Classifications

• • 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
  • C23C16/507—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 using external electrodes, e.g. in tunnel type reactors
• • 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
• • 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
  • C23C16/4412—Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
• • 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

Definitions

• the present invention relates to a coating film forming apparatus for an inner surface of a container and a method for manufacturing an inner surface coating film container.
• Plastic containers such as plastic bottles, are used to prevent the permeation of oxygen from the outside.
• Barrier film on its inner surface for example DLC (Diamond
• Patent Document 1 Attempts have been made to form carbon films such as “Like Carbon” (Patent Document 1).
• FIG. 7 of Patent Document 2 shows an external electrode having a size that surrounds a plastic container that is an object to be processed, and at least a mouth portion and a container of the plastic container when the plastic container is inserted.
• the medium electrode is inserted into the plastic container in the external electrode from the exhaust pipe side and connected to the ground side, exhaust means attached to the exhaust pipe, and medium gas is supplied to the internal electrode
• An apparatus for forming a carbon film on the inner surface of a plastic container includes a gas supply means for the purpose and a high-frequency power source connected to the external electrode.
• a PET bottle is inserted into the external electrode.
• the internal electrode provided with a gas blowing part also having an insulating material force is connected to the end face of the external electrode on the side where the mouth part of the PET bottle is located via an insulating member, and the inside of the PET bottle.
• the gas blowing part is inserted so that it is located on the bottom side of the PET bottle.
• the medium gas is supplied to the internal electrode by the gas supply means, and the gas blowing force of the internal electrode is blown out into the plastic bottle.
• the discharge region may extend not only around the internal electrode but also in the exhaust pipe (including the branch exhaust pipe communicating with it).
• Patent Document 1 Japanese Patent Laid-Open No. 8-53116
• Patent Document 2 Japanese Patent Laid-Open No. 2003-286571
• the present inventors have a configuration in which a plurality of film forming chambers for forming a barrier film on the inner surface of a plastic container which is an object to be processed are communicated with a rotary vacuum seal mechanism through an exhaust pipe made of a conductive material.
• a noble film forming device on the inner surface of a plastic container and a method for forming a noro film such as a carbon film on the inner surface of the plastic container using this noir film forming device, the discharge region was formed into a film forming chamber.
• a large plasma sheath voltage is applied between the external electrode, the deposition chamber, and the ground electrode including the exhaust pipe, and a barrier such as a medium gas dissociated in the plasma is generated.
• a barrier such as a medium gas dissociated in the plasma.
• high-energy positive ions from the polymer film-forming gas can be incident on the inner surface of the plastic container, and that a nano film such as a carbon film with good film quality can be formed on the inner surface of the plastic container at high speed.
• extending the discharge region from the film formation channel to the exhaust pipe has the problem of inducing unstable discharge and abnormal power supply due to the rotary vacuum seal mechanism as explained in the background art.
• the present invention regulates the discharge region generated in the exhaust pipe to reach the rotary vacuum seal mechanism, and can prevent unstable discharge and induction of power supply abnormality.
• An object of the present invention is to provide a coating film forming apparatus and a method for producing an inner surface coating film container.
• the present inventors have further studied, and as a result, by arranging an electric field shielding member having air permeability and conductivity at a desired position inside the exhaust pipe, which is a conductive material force.
• the present inventors have discovered that the discharge region generated in the exhaust pipe reaches the rotary vacuum seal mechanism to prevent discharge instability and power supply abnormal induction.
• the inventors configured the exhaust pipe from a pipe part made of a conductive material and a pipe part made of an insulating material.
• the tube side which is the conductive material cover
• the discharge region generated in the exhaust tube is similarly restricted from reaching the rotary vacuum seal mechanism, causing unstable discharge and abnormal power supply.
• the present invention has been discovered by investigating that it is possible to prevent the triggering of the above.
• a coating film forming apparatus and an inner surface coating film container manufacturing method for an inner surface of a container according to the present invention based on such knowledge are characterized by having the following configuration.
• a first invention is a rotary vacuum seal mechanism, and is connected to the rotary vacuum seal mechanism through an exhaust pipe to form a coating film on the inner surface of a container to be processed by plasma discharge.
• a plurality of film forming chambers, wherein the exhaust pipe is made of a conductive material, and an electric field shielding member having air permeability and conductivity is disposed inside a desired distance from the film forming chamber. It is in the coating film formation apparatus to the container inner surface characterized.
