JP4050649B2 - How to use bottles for carbon film coating beverages - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a method for using a refillable beverage bottle.
[0002]
[Prior art]
In general, plastic containers are widely used as packaging containers in various fields such as the food field and the pharmaceutical field because of their various characteristics such as easy molding, light weight, and low cost.
[0003]
However, as is well known, plastics have the property of permeating low-molecular gases such as oxygen and carbon dioxide, and further have the property of sorbing low-molecular organic compounds inside. Therefore, compared with other containers such as glass, plastic containers are subject to various restrictions in terms of usage and usage.
[0004]
Here, sorption refers to a phenomenon in which a low molecular organic compound permeates and diffuses into a plastic composition and is absorbed in the plastic.
[0005]
For example, when a carbonated beverage such as beer is filled in a plastic container, the beverage, which is the content, deteriorates over time due to oxygen that permeates the plastic and penetrates into the container. The carbon dioxide gas permeates through the plastic and is released to the outside of the container, so that the carbonated beverage becomes an unintentional beverage.
[0006]
In addition, when a beverage having a fragrance component such as orange juice is filled in a plastic container, a fragrance component (eg, limonene of orange juice) contained in the beverage is sorbed onto the plastic, There is a possibility that the composition of the fragrance component is out of balance and the quality of the beverage is deteriorated.
[0007]
In addition, for plastic containers, elution of low-molecular compounds contained in the composition may be a problem. In other words, when a plastic container is filled with contents (especially liquids) that require purity, the plasticizer, residual monomers, and other additives contained in the plastic composition are eluted into the contents. There is a possibility of impairing purity.
[0008]
On the other hand, the collection of used containers is now a social problem, and the recycling of resources is being promoted. However, even if you try to use plastic containers as refill containers, unlike glass containers, collection after use In the meantime, if left in the environment, various low molecular weight organic compounds such as musty odor will sorb into the plastic container. Since this sorbed low molecular organic compound remains in the plastic after washing, when the plastic container is used as a refill container, the sorbed low molecular organic compound is contained in the contents filled as a different component. It gradually melts, resulting in deterioration of the quality of the contents and sanitary problems. For this reason, plastic containers are rarely used as returnable containers.
[0009]
In order to suppress the low-molecular gas permeation property of the plastic container and the low-molecular organic compound sorption property inside the plastic container as described above, the plastic is oriented to improve the crystallinity, or more Although a method of laminating a low-performance plastic or aluminum thin film is also used, none of them has completely solved the problems of gas barrier properties and sorption while maintaining the characteristics of the plastic container.
[0010]
Here, in recent years, a DLC (Diamond Like Carbon) film thin film forming technique has been known, and conventionally, a laboratory apparatus such as a beaker or a flask coated with a DLC film is known. This DLC film is made of carbon-carbon SP.^Three It is an amorphous carbon mainly composed of bonds, and is a hard carbon film that is very hard, excellent in insulation, has a high refractive index, and has a very smooth morphology.
[0011]
Conventionally, such a DLC film forming technique used for coating a laboratory instrument such as a beaker or a flask is disclosed in JP-A-2-70059.
[0012]
The apparatus for forming a DLC film described in Japanese Patent Laid-Open No. 2-70059 is as follows. That is, as shown in FIG. 16, a cathode 2 is arranged in a reaction chamber 1 having a carbon source gas inlet 1A and an exhaust hole 1B, and a laboratory instrument such as a beaker is placed in a space 2A formed in the cathode 2. 3 is accommodated. After the grounded anode 4 is inserted inside the experimental instrument 3, the inside of the reaction chamber 1 is depressurized by the exhaust from the exhaust hole 1B. Then, after the carbon source gas is introduced from the introduction port 1A, a high frequency is applied from the high frequency power source 5 to the cathode 3, and the DLC film is formed on the surface of the experimental instrument 3 by the plasma generated by exciting the carbon source gas. The
[0013]
[Problems to be solved by the invention]
However, since the cathode 2 and the anode 4 are accommodated in the reaction chamber 1 and the volume of the reaction chamber 1 is very large compared to the size of the experimental instrument 3 to be coated, the DLC film forming apparatus described above is vacuum The operation takes a lot of time and energy, and the DLC film forming apparatus has a forming speed of 10 to 1000 m / min, and its generation speed is slow, so that it is difficult to continuously produce at low cost. have.
