JPH02305841A - Gas barrier material, container prepared therefrom and its production - Google Patents

Abstract

PURPOSE:To provide a gas barrier material which is transparent, excellent in gas barrier properties, etc., and desirable for use in the production of a vacuum blood sampling tube by constituting it from a fluororesin having a specified atomic ratio of the contained fluorine atoms to the contained hydrogen atoms. CONSTITUTION:The inside and/or outside of a container of a plastics is sputtered by using a fluororesin such as polytetrafluoroethylene or tetrafluoroethylene/hexafluoropropylene copolymer as a target. In this way, a gas barrier film comprising a fluororesin having an atomic ratio of the contained fluorine atoms to the contained hydrogen atoms >=1 can be formed. The obtained container such as a vacuum blood sampling tube can keep its inside vacuum even when stored for a long time, can prevent a gas such as steam from being penetrated into the inside, prevents the water in the inside from evaporating to the outside, and can maintain the contains for a long time stably.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a gas barrier bamboo material for preventing gas permeation on the wall surface of a container whose main body is made of plastic, such as a vacuum blood collection tube, and its use. This invention relates to a container using the same and a method for manufacturing the same.

[Prior Art] Generally, in a clinical test, when performing a blood biochemical test or an immune system test, blood is collected into a vacuum blood collection tube, coagulated, and serum is separated. Various components in this serum, such as proteins, fats, enzymes, electrolytes, etc., are then tested, and based on these, it is determined whether the patient is normal or abnormal.

Conventionally, glass tubes have been used as this type of blood collection tube, but recently, plastic blood collection tubes have been used because they are lightweight and less likely to break.

By the way, when such blood collection tubes are manufactured at a factory, the pressure reduction value is set to an appropriate level according to the amount of blood to be collected inside the tube, and blood collection tubes manufactured in this way are
The device is kept at the user's location for two to three years until it is used at a hospital or the like.

[Problems to be Solved by the Invention] However, conventional vacuum blood collection tubes made of plastic are more permeable to gas than those made of glass tubes. For this reason, external gas may permeate into the tube, making it impossible to maintain the desired reduced pressure value, and in blood collection tubes that have a chemical liquid sealed inside, water vapor evaporates to the outside through the tube wall, so the sealed chemical liquid, etc. There have been reports that the concentration has changed. In addition, there have been reports that water vapor can enter the blood collection tube through the tube wall, causing the medicine to absorb moisture and deteriorate in quality in tubes that contain dry, solid medicine. Such problems have similarly occurred in the packaging of foodstuffs, such as rice crackers, which are susceptible to deterioration due to moisture.

For this reason, it is common practice at present to commercialize liquid sampling tubes using packaging such as aluminum foil, but packaging using aluminum foil does not allow visual confirmation of the internal condition. During that time, there was Z. .

The present invention has been made in view of such problems, and includes:
Without sacrificing the advantages of plastic products, which are lightweight and hard to break, it maintains the desired reduced pressure value without the need for aluminum foil packaging, prevents internal liquid from evaporating, and prevents moisture absorption and deterioration of internal products, etc. To provide a gas barrier bamboo material that is suitable for long-term storage, has excellent transparency, and allows the internal state to be visually confirmed, a container using the same, and a method for manufacturing the same. The purpose is to

[Means for Solving the Problems] In order to solve the above conventional problems, the gas barrier bamboo material according to the present invention is formed of a fluororesin, and the atomic ratio of fluorine to hydrogen contained in the resin is 1. It is characterized by being larger than .0. Further, the gas barrier substrate according to the present invention is characterized in that a gas barrier coating made of the gas barrier bamboo material is formed on the surface. Furthermore, the container according to the present invention includes a container body made of plastic, an inner surface of the container body, and/or a container body made of plastic.
or a gas barrier film provided on the outer surface and formed of the gas barrier bamboo material; in particular, the gas barrier film has a thickness of 1 μm to 10 μm; It is preferable to use transparent resin.

Further, the liquid collection tube according to the present invention includes a bottomed plastic tube having one end open and the other end closed, and a sealing member for sealing the opening of the bottomed tube. The liquid pipe is characterized in that a gas barrier coating made of the gas barrier material is provided on the inner and/or outer surface of the bottomed pipe body.

Furthermore, the package according to the present invention includes a plastic package body and a gas barrier coating provided on the inner and/or outer surface of the package body and made of the gas barrier material. Features.

Furthermore, the method for manufacturing a container according to the present invention includes a step of forming a gas barrier film on the inner and/or outer surface of the plastic container body by sputtering using a fluororesin as a target. The target fluororesin is:
Polytetrafluoroethylene (PTFE), Tetraf V
loethylene-hexafluoropropylene copolymer (FEP)
), ethylene-tetrafluoroethylene copolymer (ET
FE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polyvinylidene fluoride (PVdF), polychlorotrifluoroethylene (
Preferably, the material is selected from the group of PC-FE).

