WO2004001095A1 - ロータリー型量産用cvd成膜装置及びプラスチック容器内表面へのcvd膜成膜方法 - Google Patents
ロータリー型量産用cvd成膜装置及びプラスチック容器内表面へのcvd膜成膜方法 Download PDFInfo
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- WO2004001095A1 WO2004001095A1 PCT/JP2003/007797 JP0307797W WO2004001095A1 WO 2004001095 A1 WO2004001095 A1 WO 2004001095A1 JP 0307797 W JP0307797 W JP 0307797W WO 2004001095 A1 WO2004001095 A1 WO 2004001095A1
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- film forming
- external electrode
- film
- container
- spaces
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D23/00—Details of bottles or jars not otherwise provided for
- B65D23/02—Linings or internal coatings
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
Definitions
- the present invention relates to a CVD (Chemical Vapor Deposition) chemical vapor deposition (CVD) method, a CVD film forming apparatus for coating a CVD film on the inner surface of a plastic container.
- the present invention relates to an apparatus, particularly a CVD film forming apparatus for mass production, and further covers a film forming method.
- CVD method especially plasma CVD method, is used to deposit a DLC (diamond-like carbon) film on the inner surface of plastic containers for the purpose of improving gas pliability etc.
- the used vapor deposition apparatus is disclosed in, for example, Japanese Patent Application Laid-Open No. Hei 8-5311. Further, Japanese Patent Application Laid-Open No. 10-258885 discloses a manufacturing apparatus for mass-producing a DLC film-coated plastic container and a method for manufacturing the same.
- Japanese Patent Application Laid-Open No. H10-2588825 discloses that a plurality of chambers are arranged at equal intervals on the same circle, and the external electrodes of adjacent chambers are connected by conductors. Is disclosed that is connected to a high frequency power supply by a linear conductor extending from the center of the circle. With this apparatus, simultaneous film formation is performed on a plurality of containers.
- the present inventors have developed a mass-production apparatus for depositing a CVD film on the inner surface of a container.
- the inventors of the present invention do not use a simultaneous deposition method for all the deposition chambers.
- a plurality of film forming chambers are arranged in a circle on a rotating support, and the rotating support is rotated at a constant speed. While the rotating support (turntable) is rotating, each of the film forming chambers is rotated. It was concluded that controlling the production cycle was preferable.
- the manufacturing cycle consists of (1) a container mounting process for a plastic container, (2) a gas adjusting process before film formation inside the container, (3) a CVD film forming process by plasma-forming the raw material gas, and (4) a film forming process inside the container.
- This is a cycle that includes post-membrane gas conditioning and (5) a step of removing the coated vessel.
- a CVD film forming apparatus in which a film forming chamber arranged on a circle performs one manufacturing cycle while a rotating support makes one rotation is classified as a rotary type. It is distinguished from the batch type apparatus disclosed in Japanese Patent Publication No. 0-25858825.
- the matching time by the matching box is slightly different from each other, so that the matching times can be accurately matched to each other. Can not. Specifically, there may be a gap of about 0.1 to 1 second between impedance matching in each matching box.
- the thickness of the DLC film formed on the inner surface of the plastic container is as thin as about 30 nm. Since 3 seconds is enough, it is necessary to control the film thickness relatively accurately. Because of this, 0.:! A deviation of the matching time of about 1 second greatly affects the variation in the thickness of the DLC film, especially the variation in the thickness between the plastic containers. Therefore, the quality of the DLC film varies. If one matching box is connected to one high-frequency power supply, and if one matching box is connected to a plurality of external electrodes, the variation is even greater than in the case of the above embodiment.
- the present invention has been made in view of the above circumstances, and its purpose is to accommodate a predetermined number of plastic containers in one external electrode, and to apply a high frequency to the walls of these plastic containers.
- a new external electrode structure that can generate a uniform self-bias voltage, and reduced the number of high-frequency power supplies and matching boxes to less than the number of deposition chambers. It is to provide a membrane device.
- the present inventors refer to an external electrode having a new structure as a “multiple-integrated external electrode”. Multi-integrated external electrodes can reduce thickness variations, reduce the number of components and make them compact with a simple structure, and also achieve easier maintenance and lower equipment costs. It is.
- the accommodating spaces are arranged at equal intervals on the same circumference with the center axis of the external electrode as a center point, thereby simultaneously forming a plurality of plastic containers accommodated in the integral external electrode.
- the purpose is to generate a more uniform plasma in any container when forming a film.
- the multiple integrated external electrodes it is an object of the present invention to propose, as specific embodiments of the multiple integrated external electrodes, some embodiments particularly compatible with a rotary type CVD film forming apparatus.
- a plurality of deposition chambers are arranged on a rotating support for making a one-tally type, but for example, the rotation axis of the rotating support is the center as in a beverage filling machine. It is not necessary to arrange the containers in a row in the same circumferential direction. Since the arrangement of the accommodating space for the external electrodes can be changed as appropriate under certain restrictions, the multiple integrated external electrodes have the purpose of reducing the number of high-frequency power sources and the number of matching boxes, as well as the above-mentioned circumference of the accommodating space.
- the present invention proposes a particularly preferable arrangement of a container storage space in a rotary type device in order to improve productivity and prevent the container mounting mechanism and the container unloading mechanism from being complicated.
- the present invention in particular, the case where two housing spaces are provided for one external electrode, the case where three housing spaces are provided for one external electrode, and the case where four housing spaces are provided for one external electrode
- the purpose is to propose a specific layout of the accommodation space.
- the rotary type apparatus of the present invention by completing all the film forming steps during one rotation of the rotary support, cooperation with the container supply line, the present apparatus and the coated container unloading line is achieved. It is intended to be performed in a smooth manner. It is another object of the present invention to make the rotation speed of the rotating support constant and save power.