[0014]
This conventional DLC film forming apparatus is intended for adding experimental value to laboratory equipment such as beakers and flasks, so that it does not matter production cost and production time. Since a large amount of inexpensive filling containers for beverages such as juice are required, this DLC film forming apparatus cannot be used for manufacturing beverage containers.
[0015]
Further, according to the DLC film forming apparatus described above, since the carbon source gas also enters the gap between the cathode 2 and the experimental instrument 3 to be coated, the coating can be performed only on the inner surface of the instrument 3. I can't.
[0016]
Unlike the case of a laboratory instrument such as a beaker or a flask, the filling container for beverages often has a chance of colliding or rubbing with each other in the manufacturing process in the factory or in the sales route. For this reason, when a DLC film is formed on the outer surface of a beverage filling container, the DLC film is thin and hard, and therefore, the DLC film itself may be damaged to impair the commercial value of the filling container. Therefore, for a filling container for beverages, it is required to form a DLC film only on the inner wall surface of the container.
[0017]
The present invention has been made to solve the above conventional problems. That is, the present invention eliminates the gas barrier properties and sorption problems of plastic while maintaining the characteristics of the plastic container, and enables returnable use, thereby expanding the range and form of use of the plastic container. An object of the present invention is to provide a method for using a bottle for a carbon film-coated beverage that can be produced at low cost and can be continuously produced at a low cost without causing any damage in handling.
[0018]
[Means for Solving the Problems]
  In order to achieve the above object, a method for using a carbon film-coated beverage bottle according to the present invention is a method for using a refillable carbon film-coated beverage bottle, wherein the recovered beverage bottle is washed. And a filling step of filling the beverage bottle washed by the washing step with a content, wherein the beverage bottle is formed on the inner wall surface of the integrally formed plastic bottle.By generating low temperature plasma of source gas only on the inner wall side of the bottle,A hard carbon film is formed, and the hard carbon film isObtained by applying high frequency power of 200 W or more and 1000 W or less per 700 ml volume,It is a dense hard carbon film with substantially zero sorption in a bottle of aroma components that are low molecular organic compounds.The density of the hard carbon film is 1.54 g / cm ³ The thickness of the hard carbon film is in the range of 0.05 to 5 μm.It is characterized by that.
[0019]
[Action]
  According to the carbon film-coated beverage bottle, the inner wall surface of the plastic containerUniformlyCoatedPreciseThe hard carbon film not only can significantly reduce the permeability of low-molecular inorganic gases such as oxygen and carbon dioxide, but also completely suppresses the sorption of various odorous low-molecular organic compounds. I can do it. Further, the transparency of the plastic container is not impaired by the formation of the hard carbon film. The hard carbon film is preferably a diamond-like carbon film. The diamond-like carbon film is a hard carbon film called an i-carbon film or a hydrogenated amorphous carbon film, and is an amorphous carbon film mainly composed of SP3 bonds.
[0020]
In addition, the carbon film-coated beverage bottle can be used as a returnable container instead of the conventional beverage glass container.
[0021]
【Example】
Embodiments of the present invention will be described below with reference to the drawings.
[0022]
FIG. 1 shows a production apparatus for producing a carbon film-coated beverage bottle used in the present invention. In this manufacturing apparatus, a ceramic insulating plate 11 is attached on a base 10, and an external electrode 12 is attached on the insulating plate 11. The external electrode 12 also serves as a vacuum chamber for forming a DLC film, and a space for accommodating the container 20 to be coated is formed therein. The space in the external electrode 12 is formed to be slightly larger than the outer shape of the container 20 accommodated therein. The container 20 is a beverage bottle, but may be a container used for other purposes.
[0023]
The external electrode 12 includes a main body portion 12A and a lid 12B that is detachably attached to the upper portion of the main body portion 12A so as to seal the inside of the main body portion 12A. A high frequency power supply 14 is connected to the external electrode 12 via a matching unit 13. Further, an exhaust pipe 15 is communicated with the space in the external electrode 12, and air in the space is exhausted by a vacuum pump (not shown).
