 5, by arranging the ground shield 13 around the power supply unit 2, a condition in which the surrounding plasma is not generated can be established. In addition, since the internal electrode 2 has both a function of supplying gas and a function of applying electric power, the function can be separated by connecting the gas supply pipe 12 to the power supply unit 6 through an insulating pipe u. (Fourth Embodiment) Fig. 6 is a circuit diagram showing a matching device of a bias power source connected to a bottomed cylindrical external electrode of a device for forming a carbon film in a plastic container according to the fourth embodiment. The matcher 8 is made of, for example, a 20 nF capacitor, and one end is connected to a bias power supply 7 for supplying a high frequency power supply of 0.5 · Z, and the other end is connected to a bottomed cylindrical external electrode 1. The plasma angular frequency (-) represented by the following formula (2), as described in "Electro-Positioning Basic Engineering", by Tsutsui Tsutsui, detailed by Uchida Laopu, gives the electromagnetic wave shielding conditions. Electromagnetic waves of a frequency higher than the frequency of the electric condensing angle are enough for μ to propagate in its «, but the low frequency is blocked or refracted. ~ = 2πχ0 · 897χ ^ χ η (2) However, Ne: Plasma electron density. : Secondly, the electron density of the plasma generated by the internal electrode 2 described above is ^ & The plasma angular frequency obtained by the above formula (2) becomes 283 MHz. ^ The two running modes consider the bias frequency of the bias power supply 7 as a ratio of -21 _ _ This paper size is applicable to the Central Government Standard (CNS) χ --- 548338

13.56 MHz + 0.5 MHz (for matching the bias frequency, for example, the matcher 8 is composed of 2 OnF capacitor C), compared with the above-mentioned plasma angular frequency (( 〇pe) is set to be very low, so that the ions in the plasma 9 generated around the π internal electrode 2 as described above can follow the alternating electric field and move. As a result, the ions can be promoted to the bottomed cylindrical external electrode 1 The plastic container (such as a bottle) is incident on the inside surface. In addition, when a bias frequency of 13.56 MHz is supplied by a bias power source, the matching device is installed in series between the bias power source and an external electrode. The first capacitor Ci and the reactance L 'and the connection to the power source 7 of the first capacitor Ci are divided into two sides, and are constituted by a second capacitor provided on a grounded line. (Embodiment Example 2) As an internal electrode, from the figure As shown in Figs. 2A to 2C, a gas blowout hole with a hole diameter of 1 is passed through the bottom of a stainless steel single-sided sealing tube with a diameter of 1/2 inch and a length of 200 mm, and a structure is used. 5% of the length in a plastic container In the side area of the enclosure, eight gas blow-out holes of the same diameter are respectively arranged at the same circumferential position. The internal electrode is inserted into a bott bottle housed in a bottomed cylindrical external electrode as shown in FIG. This external electrode was placed in a vacuum container, except that the bias high frequency of the bias power source was 0.5 MHz, and carbon was coated on the inside of the above-mentioned bottle under the same conditions as in Example 1 above. The bias voltage and Raman spectrum (D / G) of the external electrode under the conditions of Example 2 and Comparative Example 1 (the bias high frequency by the bias power source is 13 MHz) were investigated. 'The bias voltage and Raman spectrum were measured by the following methods: -22- This paper is sized for China National Standard (CNS) A4 (210X 297 mm)

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548338 A7 B7 V. Description of the invention (18) (D / G) ratio. (1) Bias voltage A high-voltage detector is provided at the output portion of the matcher 8 connected to the power supply for the dust-dusting, and the power waveform is observed on the oscilloscope with this detector. In addition, the high-voltage detector uses 6015A manufactured by SONY Tektronix. (2) The Raman spectrum (D / G) ratio is the structure of the carbon film formed in the inside of the bottle. The laser uses a laser Raman spectrometer (excitation wavelength 532 nm) manufactured by Japan Spectroscopy. Raman spectrometry made an inference. The carbon film has a peak shape near 1350 cm · 1 (irregular component) and 1550 cm · 1 (graphite component). The two spectral shapes were combined with two Gaussian distributions to calculate the respective distribution areas, and the ratio was calculated and used as the D / G ratio. Furthermore, if the value of the D / G ratio is high, the graphite field is growing in the membrane structure. That is, because a graphite structure having a larger lattice constant than that of a gas molecule is growing, gas permeability is reduced. Since the membrane necessary for gas barrier is a fine thin film that does not physically transmit gas molecules, a hard film having a low D / G ratio is advantageous. The evaluation method of the film quality viewed from such a Raman spectrum, for example, in the "Raman spectrum of a diamond-shaped carbon film", Masahiro Yoshikawa, NEW DIAMOND, Vol. 4, No. 2, p 16, or "based on Raman Evaluation of Diamond Film by Mann Spectroscopy ", Masahiro Yoshikawa, Surface Technology,

Vol. 42, No. 12 (1991), p 35 is described in detail. In addition, regarding the evaluation of DLC (Diamond like carbon) film characteristics, for example,