- the present invention provides a CVD film forming apparatus for mass production of a single-port type, in which a hydrocarbon-based gas or a Si-containing hydrocarbon-based gas is used as a raw material gas to form a DLC film as a CVD film.
- the purpose is to provide a method for forming a CVD film.
- the rotary type CVD film forming apparatus has a plurality of housing spaces for accommodating each plastic container in one columnar body also serving as an external electrode.
- the accommodation spaces are provided side by side on the same circumference with the central axis of each of the accommodation spaces being parallel to the central axis of the external electrode and having the central axis of the external electrode as a center point.
- An internal electrode is provided inside the mounted plastic container so that it can be inserted and removed from the mouth, and an insulating member is provided to make the internal electrode and the external electrode insulated when the internal electrode is inserted into the plastic container.
- a film-forming chamber provided with a lid for closing the accommodation space to reduce the pressure is provided, and a plurality of the film-forming chambers are arranged on the rotating support at equal intervals in a circle shape.
- Plastic stored in the membrane chamber A source gas introducing means for introducing a source gas to be converted into plasma is provided inside the plastic container, and a high frequency supply means for supplying high frequency to the external electrode of each of the film forming chambers is provided.
- the method is characterized in that a film is formed.
- the accommodating spaces are juxtaposed at equal intervals on the same circumference centered on the central axis of the external electrode.
- the film forming chambers are arranged at equal intervals on the rotating support so as to be arranged on the same circumference centered on the rotation axis of the rotating support.
- the CVD film forming apparatus wherein two accommodating spaces are provided for one external electrode, and the film forming chamber is disposed on the rotary support.
- One accommodating space is arranged outside the cycle formed by each of the film forming chambers, and the other accommodating space is arranged inside the circle, so that the accommodating space for the external electrodes is the circle of the circle. It is preferable to arrange in two rows in the circumferential direction.
- the housing space for the external electrodes is arranged outside the circle formed by the film forming chamber, and the remaining two housing spaces are arranged inside the circle. It is preferable to arrange in two rows in the direction.
- the accommodating space is arranged in a circumferential direction of the circle when the film forming chamber is disposed on the rotating support. More preferably, they are arranged so as to be adjacent to each other across the row and the circle, or are arranged in two rows in the circumferential direction and shifted from each other across the circle. Further, in the method for forming a CVD film on the inner surface of a plastic container according to the present invention, the plastic container is housed in the housing space while the rotating support is rotated once at a constant speed.
- a film forming chamber performs one manufacturing cycle during one rotation of the rotating support, and is a small, inexpensive, and highly efficient mass-produced CVD film forming apparatus. It was possible to provide a mouthpiece type mass production apparatus for forming a film. According to the present invention, in the mouth-to-mouth type apparatus, both productivity improvement and prevention of complication of the container mounting mechanism and the container removing mechanism are achieved. This equipment does not require a large pumping speed to evacuate all the film forming chambers at the same time, does not need to use wasteful power because it does not control against the rotational inertia of the rotating support.
- the container supply line, the apparatus and the unloaded container are completed by completing all the film forming steps during one rotation of the rotary support in the one-piece type apparatus of the present invention. Cooperation with the line can be performed smoothly.
- the present invention provides a CVD film forming apparatus for rotary type mass production for forming a DLC film as a CVD film by using a hydrocarbon gas or a Si-containing hydrocarbon gas as a raw material gas.
- a CVD film forming apparatus for rotary type mass production for forming a DLC film as a CVD film by using a hydrocarbon gas or a Si-containing hydrocarbon gas as a raw material gas.
- FIG. 1 is a schematic diagram showing one embodiment of a mouthpiece type mass production CVD film forming apparatus of the present invention.
- FIG. 2 is a schematic diagram showing one embodiment of a basic configuration of a film forming chamber in the rotary type CVD film forming apparatus of the present invention.
- FIG. 3 is a schematic view showing one embodiment of a plurality of integrated external electrodes composed of a single columnar body capable of simultaneously coating four plastic containers with a DLC film in the present invention.
- FIG. 4B shows a state in which the external electrode and the upper external electrode are sealed, and FIG. 4B shows a state in which the lower external electrode and the upper external electrode are open.
- FIG. 4B shows a state in which the external electrode and the upper external electrode are sealed
- FIG. 5 is a diagram showing a specific example of the form of the columnar body.
- Fig. 6 is a conceptual diagram showing the arrangement of the accommodation space when two accommodation spaces are provided for one external electrode.
- A shows the case where the accommodation spaces are arranged on a circle.
- C shows the cases where the accommodation spaces are shifted from each other with the circles interposed between them.
- FIG. 7 is a conceptual diagram showing an arrangement of the accommodation spaces when three accommodation spaces are provided for one external electrode.
- Fig. 8 is a conceptual diagram showing the layout of the housing spaces when four housing spaces are provided for one external electrode, and (a) shows two housing spaces 40x and 40y.
- the two chambers 40a and 40b are arranged inside the circle s and the space 40 of the external electrode 3 is arranged in the circumferential direction of the circle s.
- (B) is a case where two rows are arranged in the circumferential direction and are shifted from each other across the circle s.
- C) is a case where the rows are further shifted than (b). Show.
- FIG. 9 is a conceptual diagram showing one embodiment of a basic configuration including a high frequency supply means in the rotary type CVD film forming apparatus of the present invention.
- FIG. 10 is a diagram showing one form of a distribution circuit diagram, showing a parallel type and a cascade type.
- FIG. 11 is a diagram showing one mode of a manufacturing cycle.
- FIG. 12 is a diagram showing a second mode of advancing the manufacturing cycle.
- FIG. 13 is a diagram showing a third mode of the manufacturing cycle.
- FIG. 14 is a diagram showing a fourth mode of advancing the manufacturing cycle.