In addition, in this specification, "gas barrier property" is not limited to completely blocking gas containing water vapor;
I O-” g/m2・day (40℃, 90%
This includes those that permeate gases of the order of R and H), and 5 means that it has a practical gas barrier property.

[Function] With the above configuration, the gas barrier material according to the present invention has an atomic ratio of fluorine to hydrogen contained in the fluororesin of 1.
．． Since it is larger than 0, if a film is formed using this material, gas barrier properties will be significantly improved. Therefore, if a part of the container is made of a gas barrier base material whose surface is coated with the gas barrier material according to the present invention, it can be adjusted to have the desired gas barrier properties.

In addition, in the liquid collection tube according to the present invention, gas permeation is virtually eliminated, so the reduced pressure value does not decrease, the water in the chemical solution sealed inside does not evaporate, and there is no possibility that there is any dry air inside. When a chemical is encapsulated, moisture absorption and deterioration of the chemical can be suppressed. Furthermore, the container according to the present invention has the effect that the medicines, foodstuffs, etc. inside thereof do not absorb moisture or deteriorate in quality, and can be stored stably for a long period of time.

Furthermore, in the method for manufacturing the container according to the present invention, the inner and/or outer surfaces of the plastic main body are subjected to sputtering treatment targeting fluororesin. A strong gas barrier film can be easily formed.

[Example J Hereinafter, an example of the present invention will be specifically described with reference to the drawings.

FIG. 1 is a sectional view showing a reduced pressure blood collection tube according to a first embodiment of the present invention. In the figure, l is a tube made of plastic and having an opening 2 at one end. The inner wall surface of the tubular body 1 is coated with an inner surface treatment agent made of, for example, silicone resin, while the outer surface is covered with a gas barrier film 3. The opening 2 of the tubular body 1 is sealed by a sealing member 4 so as to maintain a predetermined reduced pressure state with a chemical solution 5 such as an aqueous sodium citrate solution sealed inside. This sealing member 4 is made of, for example, aluminum and has a gas barrier film member 4a that covers the opening 2 of the tube body 1, and a film member 4a that is adhesively fixed to the opening 2 on the film member 4a. It is composed of a sealing rubber member 4b, and when blood is collected, these resealing rubber members 4b and film member 4a are
A hollow puncture needle provided on a blood collection holder (not shown) is punctured and penetrated into the inside of the tube body l. That is, blood introduced from the tip of the puncture needle flows into the blood collection tube through the hollow part of the puncture needle due to the reduced pressure inside the tube body 1, and thereby blood is collected.

Materials for the tube 1 include transparent materials such as polyethylene, polypropylene, poly(4-methylpentene-1), polystyrene, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, nylon, and acrylonitrile polymers. Plastics having some degree of resistance are preferred. In addition, the coating 3 should have an atomic ratio of fluorine to hydrogen of more than 1.0 and be transparent (this can be obtained by sputtering treatment using a fluororesin as a target). If the atomic ratio of hydrogen to hydrogen is less than 1.0, it will not be possible to obtain the required gas barrier property.This atomic ratio is determined when using a photoelectron spectrometer (ESCA) with the coating 3 as the outermost layer. , for example, λ is manufactured by JEOL Ltd. (7) JP
S-9DSX can be measured. Further, although the structure of this coating 3 can be predicted to some extent depending on the type of fluororesin used as the target, it cannot be determined with certainty because the details of the treatment method called sputtering using a plasma state have not yet been elucidated.

Fu XFM pilgrimage that can be used as a target is
Polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP)
), ethylene-tetrafluoroethylene copolymer (ET
FE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polyvinylidene fluoride (PI/dF), polychlorotrifluoroethylene (PCTFE), etc. In particular, polytetrafluoroethylene (PTFE), tetrafluoroethylene Ethylene-hexafluoropropylene copolymer (FEP) is preferred.

In addition, other blood coagulation promoter members,
An anticoagulant, a serum separating agent, etc. may be enclosed (and, depending on the purpose, the inner wall surface of the tube 1 may be subjected to a water repellent treatment or a hydrophilic treatment.

That is, in the reduced pressure blood collection tube according to this embodiment, the opening 2 of the tube body 1 is sealed with a gas barrier sealing member 4, and the outer surface is sealed with a coating 3 formed of a gas barrier material. Since it is covered, gas such as water vapor will not enter the inside through the tube wall even if it is stored for a long period of time, and the chemical solution inside will not evaporate to the outside through the tube wall. Therefore, it is possible to maintain a predetermined reduced pressure value and concentration of the chemical solution for a long time, and to prevent the amount of the chemical solution from decreasing. Moreover, since the coating 3 has transparency, the internal state can be easily confirmed visually. Furthermore, since the tube 1 is made of plastic, it is lightweight and has little risk of breakage.

