WO2001032513A1 - Recipient en plastique revetu d'une couche de cda exempte d'azote, procede et appareil utilises pour sa fabrication - Google Patents

Recipient en plastique revetu d'une couche de cda exempte d'azote, procede et appareil utilises pour sa fabrication Download PDF

Info

Publication number
WO2001032513A1
WO2001032513A1 PCT/JP2000/007758 JP0007758W WO0132513A1 WO 2001032513 A1 WO2001032513 A1 WO 2001032513A1 JP 0007758 W JP0007758 W JP 0007758W WO 0132513 A1 WO0132513 A1 WO 0132513A1
Authority
WO
WIPO (PCT)
Prior art keywords
plastic container
nitrogen
gas
dlc film
film
Prior art date
Application number
PCT/JP2000/007758
Other languages
English (en)
Japanese (ja)
Inventor
Kenichi Hama
Tsuyoshi Kage
Original Assignee
Mitsubishi Shoji Plastics Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Shoji Plastics Corporation filed Critical Mitsubishi Shoji Plastics Corporation
Priority to AU10558/01A priority Critical patent/AU1055801A/en
Publication of WO2001032513A1 publication Critical patent/WO2001032513A1/fr

Links

Classifications

    • 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
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
    • B65D1/0215—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
    • 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
    • C23C16/22—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