- the meanings of the codes are as follows. 1 is a lower external electrode, 2 is an upper external electrode, 3 is an external electrode, 4a is an insulating member, 4b is a lid, 6 is a film forming chamber, 7, 7a, 7b, 7c, 7d is a plastic container, and 8 is an O-ring.
- 9, 9a, 9b, 9c, 9d are internal electrodes, 10, 11, 22 are piping, 14 is an automatic matching device, 15 is a high frequency power supply (RF power supply), 16, 17, 18 are vacuum valves, and 19 is a mass flow Controller-, 20 is source gas source, 21 is vacuum pump, 27 is leak gas (air) supply source, 28 is vacuum gauge, 29 is exhaust duct, 30 is high frequency output supply slot, 32 is high frequency output Supply lot connection contact, 40 is storage space, 41 is source gas introduction means, 49, 49a, 49b are gas outlets, ⁇ ⁇ is the center of multiple integrated external electrodes, ⁇ 2 is high frequency output supply point, X is the central axis of the multiple integrated external electrodes, and 7ax, 7bx, 7cx, and 7dx are the central points of the accommodation space of the plastic containers 7a to 7d.
- FIG. 1 is a conceptual diagram showing the relationship of the basic configuration of a CVD film forming apparatus for mass production according to the present invention.
- a rotary type CVD film forming apparatus for mass production according to the present invention comprises: a film forming chamber; a plurality of rotating supports each having a plurality of the film forming chambers arranged at equal intervals in a circle; and a brassier housed in each film forming chamber.
- a raw material gas introducing means for introducing a raw material gas to be converted into plasma inside the stick container and a high frequency supply means for supplying high frequency to the external electrode of each film forming chamber are provided to form a CVD film on the inner surface of the plastic container. I do.
- Fig. 2 is a conceptual diagram showing the structure of one of the film forming chambers in Fig. 1, focusing on one of the film forming chambers.
- the portion of the film forming chamber 16 in Fig. 2 is a conceptual sectional view cut in the container axial direction. is there.
- the film forming chamber 16 includes an external electrode 3 in the form of a single column provided with a plurality of accommodation spaces 40a and 40c for accommodating each of the plastic containers 7a and 7c, and each of the accommodation spaces 40a and 40c.
- the internal electrodes 9a, 9c that can be inserted and removed from the mouth inside the plastic containers 7a, 7c attached to the plastic container 7a, and the internal electrodes 9a, 9c when the internal electrodes 9a, 9c are inserted into the plastic containers 7a, 7c.
- the lid 4b is formed of a conductive member and supports the internal electrodes 9a and 9c.
- a space is provided in the lid 4b, which communicates with the storage spaces 40a, 40c, and forms a decompression space together with the storage spaces 40a, 40c.
- an exhaust means composed of a vacuum pump 21 and the like is connected to the lid 4b, and the storage space 40a, 40c can be depressurized by depressurizing the space of the lid 4b.
- the insulating member 4a is arranged below the lid 4b, and the external electrode 3 is arranged below the insulating member 4a. With such a positional relationship, the lid 4b, the conductive internal electrodes 9a, 9c, and the external electrode 3 are insulated by the insulating member 4a.
- the external electrode 3 includes an upper external electrode 2 and a lower external electrode 1, and is configured such that an upper portion of the lower external electrode 1 is detachably attached to a lower portion of the upper external electrode 2 via a ring 8. By detaching the upper external electrode 2 and the lower external electrode 1, the plastic containers 7a and 7c can be mounted.
- the external electrode 3 is divided into two parts, a lower external electrode 1 and an upper external electrode 2.
- the external electrode It is divided into three or more like the bottom electrode, the body electrode, and the shoulder electrode, and each electrode is made of a fluororesin sheet, polyimide film, or polyimide while securing the sealability by sandwiching a ring, for example. It may be electrically insulated with ether ether ketone (PEEK) film.
- PEEK ether ether ketone
- Spaces 40a and 40c are formed inside the external electrode 3, and these spaces are used to hold plastic containers 7a and 7c to be coated, for example, PET bottles, which are containers made of polyethylene terephthalate resin. Space.
- the accommodation spaces 40a and 40c in the external electrode 3 are formed so as to accommodate the plastic container 7 accommodated therein.
- the plastic container is formed to be slightly larger than the outer shape of the plastic container. That is, it is preferable that the inner wall surfaces of the container storage spaces 40a and 40c have a shape (similar shape) that surrounds the vicinity of the outside of the plastic containers 7a and 7c. This is because a uniform self-bias voltage is generated on the wall of the plastic container.
- the lid 4b is provided with openings that connect to the housing spaces 40a, 40c in the external electrode 3. Further, a space is provided inside the lid 4b, and this space is connected to the housing spaces 40a, 40c in the external electrode 3 via the opening.
- the storage spaces 40a and 40c are sealed from the outside by an O-ring 8 disposed between the upper external electrode 2 and the lower external electrode 1, and can be decompressed.
- the internal electrodes 9a and 9c are arranged so as to be able to be inserted into and removed from the external electrode 3, and are arranged inside the plastic containers 7a and 7c.
- the internal electrodes 9a and 9c are inserted into the housing spaces 40a and 40c in the external electrode 3 from the upper part of the lid 4b through the space in the lid 4b and the openings of the lid 4b and the insulating member 4a.
- the base ends of the internal electrodes 9a and 9c are arranged above the lid 4b.
- the tips of the internal electrodes 9a, 9c are located inside the plastic containers 7a, 7c, which are the accommodation spaces 40a, 40c of the external electrodes 3 and are accommodated in the external electrodes 3.
- Each of the internal electrodes 9a and 9c has a tubular shape whose inside is hollow. Gas outlets 49a, 49c are provided at the tips of the internal electrodes 9a, 9c. Further, the internal electrodes 9a and 9c are preferably grounded.
- the external electrode 3 is formed in a single columnar shape.