• the second invention is a rotary vacuum seal mechanism, and is communicated with the rotary vacuum seal mechanism through an exhaust pipe to form a coating film on the inner surface of a container to be processed by plasma discharge.
• a plurality of film forming chambers wherein the exhaust pipe is made of a conductive material, and an air-permeable and conductive electric field shielding member is disposed inside a desired distance away from the film forming chamber,
• the electric field shielding member is in the coating film forming apparatus on the inner surface of the container, which has a honeycomb structure or a mesh shape.
• a third invention is the first or second invention, wherein the film forming chamber includes an external electrode having a cavity that surrounds the container when the container is inserted, and a mouth of the container.
• a conductive chamber header member attached to an end face of the external electrode on the side to be positioned through an insulating member, to which the exhaust pipe is connected and grounded, and the chamber header member in the container in the external electrode
• a gas blowing member that is inserted from the side and blows out the coating film forming gas, and an electric field applying unit that applies an electric field between the external electrode and the chamber header member and the exhaust pipe that are grounded. It is in the coating film forming device on the inner surface of the container.
• a fourth invention is the invention according to the first or second invention, wherein the film forming chamber comprises an external electrode having a cavity that surrounds the container when the container is inserted, and a mouth of the container.
• a conductive chamber header member attached to an end face of the external electrode on the side to be positioned through an insulating member, to which the exhaust pipe is connected and grounded, and the chamber header member in the container in the external electrode
• a gas blowing member inserted from the side for blowing out the coating film forming gas, and an electric field applying means for applying an electric field between the external electrode and the grounded chamber header member and the exhaust pipe, and
• a spacer made of an dielectric material is interposed at least between the mouth and shoulder of the container and the external electrode when the container is inserted.
• a fifth invention is the coating film forming apparatus on the inner surface of the container according to the first or second invention, wherein the container is a plastic container.
• the coating gas generated from the gas blowing member is blown into the container, and the chamber header member and the exhaust pipe including the container are set to a predetermined gas pressure.
• D including the external electrode, the chamber header member, and the exhaust pipe portion positioned on the chamber header member from the position of the electric field shielding member by the electric field applying means. An electric field is applied to the ground electrode, plasma is generated in the chamber header member and the exhaust pipe portion including the inside of the container, and the coating film forming gas is dissociated by the plasma to form a coating film on the inner surface of the container. And forming the inner coating film container.
• the seventh invention is as follows. A step of inserting into each external electrode; and (b) a conductive chamber header member attached to the end face of the external electrode on the side where the mouth of the container is located via an insulating member. A step of inserting the inside of the container, and (c) a rotary vacuum seal mechanism is provided with a gas-permeable and conductive electric field shielding member inside and outside the container and at a desired position inside the chamber header member inside the container.
• the gas blowing member and the coating film forming gas are blown into the container, and the chamber header member and the exhaust pipe including the inside of the container are set at a predetermined gas pressure.
• a spacer made of a dielectric material is interposed between the outer electrode and the outer electrode.
• An eighth invention is a rotary vacuum sealing mechanism, and a plurality of the vacuum vacuum sealing mechanism communicated with the rotary vacuum sealing mechanism through an exhaust pipe to form a coating film on the inner surface of a container to be processed.
• the exhaust pipe is composed of a conductive tube portion made of a conductive material and an insulating tube portion also having an insulating material power, and the conductive tube portion is connected to each of the film formation chambers.
• a ninth invention is a rotary vacuum seal mechanism, and is connected to the rotary vacuum seal mechanism through an exhaust pipe to form a coating film on the inner surface of a plastic container as an object to be processed.
• a plurality of film forming chambers, and the exhaust pipe is composed of a conductive tube portion made of a conductive material and an insulating tube portion also having an insulating material force, and the conductive tube portion is connected to each of the film forming chambers.
• the film forming chamber includes an external electrode having a cavity that surrounds the container when the container is inserted, and an end surface of the external electrode on the side where the mouth of the container is located via an insulating member.
• a conductive chamber header member which is attached and connected to the exhaust pipe and grounded, and the chamber header member side cover are inserted into the container in the external electrode, and the coating film forming gas is blown out.
• an electric field applying means for applying an electric field between the external electrode and the chamber header member and the exhaust pipe that are grounded.
• the spacer having a dielectric material force is interposed between at least the mouth and shoulder of the container and the external electrode when the container is inserted.
• An apparatus for forming a coating film on the inner surface of a container is characterized in that it is present.