Understanding Diamond (Sub-theme) Catalysis of DLC ", Yamamoto Kazuhiro NEW -23- This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) 548338 A7 B7 — V. Description of Invention () DIAMOND, Vol · 16, No. 2, p 38 is described in detail. As a result, when the bias frequency of the bias power source is set to 13 MHz as in Comparative Example 1, the time-averaged bias voltage is 0V, and the bias frequency number of the bias power source is set to At 0.5 MHz, a 50V bias voltage can be applied to the external electrode. Therefore, in Comparative Example 1, the Raman spectrum (D / G) ratio is 1.22, and in Example 2, the same Raman spectrum (D / G) ratio is reduced to 0.98, and a hard, fine carbon film can be formed. (Embodiment Example 3) In Embodiment 3, a carbon film forming apparatus having the structure shown in Figs. 1, 2A to 2C, 4A to 4C, and 5 is used. That is, the basic structure of the carbon film forming apparatus is shown in Fig. 1 and the internal electrode structure is shown in Figs. 2A to 2C and Figs. 4A to 4C. The power supply unit for the internal electrodes is shown in Fig. 5. As the internal electrode, a structure was used in which a gas blow-out hole with a diameter of 1 mm was perforated at the bottom of a stainless steel single-sided tube with a diameter of 16 mm and a length of 163 mm. This internal electrode was inserted into a bott bottle housed in a cylindrical external electrode with a bottom as shown in FIG. 1, and C2H2 gas as a medium was supplied to the external electrode at a flow rate of 30 seem and 200 seem, and was supplied outside The gas pressure in the electrode is 100 mTorr and 1000 mTorr, while the high and high frequency power is 100 MHz, 300W, and 500W, and the high and high frequency of the bias power is biased at 3 MHz. The special bottle is covered with carbon film. While the above coating conditions are summarized as shown below, the coating speed is shown in Table 2 below. -24- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297 mm) 548338 A7 B7 V. Description of the invention ("Coating Conditions" • C2H2: 100% • Hole configuration of rod-shaped internal electrode: bottom One, • Plasma generation: 100 MHz, • Bias: 3 MHz, 300 νP · P. Table 2 Power at 100MHz— (W) Pressure of C2H2 (mTorr) Covering speed (nm / s) 300 100 4.0 300 1000 13.6 500 1000 26.6 It is clear from the above Table 2 that the coating speed can be increased by the increase of high-frequency power and the increase of gas pressure. (Embodiment Example 4) In this Embodiment Example 4, the above-mentioned FIG. 1 is used. 2A to FIG. 2C, FIG. 4A to FIG. 4C, and FIG. 5 of the carbon film forming device. That is, the basic structure of the carbon film forming device is as in Example 3, and the rod-shaped internal electrode structure is as shown in Example 3 and FIG. 4A to 4C, the power supply unit for the rod-shaped internal electrode is shown in Fig. 5. According to A. Bubenzer et al, J. AppI. Phys. 54 (8), August 1983, 4590, and Y. Catherine et al. , Thin Solid Film, 144 (1986) 265-280, the coating speed and The parameters are related by the following formulas (3), (4), (5). -25- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 548338 A7

B7 (3) w

Vb ^ (4) EKJ ^ (5) However, G is the coating speed, vb is the bias voltage, p is the gas pressure, w is the bias power, and E is the energy of the ions applied by the bias. According to the above formula (3), the coating speed is proportional to the product of the bias voltage and the gas pressure. In addition, the bias voltage is proportional to the bias power, and the square root of the pressure is inversely proportional. Substituting the above formula into formula (3), the covering speed is proportional to the square root of bias bias and pressure. The ion energy is proportional to the bias power and the square root of the pressure is inversely proportional. Based on this, understand the following facts. (a) To increase the coating speed, increase the bias voltage (electricity) and gas pressure by 0. (b) To increase the ion energy, increase the bias voltage to reduce the gas pressure. (c) Therefore, in order to increase the coating speed and manufacture a fine film suitable for gas barrier, increasing the ion energy becomes the opposite gas pressure condition. The effect of increasing the gas pressure is described in Example 3, and the effect of increasing the bias voltage (vb) is confirmed here. As the internal electrode, a structure was used. A gas blowout hole with a diameter of 1 mm was perforated at the bottom of a stainless steel single-sealed tube with a diameter of 16 mm and a length of 163 mm as shown in Figs. 2A to 2C. -26- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 548338 A7 B7 V. Description of the invention (Insert this internal electrode into a cylindrical external electrode with a bottom as shown in Figure 1 The inner bottle is used as a medium (2 gas is supplied to the external electrode at a flow rate from 20 sccm to 100seem. The pressure of the gas supplied in the external electrode is from 100 mTorr to 1000 mTorr. At the same time, the high frequency and high frequency of 100MHz and 50W to 500W, and the high frequency and high frequency of the bias voltage by the bias power supply are 13 MHz, and the carbon bottle is covered with the carbon film. The coating conditions are summarized as follows: "Covering conditions" • C2H2: 100% • Hole configuration of rod-shaped internal electrodes: 1 at the bottom, • Plasma generation: 100 MHz, • Bias: 13 MHz. The coating effect is shown in Figure 8 to Figure 11. In addition, Figure 8 shows the relationship between the product of the gas pressure and the bias voltage (c2h2 pressure x bias voltage) and the coating speed, and Figure 9 shows the Raman spectrum at that time. The result of the spectral D / G ratio. Figure 10 shows the gas pressure and bias power. The relationship between the product (gas pressure X bias power) and the coating speed, the results of the Raman spectral D / G ratio at that time are shown in Fig. 丨. From Figure 8 to Figure 11, it is understood that according to the above formula (3 The proportional relationship between) and (4) can increase the coating speed without deteriorating the film quality. The idea of film quality evaluation using the Raman spectral D / G ratio as an index is as described in Implementation Example 2. In Implementation Example 4 It is understood that even if the coating speed is increased, because the value is maintained around 1, the coating speed can be increased without deteriorating the film quality. As already explained above, if the present invention can provide a -27- Zhang scale is applicable to China National Standard (CNS) A4 specification (210X 297 mm) 548338 A7 B7 V. Description of the invention (a device for forming a carbon film in a plastic valley device, which is used to simultaneously improve the coating speed and film quality. In addition, according to the present invention, it is possible to provide a method for manufacturing a plastic container having a good film quality and a uniform film thickness and covered with a carbon film. Moreover, if According to the present invention, it is possible to provide a method for manufacturing a plastic container with good film quality, uniform film thickness, and a detailed, hard coating of a carbon film on the inside. ≫ -28- This paper size applies to Chinese national standards ( CNS) A4 size (210X297 mm)