- the multiple integrated external electrode shown in FIG. 3 (a) is a single columnar external electrode, but may be any columnar body such as a prism or an elliptical column.
- a columnar structure composed of a single column formed by compounding a shape surrounding each container housing space with an approximately uniform thickness may be used.
- the external electrode 3 is preferably a cylinder or a prism having a square cross section to make the transmission distance of the high frequency equal.
- housing spaces 40a, 40b, 40c, and 40d for accommodating the plastic containers 7a, 7b, 7c, and 7d one by one are provided on one pillar that also serves as the external electrode 3.
- four plastic containers are accommodated for one external electrode by accommodating the plastic containers in each accommodation space.
- the central axis of each of the storage spaces 40a, 40b, 40c, 40d and the central axis ⁇ of the external electrode 3 are parallel.
- the accommodation spaces 40a, 40b, 40c, and 40d are arranged side by side on the same circumference S having the center axis ⁇ of the external electrode as the center point.
- External electrode As shown in Fig.
- the shape of the accommodation space in 3 is such that plastic containers 7a to 7d are placed on the circumference S of radius a from the center of the external electrode ⁇ 1.
- the accommodation spaces 40a, 40b, 40c, and 40d are preferably arranged at equal intervals on the same circumference S as shown in FIG.
- a plurality of accommodation spaces for accommodating each plastic container are provided in one columnar body also serving as an external electrode, and the central axis of each accommodation space is parallel to the central axis of the external electrode, and the center of the external electrode is External electrodes in which the accommodation spaces are arranged side by side on the same circumference centered on the axis are referred to as a plurality of integrated electrodes.
- the multiple-integrated external electrode of the present invention has the same function as a multiple-type external electrode in which a plurality of combinations of an external electrode that accommodates only one plastic container and a matching box are installed.
- the external electrodes are integrated so that a plurality of plastic containers can be accommodated within one external electrode, and one matching box is used for each integrated external electrode. Boxes can be reduced.
- the external electrode by making the external electrode a single columnar body, the distance from the high-frequency supply starting point to the inner wall of the housing space can be minimized, and since there is no deviation in the distance between each housing space. A uniform self-bias voltage can be applied to the wall of the plastic container.
- internal electrodes 9a to 9d are provided for one column-shaped external electrode 3 corresponding to the accommodation spaces 40a, 40b, 40c, and 40d, respectively.
- the internal electrodes are grounded, and piping is used to supply raw material gas to each container.
- the internal electrode also serves as a raw material supply pipe.
- the high-frequency output is introduced into the high-frequency output supply rod 30.
- External electrode 1 at the lower part of the container of external electrode 3 The intersection ⁇ 2 between the bottom surface of the outer electrode 1 at the bottom of the container and the central axis X is the high-frequency output supply point.
- a conductive cable or a conductive metal rod is used for the high-frequency output supply rod 30.
- the high frequency output supply pad connection connector 32 serves as a conductive contact when assembling the lower external electrode of the container and the upper external electrode of the container when taking the container in and out.
- the connection point ⁇ 2 is provided on the lower external electrode of the container
- the connection point is provided by distributing it to the lower electrode 1 of the container and distributed to four locations near the bottom of each plastic container, or It is also possible to connect inside the electrode and on the central axis X.
- the connection point can be changed within a range where uniform plasma can be generated in each plastic container.
- the case where four plastic containers are accommodated inside one external electrode has been described, but an external electrode capable of accommodating a plurality of plastic containers other than four is used. It can also take the form.
- the compactness of the device by reducing the number of high-frequency power supplies and matching boxes by adopting a multi-integrated external electrode structure, and the use of two or more lines in the rotary support Either or both productivity doublings can be realized.
- FIGS. Figs. 6 to 8 are conceptual diagrams showing the arrangement relationship between the rotating support, the external electrodes arranged on the rotating support, and the accommodation space provided for the external electrodes. is there.
- the external electrodes of the film forming chamber are shown as prismatic in the figure, the same applies to a cylindrical or elliptical column as long as the arrangement of the accommodation space with respect to the rotary support is the same.
- FIG. 6 (a) two housing spaces 40 are provided on one external electrode 3 and the housing spaces are arranged on the same circumference with the rotation axis of the rotary support 41 as the center point z. Deposition chambers are evenly spaced on the rotating support The case was shown. In this case, the containers are arranged in a single line up to the container supply line, the rotary type 1 device, and the line for removing the film-formed container.
- FIG. 6 (b) two housing spaces are provided under one external electrode 3, and when the film forming chamber is arranged on the rotary support 41, one of the housing spaces 40x is formed by each film forming chamber.
- the two rows are the number of rows in the circumferential direction as shown in FIG. 6 (b).
- one row is sufficient for the container supply line, but it is necessary to divide the line into two rows in front of the one-piece and one-type device and enter the storage space.
- Containers installed in a rotary type device in two rows can be maintained in two rows in the device, and film-formed containers taken out from the mouth-only device can be combined from two rows into one row. preferable.
- the accommodation spaces 40 are arranged in two rows in the circumferential direction of the circle s and adjacent to each other across the circle s.
- the housing spaces 40 may be arranged in two rows in the circumferential direction and offset from each other across the cycle s.
- three housing spaces are provided under one external electrode 3, and when the film forming chamber is disposed on the rotating support 41, the two housing spaces 40x and 40y are formed. It is arranged outside the circle s formed by the film forming chamber, and the remaining one accommodation space 40z is arranged inside the circle S and two of the film forming chambers arranged next to the film forming chamber one.
- the accommodating spaces 40a and 40b are arranged inside the circle s and the remaining one accommodating space 40c is arranged outside the circle s, so that the accommodating space of the external electrode 3 is formed around the circumference of the circle s. They may be arranged in two rows in the direction.