• the chamber header including the inside of the plastic container by blowing out the gas blowing member force coating film forming gas into the container while exhausting through the exhaust pipe constituted by the pipe portion comprising the pipe portion and the insulating material force.
• the method of manufacturing an inner coating film container is characterized by the above.
• the gas blowing member force mentioned above is blown out into the container while exhausting through the exhaust pipe constituted by the chamber header member including the inside of the plastic container and the inside of the exhaust pipe.
• An inner coating film container characterized by interposing a spacer made of a dielectric material between at least the mouth and shoulder of the container and the outer electrode when inserted into the outer electrode. It is in the manufacturing method.
• a thirteenth invention comprises a film forming chamber for forming a coating film by plasma discharge on the inner surface of a container which is an object to be processed, and the film forming chamber is provided when the container is inserted. And an external electrode having a cavity of a size surrounding the container and an end face of the external electrode on the side where the mouth of the container is located via an insulating member, and the exhaust pipe is connected and grounded.
• an electric field applying means for applying an electric field between the chamber header member and the exhaust pipe.
• the exhaust pipe is made of a conductive material, and is air permeable and conductive inside a desired distance from the film forming chamber. If the area of the inner surface of the external electrode in which the container is accommodated is Sl and the area of the ground electrode is S2, the area ratio (S2ZS1) is 1 or less.
• An apparatus for producing an inner coating film container characterized by comprising the above.
• the present invention instability of discharge due to the relationship with the rotary vacuum seal mechanism and induction of power supply abnormality can be prevented, and a plurality of film forming chambers communicated with the rotary vacuum seal mechanism through the exhaust pipe.
• the apparatus for forming a NORA film on the inner surface of the plastic container capable of forming a NORA film such as a carbon film having a good film quality on the inner surface of the plastic container at a high speed can be provided.
• instability of discharge and induction of power supply abnormality can be prevented in relation to the rotary vacuum seal mechanism, and in a plurality of film forming chambers communicated with the rotary vacuum seal mechanism through an exhaust pipe.
• FIG. 1 is a plan view showing an apparatus for forming a coating film on the inner surface of a container according to a first embodiment of the present invention.
• FIG. 2 is a cross-sectional view of the main part including the film forming chamber of FIG.
• FIG. 3 is a cross-sectional view of a relevant part showing a coating film forming apparatus of another form according to the first embodiment of the present invention.
• FIG. 4 shows a coating film forming apparatus of still another embodiment according to the first embodiment of the present invention. It is principal part sectional drawing which shows a device.
• FIG. 5 is a characteristic diagram showing gas nozzle properties in Example 1 and Comparative Example 1 of the present invention.
• FIG. 6 is a cross-sectional view of a principal part showing a coating film forming apparatus according to a second embodiment of the present invention.
• baffle electric field shielding member with air permeability and conductivity
• FIG. 1 is a plan view showing the coating film forming apparatus according to the first embodiment
• FIG. 2 is a cross-sectional view of the main part including the film forming chamber of FIG.
• the rotary vacuum seal mechanism 1 of the coating film forming apparatus is a fixed platen ( For example, a rotating disk 2 that rotates in a counterclockwise direction is provided. A plurality of exhaust pipes 11 arranged radially are connected to the outer peripheral side surface of the rotating disk 2, and a film forming chamber 21 is connected to the tip of the exhaust pipe 11.
• the rotary plate 2 has a number of exhaust holes corresponding to the number of the exhaust pipes 11, and one end of the exhaust holes communicates with the exhaust pipe 11 and the other end.
• PET bottle B a container
• PET bottle B a PET bottle
• the plastic bottle B formed with the barrier film as the coating film is taken out at the point F in FIG. I have to.
• the vacuum degree in the film forming chamber 21 is gradually increased from a low vacuum to a high vacuum in four zones from the point S to the position of forming the NORA film before the point F. The degree of vacuum suitable for film formation is reached.
• FIG. 2 shows a schematic configuration of the film forming chamber 21.
• the film forming chamber 21 includes a cylindrical support member 24 having a conductive material force having flanges 23a and 23b on upper and lower ends provided on an annular base 22, and a chamber head member 32 is provided. Is suspended from the upper end flange 23a.
• An external electrode body 25 made of a cylindrical conductive material is disposed in the support member 24.
• An external electrode bottom member 26 having a disk-like conductive material force is detachably attached to the bottom of the external electrode body 25.