[0024]
The internal electrode 16 is inserted into the space of the external electrode 12 and is disposed so as to be positioned at the center of the space. The internal electrode 16 is formed so that its outer shape can be inserted from the mouth 20A of the container 20 and is substantially similar to the internal shape of the container 20. It is preferable that the distance between the external electrode 12 and the internal electrode 16 be kept substantially uniform within a range of 10 to 150 mm at any position.
[0025]
A raw material gas supply pipe 17 is connected to the internal electrode 16, and a raw material gas flows into the raw material gas supply pipe 17 via a gas flow rate controller (not shown), and a blowout hole 16 </ b> A formed in the internal electrode 16. It comes to be blown out from. In order to uniformly diffuse the blown-out source gas, it is preferable that a plurality of these blowout holes 16A be formed on the side portion of the internal electrode 16 as shown in the drawing. However, the source gas is immediately and uniformly diffused. In this case, one may be formed on the top of the internal electrode 16. The internal electrode 16 is grounded via the source gas supply pipe 17.
[0026]
2 and 3, a plurality of (four in this embodiment) grooves 11A are formed in the insulating plate 11, and as can be seen from FIG. In the state where the container 20 is accommodated and the opening 20A of the container 20 is in contact with the insulating plate 11, the outer space 21A of the container and the exhaust pipe 15 formed between the inner wall surface of the external electrode 12 and the outer wall surface of the container 20 are disposed. Are communicated through the groove 11A.
[0027]
Next, a method for forming a DLC film by the manufacturing apparatus will be described.
[0028]
A plastic container 20 is inserted into and accommodated in the external electrode 12 from the upper opening of the main body 12A with the lid 12B removed. At this time, the internal electrode 16 is inserted into the container 20 from the mouth portion 20 </ b> A of the container 20. Then, after the mouth 20A is brought into contact with the insulating plate 11 and the container 20 is positioned in the external electrode 12, the lid 12B is closed, and the inside of the external electrode 12 is sealed. At this time, the distance between the inner wall surface of the external electrode 12 and the outer wall surface of the container 20 is kept substantially uniform, and the distance between the inner wall surface of the container 20 and the outer wall surface of the internal electrode 16 is also It is kept almost uniform.
[0029]
Thereafter, the air inside the external electrode 12 is exhausted by a vacuum pump, and the inside of the external electrode 12 is evacuated. At this time, not only the inner space 21B of the container 20 but also the outer space 21A between the outer wall surface of the container 20 and the inner wall surface of the external electrode 12 is exhausted and evacuated by the groove 11A formed in the insulating plate 11. The This is because, unless the external space 21A is also evacuated, the inside of the external space 21A becomes hot during plasma generation described later, which adversely affects the plastic material of the container 20.
[0030]
The degree of vacuum at this time is 10^-2-10^-Fivetorr is desirable. This is 10^-1If the above degree of vacuum is sufficient, the container has too many impurities and 10^-FiveThis is because it takes too much time and energy to evacuate if the degree of vacuum is less than that.
[0031]
Thereafter, a raw material gas of the carbon source is supplied from a gas flow rate controller (not shown) to the raw material gas supply pipe 17 and blown out from the blowout hole 16A formed in the internal electrode 16 into the vacuum internal space 21B. The supply amount of the source gas is preferably 1 to 100 ml / min, and the pressure in the internal space 21B is adjusted within 0.5 to 0.001 torr by supplying the source gas.
[0032]
Here, since the inside of the external space 21A is exhausted through the groove 11A, the pressure in the external space 21A decreases slightly later than the pressure in the internal space 21B. For this reason, immediately after exhaust, the pressure in the external space 21A is slightly higher than that in the internal space 21B. Therefore, if the source gas is supplied immediately after exhaust, the source gas blown into the internal space 21B will not enter the outer space 21A.