- FIG. 8 (a) when the film forming chambers are arranged on the rotary support 41, the accommodation spaces are arranged in two rows in the circumferential direction of the circle s and adjacent to each other across the circle s. However, the accommodation spaces may be arranged as shown in Fig. 8 (c). Further, as shown in FIG. 8 (b), two rows may be arranged in the circumferential direction and shifted from each other across the cycle s.
- film formation can be performed simultaneously on two plastic containers by one high-frequency power supply, so that the number of power supplies and the number of matching boxes can be reduced.
- the device shown in Fig. 6 (b) (c) (d), Fig. 7 or Fig. 8 (a) (b) (c) it is possible to complete at the same timing according to the rotation of the rotating support. It is possible to secure two or more film-forming chambers for advancing the film, reducing the number of power supplies and matching boxes, and doubling the productivity per unit time.
- the use of two rows does not unnecessarily complicate the container mounting mechanism and the container unloading mechanism. Therefore, the number of rows can be improved while improving productivity and preventing the container mounting mechanism and the container unloading mechanism from becoming complicated.
- the container according to the present invention includes a container used with a lid, a stopper, or a seal, or a container used in an open state without using them.
- the size of the opening is determined according to the contents.
- the plastic container includes a plastic container having a predetermined thickness having an appropriate rigidity and a plastic container formed of a sheet material having no rigidity. Also includes container lids. Examples of the filling of the plastic container according to the present invention include beverages such as carbonated beverages, fruit juice beverages, and soft drinks, as well as pharmaceuticals, agricultural chemicals, and dry foods that dislike moisture absorption. Includes both One-Aye containers and reusable containers.
- the resin used for molding the plastic container of the present invention is polyethylene terephthalate resin (PET) or polyethylene terephthalate copolyester resin (instead of ethylene glycol as the alcohol component of the polyester, a cyclohexene is used).
- PET polyethylene terephthalate resin
- polyethylene terephthalate copolyester resin instead of ethylene glycol as the alcohol component of the polyester, a cyclohexene is used.
- the copolymer using Sandimethanol is called PETG, manufactured by Eastman), polyethylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin (PP), cycloolefin copolymer resin (C ⁇ C, (Cyclic olefin copolymer), ionomer resin, poly-4-methylpentene-1 resin, polymethyl methacrylate resin, polystyrene resin, ethylene-vinyl alcohol copolymer resin, acrylonitrile resin, polyvinyl chloride resin, polyvinyl chloride Resin, polyamide resin, polyamide imide resin, polyacetal resin, polycarbonate resin, polysulfone resin, or tetrafluoroethylene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin. Examples can be given. Among them, PET is particularly preferred.
- a raw material gas introducing means 41 introduces a raw material gas supplied from a raw material gas source 20 into a plastic container 7. That is, one side of pipes 10 and 11 is connected to the base end of the internal electrode 9, and the other side of this pipe 11 is connected to one side of a mass flow controller 19 via a vacuum valve 16. It is connected to the. The other side of the mass flow controller 19 is connected to the source gas source 20 via piping. Have been.
- This source gas generating source 20 generates hydrocarbon gas such as acetylene.
- the source gas introducing means supplies the source gas to each film forming chamber.
- the source gas introducing means may be provided for each of the film forming chambers, but the source gas may be introduced to all the film forming chambers by one source gas generating source.
- a number of branch pipes may be provided between the source gas generating source and the mass flow controller according to the number of the film forming chambers.
- the same number of mass flow controllers as the number of film forming chambers are provided. In any case, it is only required that a predetermined amount of source gas can be supplied to each of the film forming chambers.
- a source gas for example, when a DLC film is formed, aliphatic or aromatic hydrocarbons, aromatic hydrocarbons, oxygen-containing hydrocarbons, nitrogen-containing hydrocarbons, etc., which are gaseous or liquid at room temperature, are used. You. Particularly, benzene having 6 or more carbon atoms, toluene, 0-xylene, m-xylene, p-xylene, cycle hexane and the like are desirable.
- aliphatic hydrocarbons especially ethylene hydrocarbons such as ethylene, propylene or butylene, or acetylenes such as acetylene, arylene or 1-butyne Hydrocarbons are preferred.
- ethylene hydrocarbons such as ethylene, propylene or butylene
- acetylenes such as acetylene, arylene or 1-butyne Hydrocarbons
- these raw materials may be used alone or may be used as a mixed gas of two or more kinds. Further, these gases may be diluted with a rare gas such as argon or helium for use.
- a silicon-containing DLC film is formed, a hydrocarbon gas containing Si is used.
- the DLC film referred to in the present invention is a film called i-carbon film or hydrogenated amorphous carbon film (a-C: H), and includes a hard carbon film.
- the DLC film is an amorphous carbon film and has SP 3 bonds.
- a hydrocarbon-based gas for example, acetylene gas, is used as a source gas for forming the DLC film, and a Si-containing hydrocarbon-based gas is used as a source gas for forming the Si-containing DLC film.
- the space inside the conductive member 4b is connected to one side of a pipe 13 and the other side of the pipe 13 is connected to a vacuum pump 21 via a vacuum valve 18.
- This vacuum pump 21 is connected to an exhaust duct 29. Since there are a plurality of film forming chambers, the exhaust system may be integrated into one vacuum pump to perform exhaust, or the exhaust may be shared by a plurality of vacuum pumps.
- the container mounting means (not shown) of the plastic container includes, for example, lowering the lower external electrode 1 with respect to the upper external electrode 2 to accommodate the container, opening the lower external electrode 1, and placing the plastic container on the lower external electrode 1, Further, by lowering the lower external electrode 1, a seal is provided by a ring interposed between the lower external electrode 1 and the upper external electrode 2.
- the uncoated plastic container is, for example, separately taken out of the conveyor, placed on the lower external electrode 1, and supplied by a container mounting handling device (not shown).