In the first embodiment, the liquid collection tube according to the present invention was explained using a blood collection tube for collecting blood as an example.
It may also be used as a liquid collection tube for collecting other body fluids, such as ascites, urine, amniotic fluid, etc., and the inside is not limited to being under reduced pressure (it may also be at atmospheric pressure. Formation is not limited to the outer surface of the pipe body l, but may be formed on the inner surface or both surfaces. When forming on the inner surface, it is preferable to coat the inner surface treatment agent after forming the coating 3. Further, the structure of the coating 3 may be a layered coating using two or more of the above-mentioned materials.

FIG. 2 is a sectional view showing a part of a package according to a second embodiment of the present invention. This package is composed of a transparent thermoplastic resin film 11 and a gas barrier coating 12 formed on one side thereof, for example. The raw material for the resin film 11 is not particularly limited, but for example, polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), nylon (Ny
), polyvinyl chloride (PVC), polystyrene (PS
), polycarbonate (PC), etc. are used. The thickness of this film 11 is not particularly limited, but since it is used as a base material for packaging materials, it needs to have a thickness appropriate to its use.
On the other hand, it may not be strong enough and may cause tearing.
If it is too thick, processing becomes difficult. Generally, it is about 10 to 80 μm.

The material of the gas barrier film 12 is the same as that of the film 3 of the first embodiment, so its explanation will be omitted. The film thickness of this coating 12 is preferably 1 nn+ to 10 μm. Furthermore, it is preferably 30r+m to 5 μm. If it is thinner than 1 nm, gas barrier properties cannot be expected, and pinholes are likely to occur during the process of forming the coating 12.

In addition, if the thickness is 1/~10 μm, the inherent hardness of the fluororesin will be reflected, making it difficult to handle as a packaging material, and the transparency will be lost. are formed only on one side of the resin film 11, but they may be formed on both sides, or the resin film 11 and the coating 12 may be laminated alternately.Also, in order to protect the coating 12, the resin film 11 may be further laminated so that the coating 12 does not appear on the outermost surface.In that case, it may or may not be used with an adhesive, or surface treatment may be performed to improve adhesiveness. However, you don't have to do it.

Further, a part of the package may be made of a gas barrier base material coated with a gas barrier film 12, and the package may be adjusted to have a desired gas barrier property.

The package of this example is transparent and has a gas barrier.
Because of this property, the contents can be visually confirmed from the outside of the package, and the contents can be kept dry or moist for a long period of time.

Next, the inventor conducted the following experiment to confirm the effects of the present invention.

(Experimental Example 1) A tube l having the shape shown in Fig. 1 was molded using polyethylene terephthalate resin, and then sputtering was performed in an argon gas atmosphere using polytetrafluoroethylene (PTFE) as a target. The outer surface of the tube 1 has an atomic ratio of fluorine to hydrogen of 1.
A film 3 larger than 0 was formed. After that, a 3.8% aqueous solution of sodium citrate was added as a chemical solution to the inside of the tube.
65 mβ, and under reduced pressure, the opening 2 of the tube 1 was sealed with a gas barrier film member 4a made of aluminum foil as a base material, and then a resealing rubber member 4b made of natural rubber was bonded onto the film member 4a. Then, a blood collection tube with a blood sampling capacity of ff14.5mj2 was prepared. When we investigated the change over time in the amount of drug in this blood collection tube, we found that the change was within 5% in one year, and it was found to be fully usable.

(Experimental Example 2) A blood collection tube was prepared in the same manner as in Experimental Example 1, except that the tube l having the shape shown in Fig. 1 was molded from poly(4-methylpentene-1), and the drug solution from this blood collection tube was When the change in amount over time was investigated, it was found that it was within 5% in one year, which was also found to be sufficiently usable.

(Experimental Example 3) A blood collection tube was prepared in the same manner as in Experimental Example 1, except that the sputtering target was replaced with tetrafluoroethylene-hexafluoropropylene copolymer (FEPI), and the amount of drug solution in this blood collection tube was measured over time. When the change was investigated, it was found that the change was within 5% in one year, which was also found to be sufficiently usable.