• Plastic container in which a barrier film (for example, a carbon film) is formed by the external electrode body 25 and the external electrode bottom member 26 has a space of a size capable of installing a bottomed cylindrical external electrode. 27 is configured. Further, the disk-shaped insulator 28 is disposed between the base 22 and the external electrode bottom member 26.
• the external electrode bottom member 26, the disk-shaped insulator 28, and the base 22 are integrally moved up and down with respect to the external electrode body 25 by a pusher (not shown), Open and close the bottom of the main electrode body 25.
• a pusher not shown
• the base 22, the insulator 28, and the external electrode bottom member 26 may be removed in this order, but when they are closed, the external electrode bottom member 26 the insulator 28 and Even if it is built in the order of the base.
• the columnar spacer 30 has a hollow portion 29 having a shape combining a cylinder and a truncated cone corresponding to the mouth and shoulder of the plastic bottle B inserted therein, and is a dielectric material. They are organized.
• the columnar spacer 30 is inserted in the upper part of the main body 25.
• the spacer 30 is fixed by a screw (not shown) to which an annular insulating member, which will be described later, placed on the spacer 30 is screwed.
• the annular insulating member 31 is placed on the upper surface of the external electrode 27 so that the upper surface of the annular insulating member 31 is flush with the upper flange 23a of the cylindrical support member 24.
• the hollow portion of the annular insulating member 31 has the same diameter as the hollow portion 29 with which the mouth portion of the pet bottle B at the upper end of the spacer 30 abuts.
• the cylindrical spacer 30 is inserted into the upper portion of the main body 25 in the external electrode 27, and the annular insulating member 31 is fixed to the upper surface of the spacer 30 and the external electrode 27. ing.
• the upper end of the mouth of the plastic bottle B is placed in the hollow portion of the annular insulating member 31 and the mouth and shoulder of the plastic bottle B.
• the portion is accommodated in the hollow portion 29 of the spacer 30, and the other PET bottle B portion is accommodated in the external electrode 27, respectively.
• Examples of the dielectric material constituting the cylindrical spacer 30 include plastics or ceramics having a relative dielectric constant of 1.5 to 20.
• plastics can be used, especially high-frequency loss (for example, tan 0 is 20 X 10-4 or less) and excellent heat resistance fluorinated resin such as polytetrafluoroethylene Is preferred.
• high frequency loss is low (for example, tan ⁇ is 20 X 10-4 or less), alumina, steatite or mechanical strength is high, and Macor is preferred! /.
• the chamber head member 32 constituting the film forming chamber 21 will be described.
• the rectangular block-shaped chamber head member 32 having a conductive material force is connected to the side surface thereof so that the exhaust pipe 11 communicates with the discharge chamber 33.
• the above-described cylindrical support member 24 is connected to the upper flange. It hangs down through 23a, is located on the upper surface side of the annular insulating member 31, and is grounded.
• the chamber head member 32 is formed with a discharge chamber 33 having a substantially L-shaped cross section over the side surface (left side surface in FIG. 2).
• the discharge chamber 33 communicates with the hollow portion of the annular insulating member 31 (the mouth portion when the plastic bottle B is inserted) on the bottom side thereof.
• a gas supply pipe 34 that is a gas blowing member passes through the chamber head member 32 and is inserted in the vicinity of the bottom of the plastic bottle B in the external electrode body 25 of the external electrode 27.
• the gas supply pipe 34 may be made of a conductive material such as a metal such as aluminum or stainless steel, or may be manufactured of an insulating material such as a ceramic such as alumina. However, since the gas supply pipe 34 penetrates the grounded chamber head member 32, when the conductive material force is also produced, it is grounded together with the chamber head member 32.
• the matching unit 38 is interposed in the cable 36 between the high-frequency power source 35 and the power supply terminal 37.
• the exhaust pipe 11 is made of a conductive material such as a metal such as stainless steel, and is grounded by being connected to the chamber head member 32.
• the Her-cam type conductor 39 which is a breathable and conductive electric field shielding member according to the present invention is disposed at a desired position in the exhaust pipe 11.
• the her cam-shaped conductor 39 By installing the her cam-shaped conductor 39 at a desired position, the discharge region generated in the exhaust pipe 11 can be restricted by the honeycomb-shaped conductor 39 and can be prevented from reaching the rotary vacuum seal mechanism 1. . As a result, discharge instability and power supply abnormality can be prevented.