- the gas adjusting means before film formation replaces the inside of the plastic container with the material gas and adjusts the film forming pressure to a predetermined value, so that the material gas introducing means and the exhaust of the vacuum pump cooperate.
- the CVD film forming means is a means for forming a CVD film on the inner surface of the plastic container.
- the high frequency supply means, the raw material gas introducing means, and the exhaust means cooperate.
- the exhaust means includes a vacuum valve 18, a vacuum pump 21, and an exhaust duct 29.
- the gas adjusting means after film formation is a means for removing the remaining source gas in the film forming chamber and the plastic container, and for releasing the inside of the plastic container to atmospheric pressure after the film formation. Is to cooperate.
- the container removing means removes the container from the accommodation space in the film forming chamber.
- the lower external electrode 1 is lowered and opened with respect to the upper external electrode 2 to remove the container, and the coated plastic container placed on the lower external electrode 1 is removed. It is a means to move on a conveyor.
- the coated container is placed on a conveyor, for example, by a container unloading handling device (not shown) that unloads the container from the storage space in the film forming chamber, and is unloaded.
- the high-frequency supply means consists of a fixed matching box provided for each external electrode (indicated as MB in the figure), one or more high-frequency power supplies 15, and one for each high-frequency power supply 15.
- Automatic matching box (automatic matching box) 14 At this time, one high-frequency power supply may be provided for one film-forming chamber, or high-frequency power supply means may be provided to divide the high-frequency power supplied from the high-frequency power supply into a plurality of pieces before the fixed matching device.
- the high frequency power may be supplied from a single high frequency power supply to a plurality of external electrodes.
- switching may be performed by a high frequency relay so that a high frequency is sequentially supplied to the chamber that has been rotated to a predetermined position corresponding to the rotation position of the rotary type rotary support (evening table). .
- high frequency can be supplied to the external electrode of each film forming chamber.
- the fixed matching device is provided for each of the external electrodes, and performs impedance matching between the high frequency supplied by the coaxial cable and the plasma generated in the external electrode.
- the external electrodes of the fixed matching box are connected by copper plate wiring. Since the fixed matching box has a large automatic matching box with respect to the chamber, the fixed matching box is provided separately for each external electrode. However, there is no need to install them. Also, when the automatic matching unit is placed separately from the first chamber, the power is May be supplied. In this case, the fixed matching box can be omitted.
- the high-frequency power supply generates high-frequency power, which is the energy for converting raw material gas into plasma in the plastic container.
- high-frequency power is the energy for converting raw material gas into plasma in the plastic container.
- a transistor-type high-frequency power supply and a high-frequency power supply capable of performing a frequency-matching or electronic matching.
- the frequency of the high-frequency power supply is 100 kHz to 100 MHz, but for example, an industrial frequency of 13.56 MHz is used.
- Wiring from the automatic matching unit to the fixed matching unit is connected by a coaxial cable.
- the coaxial cable has, for example, a characteristic impedance of 50 ⁇ .
- the automatic matching device adjusts the impedance fluctuation on the coaxial cable.
- the high-frequency distribution means is provided when the high-frequency power supplied from the high-frequency power supply is distributed to a plurality of parts before the fixed matching box, and the high-frequency power is supplied from one high-frequency power supply to a plurality of external electrodes.
- the high frequency distribution means is composed of a distribution circuit for simultaneously and uniformly distributing high frequencies, and a switching switch for switching on / off each distribution output of the distribution circuit.
- the distribution circuit is, for example, a parallel type circuit, that is, a circuit including a coil, a resistor, and a capacitor, and distributes one input to a plurality of outputs, as shown in FIG.
- a cascaded circuit may be used.
- the switching switch is, for example, a high-frequency relay for turning on / off the output of the distribution circuit.
- the high-frequency distribution means is provided when switching is performed by a high-frequency relay so that high-frequency is supplied to chambers that have been rotated to predetermined positions corresponding to the rotational position of a rotary-type rotary support (turntable). .
- switching is performed sequentially using a high-frequency relay without using a distribution circuit. Note that distribution and switching may be combined.
- the external electrodes can be turned on / off independently of each other.
- a method for forming a DLC film inside a container using the rotary type CVD film continuous film forming apparatus of the present invention will be described. First, the manufacturing cycle will be described, and a method for forming a DLC film will be described.
- the inside of the film forming chamber 1 is opened to the atmosphere by opening the vacuum valve 17, and the lower external electrode 1 of the external electrode 3 is detached from the upper external electrode 2.
- An uncoated plastic container (undeposited film container in Fig. 1) in a com- parator (not shown) is extracted from the com- parator by a container mounting hand- ling device (not shown), placed on the lower external electrode 1, and placed on the upper external electrode 2. Insert the plastic container ⁇ into the storage space 40 by raising it toward. At this time, the internal electrode 9 is inserted into the plastic container 7, and the external electrode 3 is sealed by the o-ring 8.
- the film forming chamber 16 in FIG. 2 is a conceptual diagram of the AA ′ vertical cross section in FIG. 3 (a), and four accommodating spaces 40a, 40b, 40c, and 40d, and plastic containers 7a and 7b. , 7c and 7d and the internal electrodes 9a, 9b, 9c and 9d, but for convenience, they are referred to as the housing space 40, the plastic container 7 and the internal electrode 9 (the same applies hereinafter).
- the vacuum valve 16 is opened, a hydrocarbon gas is generated at the source gas source 20, this hydrocarbon gas is introduced into the pipe 22, and the flow rate is controlled by the mass flow controller 19. Gas outlet through piping 11, 10 and internal electrode 9 at earth potential 4 Blow out from 9. Thereby, the hydrocarbon gas is introduced into the plastic container 7.
- the pressure in the decompression chamber of the film forming chamber 16 and the inside of the plastic container 7 are adjusted to a pressure suitable for DLC film formation (for example, 6.6 to 665) by a balance between the controlled gas flow rate and the exhaust capacity. (Pa, 0.05 to 5.0 Torr).