Definitions

  • the present invention relates to a DLC (Diamond Dry Carbon) membrane suitable for beverages such as carbonated beverages or fruit juice beverages and refreshing beverages, and also for pharmaceuticals, agricultural chemicals, or dry foods that dislike moisture absorption.
  • the present invention relates to a plastic container coated with an excellent nitrogen-free DLC film, a method for producing the same, and an apparatus for producing the same. Background art
  • the DLC film is a film called an i-carbon film or a hydrogenated amorphous carbon film (a-C: H), and includes a hard carbon film.
  • a-C hydrogenated amorphous carbon film
  • a carbon film of Amorufu ⁇ focal also has SP 3 bond and SP 2 bond.
  • the DLC film is coated on the inner surface of the plastic container to provide gas barrier properties especially for carbonated beverages and high fruit juice beverages, and to prevent sorption of aroma components.
  • a vapor deposition apparatus using a (chemical vapor deposition) method is disclosed in, for example, JP-A-8-53117, and a DLC film-coated plastic container is disclosed in JP-A-8-53116. Have been.
  • the hardness of the DLC film is focused on its hardness and the recording of a cutting tool, an optical lens, a filter, or a hard disk as a protective film It was widely used for materials and other surfaces. Disclosure of the invention
  • DLC films are collectively called carbon atoms.
  • the gas barrier property of the DLC film is generally high when the hydrogen content is as high as 50% or more. It is said that the hardness decreases when the amount of hydrogen and oxygen increases, and the hardness increases when the amount of nitrogen increases, because the bonding of carbon nitride and the like increases.
  • Optimum DLC film physical properties especially when used as a carbonated beverage or high juice beverage container by coating a DLC film on the inner surface of a plastic container means that, for example, oxygen atoms are included in the DLC film together with hydrogen atoms and carbon atoms. It is presumed that the DLC film can follow the expansion and contraction of the base material instead of decreasing the film hardness, so that the film does not crack and the gas barrier properties can be maintained. .
  • An example of coating a DLC film containing oxygen atoms in this manner is described in JP-A-11-58587.
  • the DLC film will contain nitrogen atoms to a non-negligible extent, and if l (T 4 Torr vacuum reach, air components remain in the reaction chamber, so air components oxygen and nitrogen are involved in bra Zuma reaction, because oxygen compounds and nitrogen compounds are presumed to you mixed as a by-product the JP 11 -. even in 58587 JP, l (T 4 ⁇ 10 '5 It is reported that the DLC film is composed of carbon atoms, hydrogen atoms, and oxygen atoms by the reaction under reduced pressure of about Torr, but it is presumed to contain nitrogen for the same reason.
  • a DLC film for use as a protective film such as a hard disk recording material used by paying attention to the hardness of the DLC film.
  • impurities such as water vapor, oxygen, and nitrogen in the reaction chamber are removed, and the purity of toluene and the like is unrelated to the food field. is reacted at a pressure of about 10- 3 Torr by the child introduced purified easily aromatic hydrocarbon feedstock gas was deposited.
  • This method requires low cost because of low productivity, but can prevent contamination of nitrogen atoms, which are impurities, and can form a DLC film composed of carbon atoms and hydrogen atoms, which are basic constituent elements. You.
  • the oxygen atomic% is set to 0.2 at% or less.
  • the physical properties of the DLC film are determined by adjusting the constituent atomic compositions of carbon, hydrogen, oxygen, and nitrogen, but the form of nitrogen in the DLC film is not clear. It is assumed that there are those with low to high molecular weight such as CN group and NH 2 group. For example, low molecular weight NH 2 will cause odor. Therefore, it is desirable for food containers to eliminate nitrogen from the DLC membrane as much as possible. Nitrogen contained in the DLC film may be present as carbon nitride, and some have pointed out that carbon nitride is carcinogenic and has other health problems.
  • Examples of the method for producing a nitrogen-free DLC film and a DLC film include the above-described DLC film for use as a protective film such as a hard disk recording material and a coating method thereof, but the productivity is low and the method is applied to a container. In addition to this, it is impossible in terms of manufacturing cost, and as a DLC film to be formed on the inner surface of a plastic container, the expansion and contraction following production is insufficient and the film properties are inappropriate. In general, productivity is an important factor in implementing productivity in areas such as containers where productivity is required.If productivity is prioritized, vacuum pressure is reduced to l (T ft T 0 rr) without vapor deposition. Nitrogen is easily mixed in. On the other hand, aromatic hydrocarbon-based materials that are difficult to mix with impurity-derived nitrogen from the raw materials cannot be used for safety and health, so these conventional technologies are applied to containers in the technical field of the present invention. I can't do that.
  • the coated DLC film is free of cracks, has the stretchability to maintain gas barrier properties, and has high productivity during coating, it is aromatic hydrocarbon-based.
  • Source gas for film formation There is no DLC membrane-coated plastic container that does not use it as a raw material and does not contain nitrogen atoms.
  • the present inventors have found that the productivity of a DLC film-coated plastic container is high, and that the film properties required as a DLC film, that is, not only alkali resistance and acid resistance, but also flexibility that can follow the expansion and contraction of plastics Assuming that it has the properties of gas, gas barrier properties, and the ability to prevent the sorption of aroma components, from the viewpoint of safety and hygiene, we have conducted intensive research on a method for manufacturing the container that does not contain nitrogen and does not use aromatic hydrocarbon-based materials. As a result, it has been found that the above problem can be solved by using a non-aromatic hydrocarbon-based source gas having a low nitrogen content as an impurity and effectively replacing the atmosphere gas in the chamber with the source gas. The present invention has been completed.
  • an object of the present invention is to provide not only the film physical properties required for a DLC film coated on the inner surface of a plastic container, namely, alkali resistance and acid resistance, but also flexibility that can follow the expansion and contraction of plastic, and gas barrier.
  • An object of the present invention is to provide a container having excellent safety and hygiene, which has an aggressiveness and a property of preventing sorption of aroma components, and has a nitrogen content of less than 0.2 atomic% in a DLC film. Even if the nitrogen content of the DLC film is 0.2 atomic% or more, it can be used as a container for food and other fields other than those requiring safety and health, but in view of the recent situation of chemical contamination, etc. It is important not to include nitrogen compounds, which could be a safety and health problem.
  • 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 an appropriate rigidity and a predetermined thickness, and a plastic container formed of a non-rigid sheet material.
  • the filling of the plastic container according to the present invention is a beverage such as a carbonated beverage or a fruit juice beverage or a soft drink, and a pharmaceutical, agricultural chemical, or moisture-absorbing beverage. And dry foods that dislike the food.
  • a second object of the present invention is to provide a CH-0-based DLC film-coated plastic container which is considered to be useful for plastic container expansion / contraction followability.
  • An object of the present invention is to provide a plastic container.
  • a third object of the present invention is to prevent the use of an organic solvent at any time, particularly in the process of manufacturing containers for foods and the like, so that the nitrogen content of the DLC film is less than 0.2 atomic%,
  • An object of the present invention is to provide a more safe and hygienic container using a non-aromatic hydrocarbon compound, preferably acetylene, as a film forming raw material.
  • a fourth object of the present invention is to reduce the concentration of nitrogen in the raw material gas to be introduced to less than 500 ppm so that the plastic container can be manufactured using either the high-frequency plasma CVD method or the microwave plasma CVD method.
  • An object of the present invention is to provide a production method which has a film property required for a DLC film coated on an inner surface, has no DLC film containing nitrogen, and has high coating productivity.
  • the composition of the DLC film is 40 to 70 atomic% of carbon and 25 to 45 atomic% of hydrogen. %, Oxygen is 5 ⁇ : 15%.
  • about 1 atomic% of nitrogen may be mixed into the DLC film.
  • the nitrogen-free DLC film according to the present invention is a composition analysis performed by using ES CA850M based on X-ray Photoelectron Spectroscopy (X-ray Photoelectron Spectroscopy) to detect nitrogen atoms. It refers to a DLC film below the limit, that is, less than 0.2 at% of nitrogen atoms. However, the calculation is performed assuming that hydrogen atom% that cannot be detected by X-ray photoelectron spectroscopy is 0 at%.