• S1 is the area of the inner surface of the external electrode 27 in which the plastic container is accommodated
• S2 is the area of the ground electrode, that is, the inner surface of the discharge chamber 33 of the chamber head member 32 and the no-cam type This is the total area of the inner surface of the exhaust pipe 11 from the conductor 39 to the chamber head member 32.
• the gas supply pipe 34 is made of a conductive material, it functions as a ground electrode. Therefore, the outer peripheral area of the gas supply pipe 34 located in the chamber head member 32 and the external electrode 27 is also added as S2. Is done.
• the base 22 of the film forming chamber 21, the external electrode bottom member 26 and the disk-shaped insulator 28 are integrated with a pusher (not shown) to open the bottom of the external electrode body 25. Subsequently, the mouth side force of the pet bottle B is also inserted from the opened bottom side of the opened external electrode body 25. Thereafter, the external electrode bottom member 26, the disk-shaped insulator 28 and the base 22 are integrally closed in this order on the bottom side of the external electrode body 25 by a pusher (not shown). Accordingly, as shown in FIG.
• the upper end of the mouth of the plastic bottle B is placed in the hollow portion of the annular insulating member 31, and the mouth and shoulder of the plastic bottle B are placed in the hollow portion 29 of the spacer 30.
• the other PET bottles B are accommodated in the external electrode 27 so as to contact each other.
• the plastic bottle B communicates with the discharge chamber 33 of the chamber head member 32 through its mouth.
• the film forming chamber 21 in which the plastic bottle B is accommodated is rotated counterclockwise by the rotating plate 2 of the rotary vacuum seal mechanism 1.
• the discharge bottle 33 of the chamber head member 32 of the film formation chamber 21 is passed through the exhaust pipe 11 until the film formation position of the barrier film before point F is taken out.
• the gas inside and outside the PET bottle B is exhausted, and the degree of vacuum in these spaces is gradually increased from low vacuum to high vacuum in the four zones of the rotary vacuum seal mechanism 1.
• a barrier film forming gas (for example, a medium gas) is supplied to the gas supply pipe 34 and its lower end force is also blown into the PET bottle B. This medium gas further flows toward the mouth of the plastic bottle B.
• the gas supply amount and the gas exhaust amount are balanced, and the inside of the plastic bottle B is set to a predetermined gas pressure.
• high frequency power having a frequency of 13.56 MHz is supplied from the high frequency power supply 35 to the main body 25 of the external electrode 27 through the cable 36, the matching unit 38 and the power supply terminal 37.
• a discharge is generated between the external electrode 27 and the position force of the chamber head member 32 and the no-cam-shaped conductor 39, which are ground electrodes, and the exhaust pipe 11 up to the chamber head member 32 generates plasma.
• the medium gas is dissociated by the plasma, and the film-forming seed ions are deposited on the inner surface of the PET bottle B in the external electrode 27, so that the carbon film, which is a good film quality, is a high-speed carbon film.
• the medium gas is basically hydrocarbon, for example, alkanes such as methane, ethane, propane, butane, pentane, hexane, etc .; alkenes such as ethylene, propylene, butene, pentene, butadiene, etc .; acetylene, etc.
• alkanes such as methane, ethane, propane, butane, pentane, hexane, etc .
• alkenes such as ethylene, propylene, butene, pentene, butadiene, etc .
• acetylene etc.
• Alkynes Alkynes; aromatic hydrocarbons such as benzene, toluene, xylene, indene, naphthalene and phenanthrene; cycloparaffins such as cyclopropane and cyclohexane; cycloolefins such as cyclopentene and cyclohexene; methyl alcohol and ethyl alcohol
• Oxygen-containing hydrocarbons such as; nitrogen-containing hydrocarbons such as methylamine, ethylamine, and phosphorus, and other carbon monoxide and carbon dioxide can also be used.
• a rare gas such as Ar or He may be mixed with the medium gas.
• the barrier film forming gas in addition to the medium gas, a mixed gas of siloxane and oxygen such as hexamethyldisiloxane for forming a SiOx film can be used.
• the high-frequency power is generally 13.56 MHz, 100 to 1000 W.
• these electric powers may be continuous or intermittent (pulsed).
• the area ratio (S2ZS 1) of the area (S1) of the outer electrode 27 inner surface (S1) and the area of the ground electrode (S2) in which the aforementioned PET bottle B is accommodated Is preferably controlled to 1 or more.