(Experimental Example 4) A tube 1 having the shape shown in FIG. 1 was molded from poly(4-methylpentene-1), and a coating 3 was formed on its outer surface in the same manner as in Experimental Example 1. Thereafter, granular ethylenediaminetetraacetic acid dipotassium salt (EDTA-2
6a+g of K) is put in, and the opening 2 of the tube body 1 is sealed with a gas barrier film member 4a made of aluminum foil as a base material under reduced pressure.
b was adhered onto the film member 4a to prepare a blood collection tube with a blood collection volume of 5 m12. When the change over time in the amount of medicine in this blood collection tube was investigated, it was found that it was within 5% in one year, and no change was observed by visual inspection, indicating that it can be used satisfactorily.

(Experiment Example 5) Polyethylene terephthalate (PET) with a film thickness of 55 μm
One side of the film (manufactured by Toshiku Co., Ltd.) was subjected to sputtering treatment in an argon gas atmosphere using a polytetrafluoroethylene (PTFE) sheet (NR-924, manufactured by Freon Kogyo Co., Ltd.) as a target. The transmittance of this treated film at a wavelength of 500 nm was 98%, indicating high transparency. In addition, moisture permeability can be measured using a water vapor permeation measuring device (L-
80, manufactured by Lyssy), it is 1.5 g/m
"-day (40°C, 90% R, H). This packaging material was heat-sealed into a bag with a surface area of 200 em2, and 1.00 g of saturated hydrous polyvinyl alcohol gel was placed inside.
and sealed it. Then, after leaving it at room temperature for one month, the gel was taken out and its weight was measured, and it was found to be 0.9
1g, maintains sufficient water content, and is a gas barrier.
It was confirmed that it functions as a plastic packaging material.

(Experimental Example 6) Tetrafluoroethylene-hexafluoropropylene copolymer (FEP) (F -800-
As a result of carrying out the same procedure as in Experimental Example 5, except that a material (newly manufactured by Nagoya Royal Seisakusho Co., Ltd.) was used, the moisture permeability was 2.0 g/m"d.
ay (40°C, 90% R, H). This packaging material was heat-sealed to form a bag with a surface area of 200 cm, and 5.0 g of senbei (rice crackers) was placed inside and sealed.

After leaving it at room temperature for one month, the contents were taken out and weighed, which was 5.1 g, indicating that it was still sufficiently dry and functioned as a water vapor barrier packaging material. It was confirmed.

[Effects of the Invention] As explained above, the gas barrier material according to the present invention is transparent and has excellent gas barrier properties, so if a liquid collection tube is constructed using this material, it can be stored for a long period of time. , the internal reduced pressure value can be maintained, and gases such as water vapor will not enter the interior (Dried products will not absorb moisture or change in quality, and the internal moisture will not evaporate to the outside, It is also possible to maintain a moist state.
With this, the same effect can be obtained even if a container such as a package is configured. In addition, if the base material of the container body is made of transparent plastic, the internal state can be easily checked visually from the outside, and it is also lightweight and has little risk of breakage, especially for blood collection tubes and It has the advantage of being suitable for use in packaging. Furthermore, if a part of the container is made of the gas barrier base material according to the present invention, it is possible to adjust the container to have a desired gas barrier property.

[Brief explanation of drawings]

FIG. 1 is a longitudinal sectional view showing a vacuum blood collection tube according to a first embodiment of the present invention, and FIG. 2 is a sectional view showing a part of a package according to a second embodiment of the present invention. ■...Pipe body, 2...Opening 3.12-...Coating (gas barrier coating) 4...Murakami member 4a...Film member 4b...Resealing rubber member 11...Resin film

Claims (1)

Scope of Claims: (1) A gas barrier material formed of a fluororesin and characterized in that the atomic ratio of fluorine to hydrogen contained in the resin is greater than 1.0. (2) A gas barrier substrate comprising a gas barrier coating formed from the gas barrier material according to claim 1 on its surface. (3) A container body made of plastic, provided on the inner and/or outer surface of the container body, and claim 1
A container comprising a gas barrier coating formed of the gas barrier material described above. (4) The thickness of the gas barrier coating is 1 nm to 10 μm.
The container according to claim 3, wherein the container is m. (5) The container according to claim 3 or 4, wherein the container main body is made of transparent resin. (6) A liquid collection tube comprising a plastic bottomed tube with one end open and the other end closed, and a sealing member for sealing the opening of the bottomed tube, A liquid collection tube characterized in that a gas barrier coating formed of the gas barrier material according to claim 1 is provided on the inner and/or outer surface of the bottomed tube. (7) A plastic packaging body, provided on the inner and/or outer surface of the packaging body, and claim 1
A packaging body comprising a gas barrier coating formed of the gas barrier material described above. (8) A method for producing a container comprising the step of forming a gas barrier film on the inner and/or outer surface of a plastic container main body by sputtering using a fluororesin as a target. (9) The target fluororesin is polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyfluoride The method for manufacturing a container according to claim 8, wherein the container is selected from the group consisting of vinylidene and polychlorotrifluoroethylene.