Claims (1)

Patent application scope 1 'a kind of carbon film V inside a plastic container; equipped with: when a plastic container to be treated is inserted, it has a bottomed cylindrical external electrode with a size surrounding its periphery; the plastic container in the external electrode An internal electrode which is inserted into the entire length in the length direction; a gas exhausting means for excluding gas in the external electrode; a high-frequency power source connected to the internal electrode and applying high-frequency power to the internal electrode; A biasing power source biased at the outer electrode biasing port at the outer edge electrode; the inner #electrode has a bottomed cylindrical shape and also has a structure for introducing a medium gas introduction flow path supplied from a supply method; and A through hole for blowing out the medium gas is formed in a bottom area of the bottom surface or a side area in a range of 25/0 of a length inserted into the plastic container or both of them. 2. The device for forming a carbon film in a plastic container according to item 丨 of the patent application, wherein the high-frequency and high-frequency power supply is connected to the internal electrode through a matching device and a power supply unit, and the biasing power supply passes through the matching device. And the power supply unit is connected to the external probe. 3. The device for forming a carbon film in a plastic container according to item 丨 of the scope of the patent application, wherein the hollow portion in the above-mentioned internal electrode is provided with an insulator to prevent plasma from being generated in the hollow portion. 4. According to the scope of the patent application, the plastic container for carbon film formation -29- This paper size is applicable to China National Standard (CNS) A4 specification (210X297) | 548338 device, in which the above-mentioned internal electrode is provided with a plurality of above-mentioned through holes. 5. The apparatus for forming a carbon film on the inside of a plastic container according to item 2 of the scope of the patent application, wherein a ground shield is arranged around the power supply section. 6. · A method for manufacturing a plastic container covered with a carbon film, which involves the following steps when manufacturing a plastic container covered with a carbon film: (a) in a manner of surrounding the periphery of the plastic container to be treated And the process of inserting it into the bottomed cylindrical external electrode, (b) the bottomed cylindrical internal electrode having a structure that also has a medium gas introduction flow path, approximately the entire length of the plastic container in the length direction The process of inserting the inside of the plastic container, (c) exhausting the gas in the external electrode by using an exhaust means, and supplying a medium gas to the internal electrode by a gas supply means, and the internal electrode is in the plastic container A process of blowing out a medium gas, and (d) applying a high-frequency power to the internal electrode with a high-frequency power source while applying a bias voltage to the external electrode with a bias power source, and surrounding the internal electrode When the plasma is generated, the medium gas is dissociated, and the medium gas is passed through the bottom of the internal electrode or from the bottom to the plastic container. The side area within the range of 25% of the length or the through-holes provided therethrough, to supply the above-mentioned medium gas into the above-mentioned plastic container, through the mouth and inside of the above-mentioned plastic container-30- This paper size applies China National Standard (CNS) A4 specification (21 × 297 mm) Binding Mongolia A BCD 548338 VI. Scope of patent application The gap of the electrodes is exhausted, and the above-mentioned plasma gas is dissociated by the above-mentioned plasma during the circulation process. 7. According to the method for manufacturing a plastic container covered with a carbon film inside the scope of the patent application, wherein a bias voltage is applied to the external electrode by the bias power source, a matching device is interposed between the power source and Between external electrodes, the number of bias frequencies should be equal to or less than the angular frequency of the plasma. -31-This paper size applies to China National Standard (CNS) A4 (210X297 mm)