• changing the arrangement position of the her cam-shaped conductor 39 in the exhaust pipe 11 effectively changes the length of the exhaust pipe 11 that functions as a ground electrode, and controls it to a desired area ratio. So that the discharge area can be controlled. .
• the upper limit of the area ratio (S2ZS1) is preferably 5.
• the upper limit of the area ratio (S2ZS1) should be 3.5.
• the plastic bottle B is accommodated in the film forming chamber 21 that is connected to the rotating disk 2 of the rotary vacuum seal mechanism 1 through the exhaust pipe 11, and the PET bottle
• a hermetic conductor 39 which is an air shielding and conductive electric field shielding member, is disposed in the exhaust pipe 11, and only the chamber head member 32 having a conductive material force is provided.
• the arrangement position force of the her cam-shaped conductor 39 and the exhaust pipe 11 up to the chamber head member 32 also function as a ground electrode, so that the discharge area is expanded to the exhaust pipe 11 that communicates with the chamber head member 32.
• a large plasma sheath voltage can be applied between the external electrode 27 and the ground electrode including the chamber head member 32 and the exhaust pipe 11 portion, and from the barrier film forming gas such as a medium gas dissociated in the plasma. Since high-energy positive ions can be incident on the inner surface of the PET bottle B, a barrier film such as a carbon film with good film quality can be formed on the inner surface of the PET bottle B at high speed.
• the discharge region generated in the exhaust pipe 11 is regulated by the no-cam-type conductor 39 by arranging the her cam-type conductor 39 at a desired position inside the exhaust pipe 11 that also has a conductive material force. Since it is possible to prevent the rotary vacuum seal mechanism 1 from being reached, it is possible to prevent the occurrence of unstable discharge and abnormal power supply.
• the above-described PET bottle can be accommodated by changing the arrangement position of the her cam-shaped conductor 39 in the exhaust pipe 11 (that is, changing the length of the exhaust pipe 11 that effectively functions as a ground electrode).
• the area ratio (S2 ZS1) between the inner surface area (S1) of the external electrode 27 and the area of the ground electrode (S2) to 1 or more, the inner surface of the plastic bottle B has a good film quality.
• a nori film can be formed at high speed.
• a cylindrical spacer 30 made of a dielectric material having a cavity 29 is inserted into and fixed to the upper part of the external electrode 27, and at least the mouth force shoulder of the plastic bottle B is attached to the spacer 30.
• Mouth force A noble film such as a carbon film having a uniform thickness and good film quality can be formed on the inner surface of the shoulder.
• an inner surface non-coated membrane-coated PET bottle excellent in barrier properties that prevents permeation of oxygen from the outside and permeation of carbon dioxide from the inside (for example, carbonated drinking water) can be produced.
• the NORA film obtained in the present invention has a small amount of graphite (carbon atom bond is SP 2 bond) compared to diamond (carbon atom bond is SP 3 bond).
• carbon atom bond is SP 2 bond
• diamond carbon atom bond is SP 3 bond
• a soft carbon film of less than lOGPa and a hard carbon film of 10 to 20 GPa, a so-called diamond by increasing the discharge voltage to reduce the combination of graphite and reducing the hardness.
• Like carbon film DLC film
• these include films in which different atoms such as C, metal atoms, N, and O are mixed in a trace amount to a few percent.
• a noro film is taken as an example, but a film for improving chemical resistance and wear resistance is also included as the coating film of the present invention.
• examples of the container in which the barrier film is coated on the inner surface in the present invention include a glass container, a ceramic container, a paper container and the like in addition to a so-called plastic container represented by a PET bottle. Monkey.
• Examples of the container include a plastic container filled with a volatile liquid such as carbonated beverages, and a plastic automobile fuel container filled with fuel or the like.
• Examples of other containers include pharmaceutical plastic containers and food plastic containers.
• gas containers that require high gas permeability and gas nozzle properties are also included.
• plastic pipes and the like are the same as containers in the present invention, and the present invention can be applied to inner surface coating.
• the Hercame conductor is used as the air-permeable and conductive electric field shielding member disposed in the exhaust pipe 11, but the following Figs. 3 and 4 are used.
• Various forms can be used as described with reference. In FIGS. 3 and 4, the same members as those in FIG.
• Fig. 3 is a cross-sectional view of the main part showing another form of the coating film forming apparatus according to the first embodiment of the present invention.
• a plurality of, for example, three metal meshes 40 which are air-permeable and conductive electric field shielding members, are arranged at desired positions in the exhaust pipe 11! RU
• the external electrode can be changed by changing the arrangement position of the laminated metal mesh 40 in the exhaust pipe 11 (that is, changing the length of the exhaust pipe 11 that effectively functions as a ground electrode).