[0033]
As the raw material gas, aliphatic hydrocarbons, aromatic hydrocarbons, oxygen-containing hydrocarbons, nitrogen-containing hydrocarbons, etc. that are gaseous or liquid at room temperature are used. In particular, benzene, toluene, o-xylene, m-xylene, p-xylene, cyclohexane and the like having 6 or more carbon atoms are desirable. These raw materials may be used alone, or may be used as a mixed gas of two or more. Furthermore, these gases may be diluted with a rare gas such as argon or helium.
[0034]
After the supply of the source gas, electric power is supplied to the external electrode 12 from the high frequency power supply 14 via the matching unit 13. By applying this electric power, plasma is generated between the external electrode 12 and the internal electrode 16. At this time, the internal electrode 16 is grounded, but since the external electrode 12 is insulated by the insulating plate 11, a negative self-bias is generated in the external electrode 12, thereby the container 20 along the external electrode 12. A DLC film is uniformly formed on the inner wall surface.
[0035]
That is, the formation of the DLC film on the inner wall surface of the container 20 is performed by an improved plasma CVD method. According to this plasma CVD method, since the temperature at the time of forming the DLC film can be set to a relatively low temperature by using low temperature plasma, it is suitable for a case where an article having poor heat resistance such as plastic is used as a base. In addition, it is possible to form a DLC film having a relatively low cost and a large area.
[0036]
Here, the low temperature plasma is a plasma in which the electron temperature in the plasma is high and the temperature of ions and neutral molecules is significantly lower than that when the inside of the reactor is maintained at a low pressure, that is, so-called non-equilibrium. It means plasma in a state.
[0037]
When plasma is generated between the external electrode 12 and the internal electrode 16, electrons accumulate on the inner wall surface of the insulated external electrode 12, and the external electrode 12 is self-biased to a negative potential. On the external electrode 12 side, a potential drop of about 500 to 1000 V occurs due to the stored electrons. At this time, the presence of carbon dioxide gas as a carbon source in the plasma causes the positively ionized carbon source to selectively collide with the inner wall surface of the container 20 positioned along the external electrode 12. By bonding adjacent carbons, a hard carbon film made of a very dense DLC film is formed on the inner wall surface of the container 20.
[0038]
The hard carbon film made of a DLC film is a hard carbon film also called i-carbon film or hydrogenated amorphous carbon film (a-C: H), and SP.^Three An amorphous carbon film mainly composed of bonds.
[0039]
The thickness of the DLC film depends on the output of the high frequency, the pressure of the raw material gas in the container 20, the supply gas flow rate, the plasma generation time, the self-bias, the kind of the raw material, etc. In order to achieve both the improvement effect of the gas barrier property and the adhesion, durability, transparency and the like with the plastic, it is preferable to set the thickness to 0.05 to 5 μm.
[0040]
Similarly, the quality of the DLC film depends on the output of the high frequency, the pressure of the source gas in the container 20, the flow rate of the supply gas, the plasma generation time, the self-bias, the type of the source, and the like. Increasing the high frequency output, decreasing the pressure of the raw material gas in the container 20, decreasing the flow rate of the supply gas, increasing the self-bias and decreasing the carbon number of the raw material are all in the hardening of the DLC film, improvement of the denseness, compression stress Causes growth and increased brittleness. For this reason, in order to maximize the sorption suppression effect and gas barrier effect of low molecular weight organic compounds while maintaining the adhesion to the plastic and the durability of the film, the high frequency output is 50 to 1000 W, the raw material in the container 20 The gas pressure is set to 0.2 to 0.01 torr, the supply gas flow rate is 10 to 50 ml / min, the self-bias is -200 to -1000 V, and the source gas has about 1 to 8 carbon atoms. Is preferred.
[0041]
In order to further improve the adhesion between the DLC film and the plastic, before the DLC film is formed, plasma treatment is performed with an inorganic gas such as argon or oxygen so that the inner wall surface of the container 20 is activated. Also good.
[0042]
FIG. 4 shows a side cross section of a plastic container having a DLC film formed as described above. In the figure, 20A indicates a plastic material, and 20B indicates a DLC film formed on the inner wall surface of the plastic material 20A. Thus, the plastic container whose inner wall surface is coated with the DLC film 20B not only can remarkably reduce the permeability of low-molecular inorganic gases such as oxygen and carbon dioxide, but also various low-molecular substances having an odor. Sorption of organic compounds can be completely suppressed. Further, the formation of the DLC film does not impair the transparency of the plastic container.