  • a fifth object of the present invention is to provide a depressurizing step in a plastic container using a source gas containing low nitrogen, and a depressurized atmosphere gas in a plastic container.
  • a sixth object of the present invention is to make the introduction flow rate of the source gas when replacing the reduced-pressure atmosphere gas in the plastic container with the source gas two to six times the introduction flow rate of the source gas at the time of forming the DLC film.
  • the purpose of the present invention is to provide a production method for dramatically improving the source gas replacement effect. Increasing the introduction flow rate of the source gas during replacement is particularly effective when the replacement time by the source gas is short or when the vacuum pressure is low. Even if it is 6 times or more, the replacement effect is high and can be implemented, but on the contrary, the amount of source gas used increases.
  • a seventh object of the present invention is to make the DLC film non-nitrogen-containing by the replacement of the source gas by ensuring that the replacement time by the source gas is 0.1 to 1.0 second, and to improve the productivity of the coating. To provide a high production method. If the replacement time is less than 0.1 second, the replacement by the source gas becomes insufficient, and if it is more than 1.0 second, the coating productivity decreases.
  • An eighth object of the present invention is to make the DLC film non-nitrogen-containing and to use an organic solvent and avoid contact at any time in the production process of containers for foods and the like, so that non-aromatic gas is used as a raw material gas.
  • An object of the present invention is to provide a method for producing a container that uses a hydrocarbon compound to ensure safety and health.
  • a ninth object of the present invention is to use acetylene having a high reactivity, a high deposition rate, and a high safety and hygiene as a raw material gas, thereby ensuring the safety and health of the container and improving the deposition rate. Is to increase productivity and increase productivity.
  • a tenth object of the present invention is to provide a container having excellent safety and hygiene with a nitrogen content of less than 0.2 atomic% by providing a film property required for a DLC film to be coated on the inner surface of a plastic container and having a nitrogen content of less than 0.2 atomic%. It is an object of the present invention to provide a device that can be manufactured with a device. The means for solving the above problems are as follows.
  • the nitrogen-free DLC film-coated plastic container of the present invention comprises:
  • the nitrogen content of the DLC film is less than 0.2 atomic%.
  • the DLC film is preferably composed of carbon atoms, hydrogen atoms, and oxygen atoms.
  • the raw material for forming the DLC film of the nitrogen-free DLC film-coated plastic container of the present invention is a non-aromatic hydrocarbon compound.
  • the non-aromatic hydrocarbon compounds include hydrocarbon compounds of non-organic solvents such as methane, ethane, propane, ethylene, and propylene. Particularly, acetylene is preferable.
  • the method for producing a nitrogen-free DLC film-coated plastic container of the present invention is as follows: a plasma is generated using high frequency or microwaves, and a DLC film is formed on the inner surface of the plastic container by a chemical vapor deposition (CVD) method.
  • the nitrogen concentration in the source gas used in the CVD method should be less than 500 ppm. Further, it is preferable that the nitrogen concentration in the source gas used in the CVD method be less than 100 ppm. This is because the lower the nitrogen concentration in the source gas, the greater the tolerance for intrusion from other routes and the lower the absolute nitrogen content.
  • the gas in the plastic container disposed in the chamber is exhausted to reduce the pressure in the plastic container to a predetermined vacuum pressure or less.
  • the reduced-pressure atmosphere gas in the plastic container is replaced with the raw material gas. Adjusting the pressure to a predetermined film forming pressure, and forming a DLC film,
  • the predetermined vacuum pressure is 0.01 to 0.10 Torr (1.33 to:! 3.3 Pa) when using the high-frequency plasma CVD method, and 0.01 to 0.50 Torr (1.33 when using the microwave plasma CVD method). 6767 Pa).
  • the predetermined film forming pressure is 0.05 to 0.50 Torr when using the high frequency plasma CVD method, and 0.05 to 30 Torr (6.7 to 4000 Pa) when using the microwave plasma CVD method.
  • the reason why the pressure is set to be equal to or lower than the predetermined vacuum pressure is that if the pressure is reduced to a certain vacuum pressure, the absolute amount of the depressurized atmosphere gas in the plastic container is reduced to some extent. This is because nitrogen contamination can be prevented, which is preferable. However, since the time required for the depressurization process is long and the productivity decreases, the vacuum pressure is determined in consideration of the amount of nitrogen mixed and productivity.
  • the method for producing a nitrogen-free DLC film-coated plastic container of the present invention comprises introducing a raw material gas into the plastic container while exhausting a reduced-pressure atmosphere gas in the plastic container. It is preferable that the flow rate of the source gas when replacing the reduced-pressure atmosphere gas with the source gas is 2 to 6 times the flow rate of the source gas when the DLC film is formed.
  • the method for producing a nitrogen-free DLC film-coated plastic container comprises the steps of: introducing a raw material gas into the plastic container while exhausting the reduced-pressure atmosphere gas in the plastic container; The atmosphere gas is replaced with the source gas, and the pressure in the plastic container is adjusted to a predetermined film forming pressure.
  • the replacement time with the source gas is preferably set to 0 :! to 1.0 second.
  • the raw material gas is a non-aromatic hydrocarbon compound.
  • the non-aromatic hydrocarbon-based compound is acetylene.
  • the apparatus for producing a nitrogen-free DLC film-coated plastic container of the present invention is a DLC film-coated plastic container that generates plasma using high frequency or microwave and forms a DLC film on the inner surface of the plastic container by a CVD method.
  • the high-purity source gas having a nitrogen concentration of less than 500 ppm is preferably a non-aromatic hydrocarbon compound, particularly acetylene.
  • the suction means By introducing the raw material gas into the plastic container while exhausting the depressurized atmospheric gas in the plastic container by the suction means for forcibly replacing the depressurized atmospheric gas in the plastic container with the high-purity raw material gas. It is preferable to replace the reduced-pressure atmosphere gas in the plastic container with the source gas.
  • the film physical properties required as a DLC film coated on the inner surface of a plastic container that is, not only alkali resistance and acid resistance, but also flexibility that can follow the expansion and contraction of plastic.
  • a nitrogen-free DLC film-coated plastic container having a gas barrier property, prevention of sorption of aroma components, and a nitrogen content of the DLC film of less than 0.2 atomic% from the viewpoint of safety and health.
  • a CH-0-based DLC film-coated plastic container which is particularly useful for following the expansion and contraction of a plastic container, particularly a nitrogen-free DLC film-coated plastic container excellent in safety and health.
  • the nitrogen content of the DLC film is less than 0.2 atomic%, and the non-aromatic hydrocarbon compound, preferably acetylene, is used as a raw material for forming the DLC film.
  • the nitrogen concentration in the source gas to be introduced is set to less than 500 ppm, so that the high-frequency plasma CVD method or the microwave plasma CVD method can be applied to the inner surface of the plastic container. It was possible to provide a highly productive manufacturing method for a container having the necessary film properties as a DLC film to be coated and a nitrogen-free DLC film coated on the inner surface of a plastic container.
  • the invention of claim 8 it is possible to provide a production method with high productivity while ensuring that the DLC film is made non-nitrogen-containing by reliable source gas replacement.
  • the DLC film is made non-nitrogen-containing, and an organic solvent is used and a non-aromatic hydrocarbon compound is used at any time in the production process of containers for foods and the like in order to avoid contact.
  • acetylene as a raw material gas, the safety and health of the container can be ensured, and the productivity can be improved by increasing the film forming speed.
  • a container having the required film physical properties as a DLC film to be coated on the inner surface of a plastic container and having excellent safety and health with a nitrogen content of the DLC film of less than 0.2 atomic%.
  • a device that can be manufactured at a high cost could be provided.
  • Figure 1 shows a schematic diagram of an apparatus for manufacturing a nitrogen-free DLC film-coated plastic container by a high-frequency plasma CVD method.
  • Figure 2 shows a schematic diagram of an apparatus for manufacturing a nitrogen-free DLC film-coated plastic container by microwave plasma CVD.
  • 3 reference numerals in t Figure shows a schematic diagram of a nitrogen-free DLC Makuko one tee packaging plastic container manufacturing apparatus according to E CR microphone B wave plasma CVD method is as follows.