• the area ratio (S2ZS1) of the ground electrode can be controlled, and the area ratio (S2ZS1) is preferably 1 or more.
• FIG. 4 is a cross-sectional view of a main part showing a coating film forming apparatus of still another form according to the first embodiment of the present invention.
• a baffle 41 made of a conductive material that is a gas-permeable and electrically conductive electric field shielding member is disposed at a desired position in the exhaust pipe 11.
• the area of the external electrode and the ground electrode is changed by changing the arrangement position of the baffle 41 in the exhaust pipe 11 (that is, changing the length of the exhaust pipe 11 that effectively functions as a ground electrode).
• the ratio (S2ZS1) can be controlled, and the area ratio (S2ZS1) is preferably 1 or more. However, it is preferable to set the upper limit of the area ratio (S2ZS1) to 5 in consideration of the decrease in the barrier property of the barrier film formed on the inner surface of the pet bottle due to the excessive expansion of the discharge region as described above.
• the upper end of the mouth of PET bottle B In the hollow portion of the annular insulating member 31, the mouth and shoulder of the plastic bottle B in the hollow portion 29 of the spacer 30, and the other portion of the plastic bottle B in the external electrode 27.
• the external electrode 27 that accommodates the plastic bottle B by using the aluminum gas supply pipe 34 and changing the arrangement position of the her cam-shaped conductor 39 in the exhaust pipe 11 27.
• the inner surface area (S1) and the ground electrode The area ratio (S2ZS1) to the area (S2) was controlled, and a carbon film was formed on the inner surface of the PET bottle B under the following conditions.
• the upper end of the mouth of the plastic bottle B is placed in the hollow portion of the annular insulating member 31, and the mouth and shoulder of the plastic bottle B are placed in the spacer 30.
• the other PET bottle B part is accommodated in the external electrode 27 in the hollow part 29 of this, and the heart-shaped conductor is arranged at the corner part extending from the rising edge of the chamber head member 32 to the exhaust pipe 11 side.
• the exhaust tube does not function as a discharge region, and the same as in Example 1 except that the area ratio (S2ZS1) of the area (S1) of the outer electrode 27 to the area (S2) of the ground electrode is 0.7.
• a carbon film was formed on the inner surface of the PET bottle by operating the method.
• the oxygen permeability was measured using a product of Control Co., Ltd. (trade name: OXTRAN), and the oxygen permeability force converted to a carbon film having a thickness of 20 nm was determined as a relative oxygen barrier property.
• Figure 5 shows these results.
• the exhaust pipe 11 is effectively functioned as a discharge region, and the area ratio (S2ZS 1) between the area of the inner surface of the external electrode 27 (S1) and the area of the ground electrode (S2) is
• the exhaust pipe 11 does not function as a discharge region, and the carbon ratio is better, that is, the film quality is better than Comparative Example 1 in which the area ratio (S2ZS1) is 0.7. It can be seen that a film can be formed on the inner surface of pet bottle B.
• the NORA film forming apparatus on the inner surface of the plastic container according to the second embodiment has substantially the same structure as that shown in FIGS. 1 and 2 except that the exhaust pipe structure shown in FIG. 6 is different. Note that the same constituent members as those of the apparatus of the first embodiment are denoted by the same reference numerals and description thereof is omitted.
• the exhaust pipe 11 is a pipe part (conductive pipe part) 12a made of a conductive material such as a metal such as stainless steel, and a synthetic resin such as polyethylene or polypropylene.
• a tube portion (insulating tube portion) 12b having insulating material force such as ceramic such as alumina is connected to each other.
• the conductive tube portion 12a side is connected to the side surface of the chamber head member 32 of the film forming chamber 21 so as to communicate with the discharge chamber 33 of the member 32, and the insulating tube portion 12b side is rotated by the rotary vacuum seal mechanism 1. Connected to board 2 and beats.
• the aforementioned plastic bottle B is stored.
• the area ratio (S2ZS1) of the area (S1) of the inner surface of the external electrode 27 and the area (S2) of the ground electrode can be controlled, and the area ratio (S2 / S1) is preferably 1 or more.
• the upper limit of the area ratio (S2ZS1) is set to 5 and more preferably 3.5 in consideration of the decrease in the barrier property of the barrier film formed on the inner surface of the PET bottle due to the excessive expansion of the discharge region as described above. It is preferable to do this.