[0043]
The plastic material forming the container 20 is polyethylene resin, polypropylene resin, polystyrene resin, cycloolefin copolymer resin, polyethylene terephthalate resin, polyethylene naphthalate resin, ethylene-vinyl alcohol copolymer resin, poly-4-methylpentene- 1 resin, polymethyl methacrylate resin, acrylonitrile resin, polyvinyl chloride resin, polyvinylidene chloride resin, acrylonitrile / styrene resin, acrylonitrile / butadiene / styrene resin, polyamide resin, polyamideimide resin, polyacetal resin, polycarbonate resin, polybutylene terephthalate Examples thereof include resins, ionomer resins, polysulfone resins, and tetrafluoroethylene resins.
[0044]
(1) DLC film thickness, (2) DLC density, (3) Adhesion 1, (4) Adhesion 2, (5) The results of each evaluation of alkali resistance, (6) carbon dioxide gas barrier property, (7) oxygen gas barrier property, and (8) sorption property of low molecular organic compounds (aroma components) are as follows.
[0045]
In addition, each evaluation was performed with the following method.
[0046]
(1) DLC film thickness
The inner surface of the container was previously masked with magic ink or the like and coated with DLC, then the masking was removed with diethyl ether or the like, and the film thickness was measured with a surface shape measuring device DECTACK3 manufactured by Vecco.
[0047]
(2) DLC density
The weight difference before and after the film formation was measured, and the density was calculated from the film thickness obtained in (1).
[0048]
(3) Adhesion 1
About the side wall part of the container, it carried out on condition of the following according to the cross-cut tape method of JISK5400.
[0049]
(1) Clearance gap between cuts: 1mm
▲ 2 ▼ Number of eyes: 100
(4) Adhesion 2
About the side wall part of the container, it carried out on condition of the following using the Shinto Kagaku make and continuous load type scratch test machine HEIDON22. The degree of adhesion was expressed by the vertical load applied to the scratching needle when the film began to peel off.
[0050]
(1) Scratch needle material, shape: diamond, 50μR
(2) Weighted speed: 100 g / min
(3) Table speed: 1000 mm / min
(5) Alkali resistance
The inside of the container was filled with an alkali solution added with sodium hydroxide so as to be 10 wt%, and immersed in a 75 ° C. hot water bath for 24 hours, and the shape change of DLC and the presence or absence of peeling were confirmed. As a result, a sample that did not change after immersion for 24 hours or more was shown as excellent, and a sample that did not change after immersion for 12 hours or more was shown as good.
[0051]
(6) Carbon dioxide barrier properties
Carbon dioxide gas permeation was measured at 25 ° C. using a PERMATRANC-4 model manufactured by MODERN CONTROL.
[0052]
(7) Oxygen gas barrier properties
The oxygen permeation amount was measured at 40 ° C. using OX-TRANTWIN manufactured by MODERN CONTROL.
[0053]
(8) Sorption of low molecular weight organic compounds (aroma components)
Using a low molecular weight organic compound (aroma component) having an odor as a kind of environmental material, a test was conducted with reference to the method of Matsui et al. (J. Agic. Food. Chem., 1992, 40, 1902-1905). .
[0054]
The procedure is as follows.
[0055]
(1) A 0.3% sugar ester solution to which 100 ppm of various aroma components (n-octane, n-octanal, n-octanol, ethyl hexanoate, d-limonene) is added is prepared to obtain a model flavor solution.
[0056]
(2) Fill the container with 700 ml of model flavor solution, cover the container, and store at 20 ° C for 1 month.
[0057]
(3) After 1 month, the model flavor solution is discarded, and the inside of the container is washed with distilled water at 60 ° C. and then dried.
[0058]
{Circle around (4)} Fill with diethyl ether and extract the aromatic components sorbed in the container.
[0059]
(5) Remove diethyl ether from the container and add anhydrous sodium sulfate to dehydrate.