  • Nitrogen-free DLC film coated plastic container high-frequency plasma CVD method 200 nitrogen-free DLC film coated plastic container microwave plasma CVD method, 300 nitrogen-free DLC film ECR Microwave Plasma CVD Coating Equipment for Coating Plastic Container, 1 Lower External Electrode, 2 Upper External Electrode, 3 External Electrode, 4 Insulating Member, 5,37 Lid, 6,39 Chamber , 7,35,74 pet bottle, 8,360 ring, 9 internal electrode, 9a, 38a gas outlet, 10 matching unit, 11 high frequency power supply, 13,50 vacuum gauge, 14,21,52, 61 Vacuum knob, 16,54 vacuum pump, 17 duct exhaust, 12,15,20,22,24,51,53,60,62,64 piping, 23,63 mass flow 25,65 Source gas source, 26 Source gas introduction means, 31,71 Quartz chamber, 32,72 Seat De, 38 raw material gas supply nozzle, 40 matcher, 41 eye Seo regulator, 42 microphones b wave power, 43, 75 waveguide, 44 microphones filtering Introducing means, 55 duct exhaust, 66 source gas introducing means, 73
  • the high-frequency plasma CVD film forming apparatus 100 of the nitrogen-free DLC film-coated plastic container according to the present invention comprises an external electrode unit 3, an internal electrode 9, a raw material gas introducing means 26, a matching unit 10, Frequency power supply 11.
  • the external electrode part 3 forms a chamber 6 together with the conductive lid part 5 and the insulating member 4.
  • An insulating member 4 is disposed below the lid 5, and an external electrode 3 is disposed below the insulating member 4.
  • the external electrode section 3 is composed of an upper external electrode 2 and a lower external electrode 1.
  • the upper portion of the lower external electrode 1 is attached to the lower part of the upper external electrode 2 via an O-ring 8 so as to be detachably attached thereto. I have.
  • the external electrode part 3 is insulated from the lid part 5 by the insulating member 4.
  • the high-frequency plasma CVD method for nitrogen-free DLC film-coated plastic containers is described in terms of a single-vessel plastic container.However, it is also possible to deposit DLC films on the inner surface of multiple plastic containers simultaneously. This can be applied by arranging the chamber 6 and the internal electrode 9 in parallel.
  • the external electrode portion 3 is divided into the lower external electrode 1 and the upper external electrode 2, but in order to make the thickness of the DLC film uniform, the external electrode portion is, for example, a bottom electrode.
  • the electrode is divided into three or more, such as the torso electrode and the shoulder electrode, and each electrode is electrically connected with a Teflon sheet or polyimide film while securing the sealing properties with, for example, a 0 ring. It may be electrically insulated.
  • a space is formed inside the external electrode 3, and this space is for accommodating a plastic container to be coated, for example, a bottle 7 which is a container made of polyethylene terephthalate resin.
  • the space inside the external electrode section 3 is formed to be slightly larger than the outer shape of the pet bottle 7 housed therein.
  • the insulating member 4 and the lid 5 are provided with openings that connect to spaces in the external electrodes. Further, a space is provided inside the lid portion 5, and this space is connected to the space inside the external electrode portion 3 via the opening.
  • the space inside the external electrode section 3 is sealed from the outside by a ring 8 arranged between the upper external electrode 2 and the lower external electrode 1.
  • the impedance matching unit (matching unit) 10 is connected to the lower external electrode 1. Further, the matching unit 10 is connected to a high frequency power supply (RF power supply) 11 via a coaxial cable.
  • RF power supply radio frequency
  • the internal electrode 9 is arranged inside the external electrode part 3 and inside the boat bottle 7. That is, the internal electrode 9 is inserted into the space inside the external electrode part 3 from the upper part of the lid part 5 through the space inside the lid part 5 and the opening part of the lid part 5 and the insulating member 4.
  • the tip 9 a of the internal electrode 9 is a space in the external electrode portion 3 and is disposed inside the jet bottle 7 housed in the external electrode portion 3.
  • the internal electrode 9 has a tubular shape whose inside is hollow.
  • a gas outlet 9 a is provided at the tip of the internal electrode 9.
  • the internal electrode 9 is grounded via the lid 5 to the ground.
  • the source gas introduction means 26 introduces the source gas supplied from the source gas generation source 25 into the pet bottle 7. That is, one end of a pipe 20 is connected to the base end of the internal electrode 9, a vacuum valve 21 is connected to the other side of the pipe 20, and one side of a pipe 22 is connected to the other side of the vacuum valve. One side of the mass flow controller 23 is connected to the other side of the pipe 22. The other side of the mass flow controller 123 is connected to a source gas generation source 25 via a pipe 24.
  • the source gas generation source 25 generates a hydrocarbon gas such as acetylene.
  • high-purity acetylene is used as the source gas generation source 25.
  • the high-purity acetylene is a dissolved high-purity acetylene gas described later.
  • the space in the lid 5 is connected to one side of a pipe 12 in which a vacuum gauge 13 is installed, the other side of the pipe 12 is connected to one side of a vacuum valve 14, and the other side of the vacuum valve 14 is connected to a pipe. 15 is connected to one side, and the other side of the pipe 15 is connected to a vacuum pump 16. This vacuum pump 16 is connected to duct exhaust 17.
  • a vacuum valve (not shown) is opened to open the inside of the chamber 16 to the atmosphere.
  • air enters the space inside the cover 5 and the space inside the external electrode 3, and the inside of the chamber 6 is brought to atmospheric pressure.
  • the lower external electrode 1 of the external electrode section 3 is removed from the upper external electrode 2, and a pet bottle 7 is inserted from below the upper external electrode 2 into the space inside the upper external electrode 2 and installed.
  • the internal electrode 9 is inserted into the pet bottle 7.
  • the lower external electrode 1 is attached to the lower part of the upper external electrode 2, and the external electrode 3 is sealed by the 0 ring 8.
  • the film formation pressure of the DLC film is adjusted to, for example, about 0.05 to 0.5 Torr.
  • the nitrogen due to the residual air becomes almost zero, and the nitrogen concentration including the impurity nitrogen contained in the high-purity acetylene gas becomes 500 ppm or less, preferably 100 ppm or less.
  • an RF output (for example, 13.56 MHz) is supplied to the external electrode 3 from the high frequency power supply (RF power supply) 11 via the matching unit 10.
  • the high frequency applied voltage is 300-500W.
  • the matching unit 10 adjusts the impedance of the external electrode and the internal electrode by inductance and capacitance C.
  • hydrocarbon-based plasma is generated in the pet bottle 7 containing almost no nitrogen, and a nitrogen-free DLC film is formed inside the pet bottle 7.
  • the film formation time at this time is as short as about several seconds.
  • the RF output from the high-frequency power supply 11 is stopped, and the supply of the source gas is stopped by closing the vacuum valve 21.
  • the microwave plasma CVD method film forming apparatus 200 of the nitrogen-free DLC film coating plastic container according to the present invention shown in FIG. 2 includes a chamber 39, a microwave introduction means 44, and a source gas supply nozzle 38. And source gas introduction means 66.
  • the chamber 39 includes a microwave shield 32, a quartz chamber 31 housed in the inner space of the shield 32, and a lid 37 for sealing the inside of the shield 32.
  • the quartz chamber 31 and the quartz chamber 31 are configured to be detachably attached via a 0-ring 36. Further, the shield 32 is grounded to the ground.
  • a space is formed inside the quartz chamber 131, and this space is for accommodating a pet bottle 35 to be coated, for example, a pet bottle which is a container made of polyethylene terephthalate resin. is there.
  • the upper part of the shield 32 is provided with an opening to the space in the quartz chamber 31 and a space in the upper part thereof, and this space is connected to the space in the quartz chamber 31 through the opening. I have.
  • the space in the quartz chamber 31 is sealed from the outside by an O-ring 36 disposed between the quartz chamber 31 and the shield 32.
  • Nitrogen-free DLC film coating Microwave plasma CVD method for plastic containers Depositing a single plastic container is described in the 200 CVD system, but the DLC film is formed simultaneously on the inner surface of multiple plastic containers. In this case, it can be applied by arranging 39 chambers in parallel.
  • the microwave introducing means 44 is connected to a waveguide 43 whose one side is connected to the bottom of the shield 32, a matching device 40 where the other side of the waveguide 43 is connected, and a matching device 40.
  • An isolator 41 and a microwave power supply 42 connected to the isolator 41 are provided.
  • the bottom of the shield 32 is provided with an opening for transmitting the microwave transmitted from the waveguide 43 into the shield 32.
  • a quartz chamber 31 is provided so that the inside of the chamber 39 can be kept in a vacuum even with this opening.