• the plastic bottle B is accommodated in the film forming chamber 21 connected to the rotating disk 2 of the rotary vacuum seal mechanism 1 shown in FIG.
• the exhaust pipe 11 is composed of a conductive tube portion 12a and an insulating tube portion 12b, and the conductive tube portion 12a is formed on the chamber head member 32 of the film forming chamber 21. It is connected to the side so as to communicate with the discharge chamber 33 of the member 32, and is made of a conductive material.
• the discharge region is expanded from the chamber head member 32 to the conductive pipe portion 12a of the exhaust pipe 11 communicating therewith.
• a plasma sheath voltage can be applied between the external electrode 27 and the ground electrode including the chamber head member 32 and the exhaust pipe 11 portion, and a high energy energy from a noble film forming gas such as a medium gas dissociated in the plasma can be obtained. Since positive ions can be incident on the inner surface of the PET bottle B, a barrier film such as a carbon film having a good film quality can be formed on the inner surface of the PET bottle B at high speed.
• the exhaust pipe 11 is composed of the conductive tube portion 12a and the insulating tube portion 12b, thereby restricting the discharge region within the conductive tube portion 12a of the exhaust pipe 11 and providing the rotary vacuum seal mechanism 1. Can be prevented, leading to unstable discharge and induction of power failure.
• the above-described PET bottle B is stored.
• the area ratio (S2ZS1) between the inner surface area (S1) of the external electrode 27 and the ground electrode area (S2) is controlled to 1 or more, the inner surface of the plastic bottle B is not like a carbon film with good film quality. A rear film can be formed at high speed.
• a highly reliable plastic capable of forming a noble film such as a carbon film with good film quality on the inner surface of the plastic bottle B at high speed.
• a device for forming a NORA film on the inner surface of the container can be provided.
• an inner surface non-coated membrane-coated PET bottle with excellent barrier properties that prevents permeation of oxygen from the outside and permeation of carbon dioxide from the inside (for example, carbonated drinking water) can be produced.
• the upper end of the mouth of the plastic bottle B is placed in the hollow portion of the annular insulating member 31, and the mouth and shoulder of the plastic bottle B are placed in the spacer 30.
• the other portion of the plastic bottle B is accommodated in the external electrode 27, the aluminum gas supply pipe 34 is used, and the length of the conductive pipe part 12a constituting the exhaust pipe 11 Change the external electrode 27 to store the PET bottle B.
• the area ratio (S2ZS1) to the area (S2) of the pole was controlled, and a carbon film was formed on the inner surface of the plastic bottle B under the following conditions.
• the gas supply pipe 34 made of aluminum was used.
• the gas supply pipe made of ceramics such as alumina is replaced with a gas supply pipe, the gas noirability is slightly reduced.
• a carbon film having a good film quality comparable to that of PET bottle B could be formed. This is because a gas supply pipe made of ceramic does not function as a ground electrode, and the area ratio (S2ZS1) is slightly lowered.
• the high frequency power source connected to the external electrode is used as the electric field applying means.
• a bias power source and a gas supply pipe (internal electrode) connected to the external electrode are used.
• the high-frequency power source connected to () may constitute an electric field applying means, and the gas exhaust pipe may be set to the ground potential. According to such a configuration, it becomes possible to increase the formation speed of the carbon film which is the NORA film.
• the coating film forming apparatus for coating the inner surface of the container of the present invention has been described using the film forming chamber 21 shown in FIG. 2, but the film forming chamber is not limited to this.
• the film forming chamber for forming the coating film on the inner surface is used.
• the film forming chamber for coating not only the inner surface of the container but also the outer surface may be used.
• a film forming device for the inner surface of a plastic container with excellent mass productivity that can form a carbon film such as a carbon film with good film quality at high speed on the inner surface of the plastic container. can do.
• the present invention provides a method for producing a plastic container useful for beverage bottles and the like, in which a noble film such as a carbon film with good film quality is formed on the inner surface and has excellent barrier properties against oxygen and carbon dioxide. Can do.

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• 2005
  • 2005-07-12 CN CN2005800510696A patent/CN101223299B/zh not_active Expired - Fee Related
  • 2005-07-12 KR KR1020087000710A patent/KR101029657B1/ko active IP Right Grant
  • 2005-07-12 WO PCT/JP2005/012823 patent/WO2007007395A1/ja active Application Filing
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