- a high-frequency output of, for example, 50 to 200 W is supplied to the external electrode 3 to convert the source gas into plasma in the plastic container 7 to form a DLC film on the inner surface of the plastic container 7.
- the RF output (for example, 13.56 MHz) is supplied to the film forming chamber 16 in the CVD film forming step by the high frequency supply means.
- a voltage is generated between the external electrode 3 and the internal electrode 9.
- the automatic matching device adjusts the impedance by the inductance L and the capacitance C so that the reflected wave from the entire electrode supplying the output is minimized.
- the fixed matching box converts the impedance of the coaxial cable into the impedance of the plasma.
- hydrocarbon-based plasma is generated in the plastic container 7, and a DLC film is formed on the inner surface of the plastic container 7.
- the distance between the high-frequency supply starting point and the inner wall of the housing space is minimized by using a single columnar body for the external electrodes, and the distance between each housing space is not uneven.
- a uniform self-bias voltage can be applied to the container wall.
- the film forming time is as short as several seconds.
- the RF output from the high frequency supply unit is stopped, the plasma is extinguished, and the deposition of the DLC film is completed.
- the vacuum valve 16 is closed to stop supplying the source gas.
- a DLC film is simultaneously formed on the inner surfaces of a plurality of plastic containers in the same film forming chamber.
- the vacuum valve 18 is opened, and the decompression chamber of the deposition chamber 16 and the plastic container 7 are opened.
- the hydrocarbon gas inside is evacuated by the vacuum pump 21.
- the pressure in the film forming chamber 6 is 6.6 to 665 Pa (0.05 to 5.00 Tori ').
- the vacuum valve 17 is opened.
- the container removal process for removing the coated container will be described.
- the lower external electrode 1 of the external electrode 3 is detached from the upper external electrode 2.
- the plastic container 7 accommodated in the accommodation space in the upper external electrode 2 is taken out from the lower side of the upper external electrode 2 by a container take-out handling device (not shown).
- the coated container film-formed container in Fig. 1 is placed on a conveyor (not shown) and transported.
- the high-frequency distribution means advances the CVD film forming process for some of the film forming chambers on the rotating support, and simultaneously advances a plurality of manufacturing cycles for each film forming chamber at a fixed interval.
- the system is preferred. For example, it is a method of proceeding in the evening shown in FIG. 11 or FIG. Fig. 11 shows the case where there are 32 film forming chambers, which are supplied with high frequency by two high frequency power supplies (A and B).
- FIG. 12 shows a case where there are 32 film forming chambers and this is supplied with high frequency by four high frequency power supplies (,: 8, 0 and 0). Further, as shown in FIG. 13 or FIG.
- a unit may be formed by grouping several film forming chambers, and the manufacturing cycle may be shifted at regular intervals.
- Fig. 13 shows the case where there are 32 film forming chambers and this is supplied with high frequency by two high frequency power supplies (A and B).
- Fig. 14 shows the case where there are 32 film forming chambers, which are supplied with high frequency by four high frequency power supplies (A, B, C and D).
- the numbers 1 to 32 in the figure are the numbers when the film forming chambers on the rotating support are numbered in order.
- the predetermined position of the rotating support is set to 0 °, and the 0 ° is set as a reference. The rotation angle was set on the horizontal axis of the figure.
- each accommodation space and each film forming chamber When supplying a high frequency at the same time, it is preferable to supply a uniform high frequency in each accommodation space and each film forming chamber.
- the plurality of film forming chambers arranged on the rotating support as shown in FIG. 1 are sequentially rotated according to the rotation angle of the rotating support while the rotating support makes one rotation at a constant speed.
- DLC film-coated plastic containers are mass-produced.
- the number of components such as the number of film forming chambers and the number of high-frequency power supplies may be changed as appropriate according to the required capacity of the apparatus.
- a PET bottle for beverages is used as a container for forming a thin film therein, but a container used for other purposes can be used.
- the DLC film or the Si-containing DLC film is used as a thin film to be formed by the CVD film forming apparatus.
- the above film forming apparatus is used. Is also possible.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/516,732 US7603962B2 (en) | 2002-06-24 | 2003-06-19 | Rotary type CVD film forming apparatus for mass production |
EP03760909A EP1516941B1 (en) | 2002-06-24 | 2003-06-19 | Rotary type mass-producing cvd film forming device and metod of forming cvd film on surface in plastic conteiner |