  • the microwave sent from the waveguide 43 passes through the above-described opening and the quartz window at the bottom of the quartz chamber 31, and is disposed in the chamber 39 and the chamber 39. You can reach the interior space of Torr 35.
  • the source gas supply nozzle 38 is arranged inside the shield 32 and inside the bed bottle 35. That is, the raw material gas supply nozzle 38 is inserted into the space inside the quartz chamber 31 through the space above the shield 32 and the opening below the space above the shield 32 from above the lid 37. ing.
  • the outlet 38 a of the raw material gas supply nozzle 38 is located in the space of the quartz chamber 31 and inside the jet bottle 35 housed in the quartz chamber 31.
  • the source gas supply nozzle 38 has a tubular shape having a hollow inside. A gas outlet 38a is provided at the tip of the source gas supply nozzle 38.
  • the source gas introduction means 66 introduces the source gas supplied from the source gas generation source 65 into the pet bottle 35. That is, one end of a pipe 60 is connected to the base end of the raw material gas supply nozzle 38, and the other side of the pipe 60 is connected to a vacuum valve 61. One side of a pipe 62 is connected to one side, and one side of a mass flow controller 63 is connected to the other side of the pipe 62. The other side of the masph opening-controller 63 is connected to a source gas generating source 65 via a pipe 64.
  • the source gas generation source 65 generates hydrocarbon gas such as acetylene.
  • the source gas generating source 65 uses high-purity acetylene as in the first embodiment.
  • the space inside the upper part of the shield 32 is connected to one side of a pipe 51 in which the vacuum gauge 50 is installed, and the other side of the pipe 51 is connected to one side of a vacuum valve 52, and the other side of the vacuum valve 52 is connected to the other side.
  • One side of the pipe 53 is connected, and the other side of the pipe 53 is connected to a vacuum pump 54.
  • the vacuum pump 54 is connected to a duct exhaust 55.
  • a vacuum valve (not shown) is opened to open the inside of the quartz chamber 31 to the atmosphere.
  • air enters the space in the upper part of the shield 32 and the space in the quartz chamber 31, and the inside of the quartz chamber 31 is brought to atmospheric pressure.
  • the quartz chamber 31 is removed from the shield 32, and a bottom bottle 35 is inserted into the space inside the shield 32 from below the shield 32 and installed.
  • the source gas supply nozzle 38 is inserted into the pet bottle 35.
  • the quartz chamber 31 is mounted inside the shield 32, and the quartz chamber 31 is tightly closed by the O-ring 36.
  • the vacuum valve 52 is opened and the vacuum pump 54 is operated.
  • the inside of the quartz chamber 31 including the inside of the pet bottle 35 is exhausted through the pipe 51, and the inside of the quartz chamber 31 is evacuated.
  • the vacuum pressure in the quartz chamber 31 is 0.01 to 0.50 Torr.
  • the vacuum valve 61 is opened, high-purity acetylene gas is generated in the source gas generation source 65, and the high-purity acetylene gas is introduced into the pipe 60, and the mass flow controller 63 The high-purity acetylene gas whose flow rate is controlled by the gas is blown out from the gas blowout port 38a through the pipe 60 and the raw material gas supply nozzle 38.
  • high-purity acetylene gas is introduced into the pet bottle 35.
  • the supply of high-purity acetylene gas and the exhaust of the remaining gas are performed simultaneously for a predetermined time, for example, 0 :!
  • the high-purity acetylene gas supplies the inside of the pet bottle 35. Is replaced to satisfy.
  • the deposition pressure of the DLC film is adjusted to, for example, about 0.05 to 0.50 ⁇ .
  • the nitrogen due to the residual air is almost zero, and the nitrogen concentration including the impurity nitrogen contained in the high-purity acetylene gas is 500 ppm or less, preferably 100 ppm or less.
  • the inside of the pet bottle 35 is blown with the raw material gas and replaced with the raw material gas by simultaneously performing the above-described pressure reduction and raw material gas supply.
  • MW output (for example, 2.45 GHz) is supplied from the microwave power supply 42 through the waveguide 43.
  • the matching device 40 plays a role of performing impedance matching and efficiently sending power to the quartz chamber 31.
  • ISO 41 has been developed to protect the magnetron, which is a micro wave generation element, when matching (matching) is deviated and reflected waves (waves from the chamber to the microwave power supply) are generated. Absorbs reflected waves.
  • plasma is ignited in the pet bottle 35.
  • hydrocarbon-based plasma is generated in the pet bottle 35 containing almost no nitrogen, and a nitrogen-free DLC film is formed inside the pet bottle 35.
  • the film formation time at this time is as short as about several seconds.
  • the MW output from the microwave power supply 42 is stopped, and the supply of the source gas is stopped by closing the vacuum valve 61.
  • the pet bottle 35 The high-purity acetylene gas inside is evacuated by the vacuum pump 54.
  • the vacuum valve 52 is closed, and the vacuum pump 54 is stopped. Pressure at this time Nope' topo Torr in 35 1 0 - a 1 Torr - 2 ⁇ 1 0.
  • a vacuum valve (not shown) is opened to open the inside of the quartz chamber 31 to the atmosphere, and the above-described film forming method is repeated, whereby a DLC film is formed in the next pet bottle.
  • the film forming pressure may be set to a pressure of from: to 30 Torr (133 to 4000 Pa).
  • the present invention is not limited to the first and second embodiments, but can be implemented with various modifications.
  • the source gas source is not limited to a source of high-purity acetylene gas, and various other sources such as a hydrocarbon gas source having a low nitrogen content can be used.
  • a Si-containing non-aromatic hydrocarbon-based raw material or the like can be used.
  • a pet bottle for beverages is used as a container for forming a thin film inside, but a container used for other purposes can be used.
  • the DLC film or the Si-containing DLC film is mentioned as the thin film formed by the CVD film forming apparatus.
  • the above-mentioned film is formed. It is also possible to use a membrane device.
  • acetylene of welding standard JIS: K1902 and dissolved high-purity acetylene gas were used as raw material gases.
  • Acetylene of JIS: K 1902 standard for welding is used for welding and cutting of metals, etc.
  • Acetone or dimethylformamide is infiltrated as a solvent into a porous material evenly packed in a high-pressure gas container, The refined case It is obtained by compressing and dissolving tylene gas.
  • the acetylene purity was 98.0 vol% or more according to the standard, and the analytical value was 98.3 vol%.
  • the breakdown of impurities is solvent 0.3%, air 1.3% (nitrogen 1.0%, oxygen 0.3%) and other 0.1%. Therefore, the nitrogen concentration is about 1.0% (I0,000 ppm).
  • dissolution-type high-purity acetylene gas in standard a purity 99.6Vol%, impurities (ppm), the solvent component (acetone or Jimechiruhoru Muami de), H 2 ° 50, 0 2 ° 50, N 2 ⁇ 70 a CO ⁇ 20, CH 4 ° 100, CO 2 ⁇ 100.
  • the analytical value was that the nitrogen concentration in acetylene gas was 50 ppm or less (18-30 ppm).
  • the contents of nitrogen, oxygen, and carbon were analyzed using Shimadzu ESCA850M based on X-ray Photoelectron Spectroscopy. According to this device, the detection limit for nitrogen atoms is 0.2 at%. However, since hydrogen atomic% cannot be measured by this method, nitrogen atomic%, oxygen atomic%, and carbon atomic% were calculated assuming that hydrogen atomic% was 0%. It is estimated that the hydrogen atom percentage in the DLC film is 25 to 45 at%.
  • a pet bottle was used as a plastic container.
  • High-purity acetylene gas with a nitrogen concentration of 30 ppm is used as the source gas. Evacuate the residual air gas in the chamber and plastic container, reduce the vacuum pressure in the plastic container to 0.05 Torr, and continue evacuation. The raw material gas is introduced into the plastic container while the remaining gas in the plastic container is replaced with the raw material gas. The replacement raw material gas flow rate is set to 24 sccm, and the raw material gas replacement time is set to 0.3 seconds. The deposition pressure was adjusted to 0.1 OTorr, and a DLC film was formed at a raw material gas flow rate of 24 sccm. The composition of the DLC film was 85.3 at% for carbon atoms, 14.7 at% for oxygen atoms, and ND for nitrogen atoms (below the detection limit). Table 1 shows the above film forming conditions and evaluation results.
  • Example 1 was used under the film forming conditions of Examples 2 to 12 shown in Table 1. DLC films were formed for Examples 2 to 12 by the same operation. Table 1 shows the evaluation results. Acetylene of JIS: K 1902 for welding had a nitrogen concentration of 10,000 ppm. In Examples 10 to 12, before venting, insert a carbon dioxide gas injection pipe into the pet bottle up to the middle of the pet bottle height, and put in a carbon dioxide gas flow rate of 30 L / min for 15 seconds (pet The air in the bottle was replaced with carbon dioxide gas. More than 95% of the air in the pet bottle was replaced by carbon dioxide. After that, evacuation was started. In addition, a DLC film was formed at a source gas flow rate of 24 sccm.
  • the DLC film was formed at a flow rate of the source gas of 24 sccm.
  • Examples 1 to 12 high-purity acetylene gas was used, the vacuum pressure was 0.01 to 0.05 Torr, the raw material gas flow rate during replacement was 24 to 72 sccm, and the raw gas replacement time was 0 :! Since the time was set to ⁇ 1.0 sec, the atomic% of nitrogen in the DLC film was below the detection limit, and the hygienic evaluation was ⁇ .