[0060]
(6) Perform quantitative analysis by gas chromatography using amylbenzene as an internal standard. As a result, when an aqueous solution containing 1 ppm of a fragrance component is present in the container, the amount of the fragrance component sorbed in the container is displayed in μg. Therefore, the unit is μg / ppm / bottle.
[0061]
[Test 1]
A 700-ml polyethylene terephthalate resin container (Mitsui PET Resin Co., Ltd. PET resin, type L125) was accommodated in the external electrode 12 of FIG. 1 and fixed as a plastic container.
[0062]
Next, the vacuum pump is operated, and the inside of the external electrode 12 is set to 10^-FourAfter vacuuming (back pressure) to torr or less, as a pretreatment, argon is introduced into the plastic container at a flow rate of 30 ml / min so that the pressure becomes 0.04 torr, and 300 W of Rf power is applied to inject the inner surface of the container. Plasma treatment was performed. Thereafter, argon was used as an auxiliary gas, and toluene, cyclohexane, benzene or p-xylene was introduced into the container as a source gas, and DLC was uniformly coated on the inner surface of the container under the conditions shown in FIG.
[0063]
Test results
The results of each evaluation of film thickness, film formation rate, density, adhesion 1, adhesion 2, and alkali resistance are as shown in FIG. The density is 2.00 g / cm for both^Three The film was extremely dense.
[0064]
As a result of the cross-cut test, it was revealed that the adhesion with the polyethylene terephthalate resin was good and could withstand actual use. Further, it was found that the alkali resistance was not a problem, the DLC film was very stable, and the polyethylene terephthalate resin was completely protected.
[0065]
The results of oxygen permeability, carbon dioxide permeability and the degree of sorption of various aroma components are shown in FIG. The dense DLC film not only completely suppressed the sorption of aroma components, but also effectively suppressed the permeation of oxygen and carbon dioxide.
[0066]
Moreover, the transmission spectrum in the ultraviolet visible region of the trunk | drum of the plastic container which coat | covered DLC on the inner surface is shown by FIG.
[0067]
The transmittance decreased rapidly from about 500 nm to the ultraviolet region, suggesting that the coating of the DLC film is effective in suppressing deterioration of the contents due to ultraviolet rays.
[0068]
FIG. 9 is a Raman spectrum of a thin film coated on the body of a plastic container under the conditions of Test 1.
[0069]
[Test 2]
A DLC film was formed on the inner surface of the container by the same method as in Test 1, except that a polyacrylonitrile / styrene copolymer resin container (manufactured by Mitsubishi Monsanto Kasei: PAN resin, type L700) having a capacity of 700 ml was used as the plastic container. The conditions for forming the DLC film are as shown in FIG. Further, in the same manner as in Test 1, each test was conducted with respect to film thickness, density, adhesion 1, adhesion 2, alkali resistance, carbon dioxide gas barrier property, oxygen gas barrier property, and low molecular organic compound sorption.
[0070]
Test results
The test results for film thickness, film formation speed, density, adhesion 1, adhesion 2 and alkali resistance are as shown in FIG. The film thickness and density were good as in Test 1. As for Adhesion 1 and Adhesion 2, there was no problem as in Test 1, and the adhesion between DLC and acrylonitrile / styrene copolymer resin was the same as that of polyethylene terephthalate resin, and it was found that there was no practical problem. did.
[0071]
The results of oxygen permeability, carbon dioxide permeability, and the degree of sorption of various aroma components are shown in FIG. That is, it has been clarified that acrylonitrile / styrene copolymer resin is inherently excellent in gas barrier properties, and further, the permeation amount of oxygen and carbon dioxide reaches a very low level by coating DLC. The sorption amount of various fragrance components was below the detection limit as in Test 1, and there was no problem in sensory evaluation.
[0072]
[Test 3]
The container was coated with DLC in the same manner as in Test 1 except that a 700 ml cycloolefin copolymer resin container (Mitsui Petrochemical Co., Ltd .: COC resin type APL6015) was used as the plastic container. The conditions for forming the DLC film are shown in FIG. Further, in the same manner as in Test 1, film thickness, density, adhesiveness 1, adhesiveness 2, alkali resistance, carbon dioxide gas barrier property, oxygen gas barrier property, and low molecular organic compound sorption properties were tested.