AU2003244311A AU2003244311A1 (en) | 2002-06-24 | 2003-06-19 | Rotary type mass-producing cvd film forming device and metod of forming cvd film on surface in plastic conteiner |
KR1020047020694A KR101089535B1 (ko) | 2002-06-24 | 2003-06-19 | 대량 생산용 로터리형 cvd 막형성 장치 및 플라스틱 용기 내부 표면상의 cvd 막형성 방법 |
AT03760909T ATE546564T1 (de) | 2002-06-24 | 2003-06-19 | Cvd-filmherstellungsvorrichtung vom rotationstyp für die massenproduktion und verfahren zur herstellung von cvd-film auf der oberfläche in einem kunststoffbehälter |
HK06100078.9A HK1080121B (zh) | 2002-06-24 | 2006-01-04 | 旋轉型的批量生產用cvd成膜裝置和在塑料容器的內表面形成cvd膜的成膜方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002-183309 | 2002-06-24 | ||
JP2002183309A JP4149748B2 (ja) | 2002-06-24 | 2002-06-24 | ロータリー型量産用cvd成膜装置及びプラスチック容器内表面へのcvd膜成膜方法 |
Publications (1)
Publication Number | Publication Date |
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WO2004001095A1 true WO2004001095A1 (ja) | 2003-12-31 |
Family
ID=29996676
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2003/007797 WO2004001095A1 (ja) | 2002-06-24 | 2003-06-19 | ロータリー型量産用cvd成膜装置及びプラスチック容器内表面へのcvd膜成膜方法 |
Country Status (9)
Country | Link |
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US (1) | US7603962B2 (ja) |
EP (1) | EP1516941B1 (ja) |
JP (1) | JP4149748B2 (ja) |
KR (1) | KR101089535B1 (ja) |
CN (1) | CN100350072C (ja) |
AT (1) | ATE546564T1 (ja) |
AU (1) | AU2003244311A1 (ja) |
HK (1) | HK1080121B (ja) |
WO (1) | WO2004001095A1 (ja) |
Cited By (2)
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DE102009001343A1 (de) | 2009-03-05 | 2010-09-09 | Coiffeur Consulting Team Cosmetics Gmbh | Kosmetisches Haarstimulierungs-Set und Verfahren zur Stimulierung des Haarwachstums |
EP3461848A1 (en) | 2014-10-22 | 2019-04-03 | Crescendo Biologics Limited | Transgenic mice |
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WO2000071780A1 (fr) * | 1999-05-19 | 2000-11-30 | Mitsubishi Shoji Plastics Corporation | Film dlc, contenant en plastique recouvert de dlc, et procede et appareil de fabrication de contenant en plastique recouvert de dlc |
CN100335376C (zh) * | 2002-04-26 | 2007-09-05 | 北海制罐株式会社 | 内表面经涂覆的塑料容器及其制造方法 |
JP4604541B2 (ja) * | 2004-04-16 | 2011-01-05 | 凸版印刷株式会社 | 成膜装置及び成膜方法 |
FR2889204B1 (fr) * | 2005-07-26 | 2007-11-30 | Sidel Sas | Appareil pour le depot pecvd d'une couche barriere interne sur un recipient, comprenant une ligne de gaz isolee par electrovanne |
JP4611170B2 (ja) * | 2005-10-19 | 2011-01-12 | 三菱重工業株式会社 | バリヤ膜形成装置 |
FR2907037B1 (fr) * | 2006-10-13 | 2009-01-09 | Sidel Participations | Installation de depot,au moyen d'un plasma micro-ondes,d'un revetement barriere interne dans des recipients thermoplastiques |
FR2907351B1 (fr) * | 2006-10-18 | 2009-02-06 | Sidel Participations | Machine de traitement de recipients par plasma,comprenant des circuits de depressurisation et de pressurisation decales |
FR2929295A1 (fr) * | 2008-03-25 | 2009-10-02 | Becton Dickinson France Soc Pa | Appareil pour le traitement par plasma de corps creux |
DE102010023119A1 (de) * | 2010-06-07 | 2011-12-22 | Khs Corpoplast Gmbh | Vorrichtung zur Plasmabehandlung von Werkstücken |
JP5603201B2 (ja) * | 2010-10-27 | 2014-10-08 | サントリーホールディングス株式会社 | 樹脂製容器の表面改質方法および樹脂製容器の表面改質装置 |
DE102012204690A1 (de) * | 2012-03-23 | 2013-09-26 | Krones Ag | Vorrichtung zum Plasmabeschichten von Füllgutbehältern, wie Flaschen |
JP6093552B2 (ja) * | 2012-11-08 | 2017-03-08 | 日精エー・エス・ビー機械株式会社 | 樹脂容器用コーティング装置 |
WO2014103677A1 (ja) * | 2012-12-26 | 2014-07-03 | 麒麟麦酒株式会社 | 薄膜の成膜装置 |
WO2014112533A1 (ja) * | 2013-01-18 | 2014-07-24 | 日精エー・エス・ビー機械株式会社 | 樹脂容器用コーティング装置および樹脂容器製造システム |
CN105228330B (zh) * | 2015-09-01 | 2018-09-14 | 沈阳拓荆科技有限公司 | 一种射频等离子体设备匹配器 |
CA3189169A1 (en) * | 2020-08-12 | 2022-02-17 | Ahmad TAHA | Pulsed plasma enhanced chemical vapor deposition process, system and coated vessels |
DE102021120056A1 (de) * | 2021-08-02 | 2023-02-02 | Khs Gmbh | Verfahren zum Beschichten von Behältern aus Kunststoff |
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- 2003-06-19 AU AU2003244311A patent/AU2003244311A1/en not_active Abandoned
- 2003-06-19 CN CNB038148919A patent/CN100350072C/zh not_active Expired - Fee Related
- 2003-06-19 AT AT03760909T patent/ATE546564T1/de active
- 2003-06-19 KR KR1020047020694A patent/KR101089535B1/ko active IP Right Grant
- 2003-06-19 US US10/516,732 patent/US7603962B2/en not_active Expired - Fee Related
- 2003-06-19 EP EP03760909A patent/EP1516941B1/en not_active Expired - Lifetime
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EP3461848A1 (en) | 2014-10-22 | 2019-04-03 | Crescendo Biologics Limited | Transgenic mice |
Also Published As
Publication number | Publication date |
---|---|
US20050155553A1 (en) | 2005-07-21 |
CN100350072C (zh) | 2007-11-21 |
AU2003244311A8 (en) | 2004-01-06 |
HK1080121A1 (en) | 2006-04-21 |
CN1662675A (zh) | 2005-08-31 |
EP1516941B1 (en) | 2012-02-22 |
KR20050023316A (ko) | 2005-03-09 |
HK1080121B (zh) | 2008-03-28 |
AU2003244311A1 (en) | 2004-01-06 |
EP1516941A4 (en) | 2009-01-07 |
KR101089535B1 (ko) | 2011-12-05 |
JP4149748B2 (ja) | 2008-09-17 |
US7603962B2 (en) | 2009-10-20 |
EP1516941A1 (en) | 2005-03-23 |
JP2004027271A (ja) | 2004-01-29 |
ATE546564T1 (de) | 2012-03-15 |
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