  • the source gas replacement time is as short as 0.1 second as in Examples 6 and 8
  • the source gas flow rate during replacement is 48 to 72 sccm, which is two to three times the source gas flow rate during DLC film formation of 24 sccm. Since the source gas was flown, the replacement effect was enhanced, and the atomic% of nitrogen fell below the detection limit.
  • Comparative Example 8 compared with Comparative Example 3, 95% of the nitrogen in the DLC film was reduced to 0.2 at% by replacing the inside of the plastic container with carbon dioxide gas by 95% before evacuation. It was found that gas replacement alone was not enough. According to Comparative Example 4, even when the high-purity acetylene gas was used and the vacuum pressure was 0.05 Torr, the source gas replacement time was as short as 0.1 second, and the source gas flow rate during replacement was as small as 24 sccm. It was found to be as high as 0.2 at%.
  • Comparative Example 5 since the vacuum pressure was as high as 0.09 Torr, high-purity acetylene gas was used, and even if the source gas replacement time was 0.5 seconds, the nitrogen atom% in the DLC film increased to 0.2 at%. I understood. It is also considered that the source gas flow rate during replacement is as low as 24 sccm. According to Comparative Example 9, even if the source gas replacement was performed for 0.1 seconds in addition to the conditions of Comparative Example 8, the nitrogen atom% in the DLC film was 0.2 at%, and the source gas replacement was insufficient.
  • the vacuum pressure must be less than 0.09 Torr in order to maintain a limited source gas replacement time (1 second or less) from the viewpoint of maintaining productivity. It is preferable that If the flow rate of the source gas at the time of replacement is set to at least two to three times the flow rate of the source gas at the time of film formation, the replacement effect is doubled, so that the source gas exhaust time can be reduced to about 0.1 second.
  • Example 2 it was 84.91 carbon atom%, 15.03 oxygen atom%, and 0.06 nitrogen atom%, and in Example 6, it was 85.48 carbon atom%, 14.45 oxygen atom%, and 0.07 nitrogen atom%. It was confirmed that the nitrogen-free DLC film-coated plastic container of the present invention had almost zero nitrogen atoms.
  • the oxygen permeability of the DLC membrane coating pot of the above example was measured using Oxtran manufactured by Modern Control under the conditions of 22 ° C and 60% RH. ⁇ Container) and had sufficient gas barrier properties.
  • High-purity acetylene gas with a nitrogen concentration of 30 ppm is used as the source gas.
  • the residual air gas in the chamber and the plastic container is exhausted, the vacuum pressure in the plastic container is reduced to 0.05 Torr, and the source gas is introduced into the plastic container while continuing the evacuation.
  • the replacement source gas flow rate was set to 24 sccm
  • the source gas replacement time was set to 0.5 seconds
  • the deposition pressure in the plastic container was adjusted to O.l OTorr after the replacement.
  • the DLC film was formed at the source gas flow rate of 24 sccm.
  • the membrane was performed.
  • the composition of the DLC film is charcoal Elemental atoms were 86.2 at%, oxygen atoms were 13.8 at%, and nitrogen atoms were ND (below the detection limit). Table 2 shows the above film forming conditions and evaluation results.
  • DLC films were formed on Examples 14 to 18 in the same manner as in Example 13 under the film forming conditions of Examples 14 to 18 shown in Table 2.
  • Table 2 shows the evaluation results. JIS for welding: ⁇ 1902 acetylene had a nitrogen concentration of 10,000 ppm.
  • a DLC film was formed at a source gas flow rate of 24 sccm.
  • DLC films were formed on Comparative Examples 10 to 14 in the same manner as in Example 13 under the film forming conditions of Comparative Examples 10 to 14 shown in Table 2. Table 2 shows the evaluation results. In addition, a DLC film was formed at a source gas flow rate of 24 sccm.
  • Comparative Examples 11 to 14 since acetylene of JIS: K 1902 standard for welding was used, even if the vacuum pressure was 0.05 to 0.15 Torr and the raw material gas replacement time was 0.3 to 0.5 seconds, nitrogen was used. Atomic% was included in the range of 0.2 to 1.0 at%, and the hygienic evaluation of the membrane was ⁇ or X. In Comparative Example 10, the source gas replacement time was shorter than 0.5 seconds in Example 13 by 0.3 seconds in Comparative Example, so that the nitrogen atom% in the DLC film was 0.2 at%. all right.
  • the vacuum pressure is preferably 0.50 Torr or less in order to limit the source gas replacement time (1 second or less).
  • the source gas flow rate during replacement is reduced to the source gas flow rate during film formation. It was found that it was necessary to sufficiently blow the inside of the plastic container with the raw material gas to increase the replacement effect, at least 2 to 6 times.
  • the oxygen permeability of the coating bottle of the DLC membrane in the above example was determined using Oxtran manufactured by Modern Control Co. 22. When measured under the conditions of C and 60% RH, all were 0.002 to 0.004 cc / (container per day), indicating that they had sufficient gas barrier properties.
  • FIG. 3 shows the configuration of the ECR microwave plasma CVD film deposition system 300 in a nitrogen-free DLC film-coated plastic container.
  • the side of the quartz chamber 71 and the shield 72 The only difference is that the magnet coil 73 is placed between the side of the magnet.
  • the magnets are arranged because the ECR plasma is generated or the plasma density is increased by the auxiliary magnetic field depending on the film forming pressure, and in any case, it contributes to high-speed film forming.
  • high-purity acetylene is used as a source gas, and the concentration of nitrogen gas in the source gas is 30 ppm.
  • Nitrogen gas and acetylene gas as a source gas were each reduced to 1 kg / cm 2 , and the concentration ratio of acetylene gas and nitrogen gas was adjusted by controlling the nitrogen gas concentration with respect to the source gas using a flow meter. Gas mixtures with concentrations of 50, 100, 1000, and 100 ppm, respectively, were prepared.
  • the mixed gas of the specified concentration prepared by the above method is vacuum pumped into the pet bottle 74 installed in the quartz chamber 71.
  • the gas was blown for 10 seconds while depressurizing, and the inside of the container was completely replaced with a predetermined mixed gas.
  • the inside of the quartz chamber 71 was evacuated by operating a vacuum pump, and each mixed gas was introduced until a predetermined film forming pressure (1 Torr, 5 Torr, and 30 Torr) was reached.
  • a microwave of 2.45 GHz is introduced into the quartz chamber 71 through the waveguide 75, and a magnetic field is formed in the quartz chamber 71 by the magnetic coil 73, particularly in the bottle bottle container 74.
  • a plasma was generated.
  • a DLC film was formed on the inner wall surface of the bottle 74.
  • the flow rate of the mixed gas is 50 cc / min under standard conditions, and the deposition time is 3 seconds.
  • Table 3 shows Examples 19 to 24 and Comparative Examples 15 to 23 in which DLC films were formed by changing the nitrogen concentration of the mixed gas and the film forming pressure (pressure of the source gas). It shows the results of elemental analysis (analysis of nitrogen content) and oxygen permeability of the DLC film in Fig.
  • the nitrogen concentration was changed in five steps of 50, 100, 1000, and 100 ppm, and the deposition pressure was changed in three steps of 1, 5, and 30 Torr (133, 666, and 4000 Pa).
  • Oxygen permeability was measured using a modern control Oxtran at 22 ° (:, 60% RH).
  • the values in Table 3 show the oxygen permeability measured in a day (24 hours) per bottle. It is shown in terms of the volume of oxygen passing through.
  • the nitrogen content of the DLC film was in the range of 0.4 to 2.1 at%.
  • the nitrogen content of the mixed gas was in the range of 50 to: LOO ppm, and the nitrogen content of the DLC film in this case was 0.2 at. %, which was extremely small, and provided a container excellent in safety and health.
  • the oxygen supply source is either water absorbed in the PET bottle, water adsorbed on the inner wall of the chamber, or oxygen constituting PET.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'invention concerne un récipient en plastique sûr et hygiénique, possédant une surface intérieure revêtue d'une couche de CDA (carbone sous forme de diamant) présentant un pourcentage atomique d'azote inférieur à 2 et les propriétés physiques requises d'une couche appliquée sur la surface intérieure. Ledit récipient en plastique est fabriqué selon un procédé consistant à utiliser une matière première gazeuse pour le revêtement, présentant une teneur en azote inférieure à 500 ppm, ou de préférence selon un procédé consistant en une étape de réduction de la pression dans le récipient jusqu'à l'obtention d'une pression négative spécifique ou inférieure, et en une étape d'introduction de la matière première gazeuse dans le récipient pendant que ce dernier est vidé, ce qui permet le remplacement du gaz d'origine à la pression négative spécifique par la matière première gazeuse.
PCT/JP2000/007758 1999-11-04 2000-11-02 Recipient en plastique revetu d'une couche de cda exempte d'azote, procede et appareil utilises pour sa fabrication WO2001032513A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU10558/01A AU1055801A (en) 1999-11-04 2000-11-02 Nitrogen-free dlc film coated plastic container, and method and apparatus for manufacturing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/313464 1999-11-04
JP31346499 1999-11-04