[0073]
Test results
The results of each test of film thickness, film formation speed, density, adhesion 1, adhesion 2, and alkali resistance are shown in FIG. Similar to Test 1 and Test 2, there was no problem with any of the test items, and in particular, the adhesion between the plastic container and DLC was very good.
[0074]
The results of oxygen permeability, carbon dioxide permeability, and sorption of various aroma components are shown in FIG. Since cycloolefin copolymer resin is an olefin resin, it has been found that oxygen permeability, carbon dioxide permeability, and aroma component sorption amount are relatively large, but can be suppressed to a considerable level by coating with DLC.
[0075]
【The invention's effect】
As described above, the carbon film-coated beverage bottle used in the present invention has excellent gas barrier properties and can completely suppress the sorption of low organic compounds such as odor components, and can be used in a wide range of packaging containers. And can be used as a refillable returnable container. Moreover, since the hard carbon film is formed on the inner wall surface of the container in this carbon film-coated beverage bottle, there is no possibility that the formed hard carbon film is damaged during the handling of the container.
[0076]
In the case where the hard carbon film formed on the inner wall surface of the container is a diamond-like carbon film, the above effect becomes more remarkable.
[0077]
Further, the carbon film-coated beverage bottle can be used as a returnable container instead of the conventional beverage glass container.
[Brief description of the drawings]
FIG. 1 is a side sectional view showing one embodiment of a production apparatus used for producing a carbon film-coated beverage bottle used in the present invention.
FIG. 2 is an enlarged cross-sectional view showing a part of the embodiment.
FIG. 3 is a plan view showing an insulating plate of the same example;
FIG. 4 is a side sectional view showing one embodiment of a carbon film-coated beverage bottle.
FIG. 5 is a table showing conditions for forming a hard carbon film.
6 is a table showing evaluation results such as a film thickness of a hard carbon film formed under the conditions of FIG.
7 is a table showing evaluation results such as oxygen permeability of a hard carbon film formed under the conditions of FIG.
8 is a graph showing a transmission spectrum in an ultraviolet-visible region of a plastic container in which a hard carbon film is formed under the conditions of FIG.
9 is a graph showing a Raman spectrum of a hard carbon film formed under the conditions of FIG.
FIG. 10 is a table showing other conditions for forming a hard carbon film.
11 is a table showing evaluation results such as a film thickness of a hard carbon film formed under the conditions of FIG.
12 is a table showing evaluation results such as oxygen permeability of a hard carbon film formed under the conditions of FIG.
FIG. 13 is a table showing still other conditions for forming a hard carbon film.
14 is a table showing evaluation results such as a film thickness of a hard carbon film formed under the conditions of FIG.
15 is a table showing evaluation results such as oxygen permeability of a hard carbon film formed under the conditions of FIG.
FIG. 16 is a cross-sectional view showing a conventional technique.
[Explanation of symbols]
20 Container (plastic bottle)
20B DLC film (hard carbon film)

Claims (3)

A method of using a refillable carbon film-coated beverage bottle, a washing step for washing the collected beverage bottle, and a filling step for filling the beverage bottle washed by the washing step with contents The beverage bottle has a uniform hard carbon film formed on the inner wall surface of the integrally formed plastic bottle by generating low temperature plasma of the raw material gas only on the inner wall side of the bottle. The hard carbon film is a dense hard carbon film obtained by applying high-frequency power of 200 W or more and 1000 W or less per 700 ml volume and having substantially zero sorption in a bottle of a fragrance component which is a low molecular organic compound. der is, the density of the carbon film is at 1.54 g / cm ³ or more, carbon film thickness of the hard carbon film is characterized in that in the range of 0.05~5μm How to use the bottle for computing drinks.   The use of the carbon film-coated beverage bottle according to claim 1, wherein the hard carbon film is a dense hard carbon film having substantially zero sorption of d-limonene as the aroma component. Method.   The said hard carbon film is formed only in the inner wall surface of the said plastic bottle, The usage method of the bottle for carbon film coating drinks of Claim 1 or 2 characterized by the above-mentioned.

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