Publications (1)

Publication Number Publication Date
WO2001032513A1 true WO2001032513A1 (fr) 2001-05-10

Family

ID=18041629

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2000/007758 WO2001032513A1 (fr) 1999-11-04 2000-11-02 Recipient en plastique revetu d'une couche de cda exempte d'azote, procede et appareil utilises pour sa fabrication

Country Status (2)

Country Link
AU (1) AU1055801A (fr)
WO (1) WO2001032513A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1500600A1 (fr) * 2002-04-26 2005-01-26 Hokkai Can Co., Ltd Recipients en plastique comportant un revetement sur leur surface interieure et procede de production de ces recipients
JP2005531688A (ja) * 2002-05-24 2005-10-20 ショット アーゲー ワークピースの処理装置および処理方法
JP2006111967A (ja) * 2004-09-17 2006-04-27 Mitsubishi Heavy Ind Ltd ガスバリア膜及び容器
KR100685594B1 (ko) * 2001-12-13 2007-02-22 미츠비시 쥬고교 가부시키가이샤 플라스틱 용기 내면에의 탄소막 형성 장치 및 내면 탄소막피복 플라스틱 용기의 제조 방법
JP2007131888A (ja) * 2005-11-09 2007-05-31 Toppan Printing Co Ltd プラズマ処理装置
US7754302B2 (en) 2002-05-28 2010-07-13 Kirin Brewery Company, Limted DLC film coated plastic container, and device and method for manufacturing the plastic container
WO2010095011A1 (fr) 2009-02-18 2010-08-26 Council Of Scientific & Industrial Research Procédé pour déposer du carbone de type diamant sous la forme d'un revêtement protecteur sur une surface interne d'un objet façonné
CN106986085A (zh) * 2016-01-20 2017-07-28 铨宝工业股份有限公司 确保包装饮用水完全出水的包装饮用水充填方法
WO2020148487A1 (fr) * 2019-01-17 2020-07-23 Innovative Systems Et Technologies (Isytech) Procede et dispositif de traitement pour le depot d'un revetement a effet barriere
WO2022187444A3 (fr) * 2021-03-04 2022-10-13 Yeti Coolers, Llc Revêtement de surface de nécessaire à boire
US12129078B2 (en) 2022-03-03 2024-10-29 Yeti Coolers, Llc Surface coating of drinkware

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62174378A (ja) * 1986-01-27 1987-07-31 Meijiyou Univ 硬質炭素薄膜の形成方法
JPH1081586A (ja) * 1996-09-03 1998-03-31 Sumitomo Electric Ind Ltd 気相合成ダイヤモンドおよびその製造方法
JPH10258825A (ja) * 1997-03-14 1998-09-29 Kirin Brewery Co Ltd 炭素膜コーティングプラスチック容器の製造装置および製造方法
JPH11256331A (ja) * 1998-03-16 1999-09-21 Ulvac Corp ダイヤモンド状炭素膜形成方法及び製造装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62174378A (ja) * 1986-01-27 1987-07-31 Meijiyou Univ 硬質炭素薄膜の形成方法
JPH1081586A (ja) * 1996-09-03 1998-03-31 Sumitomo Electric Ind Ltd 気相合成ダイヤモンドおよびその製造方法
JPH10258825A (ja) * 1997-03-14 1998-09-29 Kirin Brewery Co Ltd 炭素膜コーティングプラスチック容器の製造装置および製造方法
JPH11256331A (ja) * 1998-03-16 1999-09-21 Ulvac Corp ダイヤモンド状炭素膜形成方法及び製造装置

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100685594B1 (ko) * 2001-12-13 2007-02-22 미츠비시 쥬고교 가부시키가이샤 플라스틱 용기 내면에의 탄소막 형성 장치 및 내면 탄소막피복 플라스틱 용기의 제조 방법
EP1500600A1 (fr) * 2002-04-26 2005-01-26 Hokkai Can Co., Ltd Recipients en plastique comportant un revetement sur leur surface interieure et procede de production de ces recipients
EP1500600A4 (fr) * 2002-04-26 2008-03-26 Hokkai Can Recipients en plastique comportant un revetement sur leur surface interieure et procede de production de ces recipients
JP2005531688A (ja) * 2002-05-24 2005-10-20 ショット アーゲー ワークピースの処理装置および処理方法
US7810448B2 (en) 2002-05-24 2010-10-12 Schott Ag Apparatus and method for the treating of workpieces
US7754302B2 (en) 2002-05-28 2010-07-13 Kirin Brewery Company, Limted DLC film coated plastic container, and device and method for manufacturing the plastic container
JP4545073B2 (ja) * 2004-09-17 2010-09-15 三菱重工業株式会社 ガスバリア膜及び容器
JP2006111967A (ja) * 2004-09-17 2006-04-27 Mitsubishi Heavy Ind Ltd ガスバリア膜及び容器
JP2007131888A (ja) * 2005-11-09 2007-05-31 Toppan Printing Co Ltd プラズマ処理装置
JP4736723B2 (ja) * 2005-11-09 2011-07-27 凸版印刷株式会社 プラズマ処理装置
WO2010095011A1 (fr) 2009-02-18 2010-08-26 Council Of Scientific & Industrial Research Procédé pour déposer du carbone de type diamant sous la forme d'un revêtement protecteur sur une surface interne d'un objet façonné
CN106986085A (zh) * 2016-01-20 2017-07-28 铨宝工业股份有限公司 确保包装饮用水完全出水的包装饮用水充填方法
WO2020148487A1 (fr) * 2019-01-17 2020-07-23 Innovative Systems Et Technologies (Isytech) Procede et dispositif de traitement pour le depot d'un revetement a effet barriere
FR3091875A1 (fr) * 2019-01-17 2020-07-24 Innovative Systems Et Technologies (Isytech) Procédé et dispositif de traitement pour le dépôt d’un revêtement à effet barrière
AU2019423598B2 (en) * 2019-01-17 2022-09-01 Innovative Systems Et Technologies (Isytech) Treatment method and device for depositing a barrier-effect coating
US11898241B2 (en) 2019-01-17 2024-02-13 Innovative Systems Et Technologies (Isytech) Method for a treatment to deposit a barrier coating
WO2022187444A3 (fr) * 2021-03-04 2022-10-13 Yeti Coolers, Llc Revêtement de surface de nécessaire à boire
US12129078B2 (en) 2022-03-03 2024-10-29 Yeti Coolers, Llc Surface coating of drinkware

Also Published As

Publication number Publication date
AU1055801A (en) 2001-05-14

Similar Documents

Publication Publication Date Title
KR100532930B1 (ko) 계면층을 갖는 플라스마증착 장벽코팅, 이러한 장벽코팅의 코팅방법과, 이러한 방법으로 코팅된 용기
US5704983A (en) Methods and apparatus for depositing barrier coatings
EP1852522B1 (fr) Film depose par evaporation sous vide par un procede de depot chimique en phase vapeur assiste par plasma
KR100545908B1 (ko) 장벽코팅
JP5023056B2 (ja) 側面の少なくとも１つにプラズマにより形成された薄膜コーティングを有するポリマー製品およびこのような製品の製造方法
FR2918301A1 (fr) Revetement barriere depose par plasma comprenant au moins trois couches, procede d'obtention d'un tel revetement et recipient revetu d'un tel revetement
WO2001032513A1 (fr) Recipient en plastique revetu d'une couche de cda exempte d'azote, procede et appareil utilises pour sa fabrication
JP4566719B2 (ja) 炭素膜コーティングプラスチック容器の製造方法、プラズマｃｖｄ成膜装置及びそのプラスチック容器
EP2420592B1 (fr) Procédé pour fabriquer un récipient en matière plastique revêtu d'un film mince de barrière vis-à-vis des gaz
WO2003085165A1 (fr) Appareil de formation d'un film cvd plasma et procede de fabrication d'un conteneur plastique de revetement de film cvc
JP2004307935A (ja) ガスバリア性薄膜コーティングプラスチック容器の製造方法
EP1500600A1 (fr) Recipients en plastique comportant un revetement sur leur surface interieure et procede de production de ces recipients
JP4664658B2 (ja) プラズマｃｖｄ成膜装置及びガスバリア性を有するプラスチック容器の製造方法
JP4279127B2 (ja) ガスバリア性薄膜コーティングプラスチック容器の製造装置及びその製造方法
JP4945398B2 (ja) 口部極薄炭素膜コーティングプラスチック容器の製造方法
JP3123979U (ja) 成膜装置
US20080145651A1 (en) Method for Manufacturing a Pecvd Carbon Coated Polymer Article and Article Obtained by Such Method
DK1893788T3 (en) POLYMER ARTICLE WITH A THIN COATING MADE ON AT LEAST ITS PLASMA SIDE
JP2003321031A (ja) 内面被覆プラスチック容器及びその製造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref country code: JP

Ref document number: 2001 534680

Kind code of ref document: A

Format of ref document f/p: F

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 10110664

Country of ref document: US

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase