JP2001231771A - Plug for vacuum sample collection container and method for producing the same - Google Patents

Abstract

(57) [Summary] [Problem] A detachable vacuum sample collection that is excellent in productivity, can sufficiently maintain the degree of decompression in a sample collection container, and is excellent in needle tube finger penetration and needle hole sealability. Provided is a container plug and a method for producing the same. SOLUTION: This is a plug for a vacuum sample collection container capable of hermetically sealing the open end of the sample collection tube so that the inside of the sample collection tube can be maintained in a reduced pressure state. A plug for a vacuum sample collection container formed with a coating of an object.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vacuum sample collecting container for collecting a sample in an analysis test of a liquid sample such as blood or urine or a gaseous sample such as breath or the atmosphere of a working environment. The present invention relates to a plug for a specimen collection container and a method for producing the same.

[0002]

2. Description of the Related Art Samples of a vacuum sample collection system include:
Blood is the most common. Therefore, in the following description, a vacuum blood collection container will be described as an example of a vacuum sample collection container.

A typical conventional vacuum blood collection system is described in, for example, Japanese Patent Application Laid-Open No. 62-227316. A vacuum blood collection container is provided with a bottomed tubular blood collection tube main body and an open end of its tube. And an airtightly fitted plug.
Also, JP-A-59-228831 and JP-A-3-5-5
No. 05320 describes a variation of the plug.

[0004] As a material used for the stopper, a gas barrier property for maintaining the degree of decompression inside the blood collection container is required, and a needle hole sealing property after removing the needle tip is required. Therefore, the stopper is made of a crosslinked butyl rubber (crosslinked II) which is a rubber elastic body that can be pierced with a needle and has excellent gas barrier properties.
R, also referred to as crosslinked isobutylene / isoprene rubber).

However, the crosslinked butyl rubber has a problem that it requires a long time in the vulcanization reaction step, and furthermore, it has to remove water-soluble substances by washing with water. For this reason, JP-A-57-59536, JP-A-58-58057 and JP-A-61-64253 propose plugs made of injection-moldable thermoplastic resin or thermoplastic elastomer. Have been.

Japanese Patent Application Laid-Open No. 57-59536 discloses that a plug having a high gas barrier property is applied to a stopper body made of a thermoplastic elastomer having a poor gas barrier property, or a film having a high gas barrier property is formed of a thermoplastic elastomer. Plugs buried inside have been proposed. However, the need for such a deposition or embedding step sacrifices the greatest advantage of employing a thermoplastic elastomer, high productivity.

JP-A-58-58057 and JP-A-6-58057
Japanese Patent Application Laid-Open No. 1-64253 and the like propose a plug body which can be injection-molded and has excellent productivity. In these methods, a thermoplastic resin or a thermoplastic elastomer is used as a material that can be injection-molded, but in order to ensure elasticity and gas barrier properties, uncrosslinked butyl rubber or a flat inorganic filler is used. Has been blended. However, since such a compound is inferior in the needle hole sealing property, it is necessary to incorporate a different kind of thermoplastic elastomer member into the needle tube piercing portion, and it cannot be said that the productivity is not significantly improved.

Further, Japanese Patent Application Laid-Open No. S57-154057,
JP-A-1-76831, JP-A-2-174835
In the publication, a plug body is proposed in which a thin sheet of aluminum foil or nylon and a needle-hole-sealing rubber sheet or a rubber chip or the like are laminated and adhered directly to the opening end of the blood collection container or bonded. I have. This sheet-shaped plug uses a gas-impermeable material such as aluminum foil, so that it has excellent gas barrier properties, and because of its thinness, the penetration resistance of the blood collection needle is extremely small. It is said that the work load can be greatly reduced. Also, productivity is high.

However, since the above-mentioned sheet-like plugs are made by laminating and sticking materials having extremely different elasticities, they are separated from each other by insertion resistance of a blood sampling needle or a sampling nozzle needle of an analyzer. High risk of destruction. Also, once opened, it cannot be re-attached (re-sealed), of course, so that the storage of the sample has to be provided with a separately removable plug. Therefore, as a stopper for a vacuum sample collection container, it is excellent in productivity, and can sufficiently maintain the degree of decompression in the sample collection container, and is detachable and excellent in needle tube piercing property and needle hole sealing property. Things were sought.

[0010]

SUMMARY OF THE INVENTION In view of the above, the present invention has excellent productivity, can maintain a sufficient degree of reduced pressure in a sample collection container, and has a needle tube piercing property and a needle hole sealing property. An object of the present invention is to provide an excellent detachable plug for a vacuum sample collection container and a method for manufacturing the same.

[0011]

DISCLOSURE OF THE INVENTION The present invention provides a plug for a vacuum sample collection container which can hermetically seal the open end of the sample collection tube so that the inside of the sample collection tube can be maintained in a reduced pressure state. It is a plug for a vacuum sample collection container having a metal oxide film formed on the surface. Hereinafter, the present invention will be described in detail.

The plug for a vacuum sample collection container of the present invention can hermetically seal the open end of the sample collection tube so that the inside of the sample collection tube can be maintained at a reduced pressure.
The form of the plug for a vacuum collection container of the present invention that seals the open end of the sample collection tube is not particularly limited, and may be a type that can be detachably fitted to the open end of the sample collection tube. Although it may be of the type that is sealed by fusing directly to the open end of the sample collection tube, it can be easily resealed once opened, and it is necessary to prepare another stopper for storing the sample. Therefore, it is preferable that it can be detachably fitted to the open end of the sample collection tube.

In the plug for a vacuum sample collection container of the present invention, the material of the plug itself (hereinafter, referred to as a plug) is not particularly limited.
Polybutene, polyester, polyacrylonitrile, polyamide, polyarylate, polyacetal, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyurethane, ethylene-vinyl alcohol copolymer, acrylonitrile-styrene copolymer, ethylene-ethyl acrylate copolymer, Thermoplastic resin or thermoplastic elastomer such as ethylene-vinyl acetate copolymer, styrene-hydrogenated butadiene block copolymer, styrene-hydrogenated isoprene block copolymer; crosslinked butyl rubber, thermoplastic elastomer, polyisobutylene and crosslinked butyl rubber; And the like. These may be used alone or in combination of two or more. When a plurality of types are used in combination, a plurality of types of material layers may be laminated, or a plurality of types may be mixed and used.

The shape (structure) of the stopper is not particularly limited. For example, as long as the stopper is removably fitted to the open end of the sample collection tube, as shown in FIG. Has a gripper 1 for gripping and holding with a fingertip during attachment / detachment work.
0, and a lower portion in which a fitting portion 30 having a substantially cylindrical shape to be fitted to the sample collection tube is formed.

The method of forming the plug is not particularly limited, and examples thereof include injection molding, vacuum molding, and extrusion molding. As described above, the material, shape (structure), molding method, and the like of the plug used for the plug for a vacuum sample collection container of the present invention are not particularly limited, but from the viewpoint of production efficiency, thermoplastic resin or heat It is preferable that the elastomer is produced by injection molding or the like by combining one or more kinds of plastic elastomers.

The plug for a vacuum sample collection container according to the present invention comprises a metal oxide film formed on the surface of the plug. By forming a metal oxide film on the surface of the plug, the plug is provided with excellent gas barrier properties.
In addition, since the metal oxide film has a dense structure,
Since the gas barrier property is extremely high even for a thin film of 1 μm or less, there is no need to give a thickness to the metal oxide film, and even when laminated on a plug made of a resin or the like, it can be adapted to the bending deformation of the plug. Following this, the risk of delamination or destruction is significantly reduced as compared to when aluminum sheets are laminated and bonded.

In the plug for a vacuum sample collection container of the present invention, the method of forming a metal oxide film on the surface of the plug is not particularly limited, and a spraying method, a plasma CVD method, a sol-gel method, and a sintering method can be used. Any known method such as a method of combining the above may be used. When the plug is made of a thermoplastic resin, a thermoplastic elastomer, or the like, a plasma CVD method is preferable because processing (film formation) can be performed at a relatively low temperature. In addition, the film formed by the plasma CVD method includes:
Since the film thickness is small, the material cost is low and the film can be formed in a short time, so that the production cost is low.

The configuration of the apparatus for carrying out the above-mentioned plasma CVD method, a reactive gas such as metal alkoxide and oxygen which are constituents of a metal oxide, and a carrier gas such as argon and helium (hereinafter, both gases are collectively referred to as There are no particular restrictions on the operating conditions and the like, and examples thereof include a method for treating a sheet-like material disclosed in JP-A-7-90592, JP-A-7-304127, and the like;
JP-A-5-192374, JP-A-60-2255
Conventionally known examples, such as a method used for forming a coating on the surface of the blood collection tube main body disclosed in Japanese Patent Publication No. 40 and the like, may be used.

However, by the plasma CVD method,
Even if a metal oxide film is formed on the surface of the plug, if the adhesion between the plug and the film is poor, the film may be easily peeled off due to abrasion or the like. The material of the stopper is ethylene,
In the case of a non-polar olefin resin such as propylene or a non-polar elastomer such as styrene / butadiene / styrene (SBS) or styrene / isoprene / styrene (SIS), there is a risk that the coating of the metal oxide will peel off from the plug. Will be even higher.

Therefore, in the plug for a vacuum sample collection container according to the present invention, the metal oxide film is formed by introducing a polar group containing oxygen and / or nitrogen into the surface of the plug in advance. Preferably, there is. Before forming a metal oxide film, oxygen and / or
Alternatively, when a polar group containing nitrogen is introduced, and then a metal oxide is formed so as to be laminated on the surface, the adhesion between the plug and the metal oxide film can be improved.

In order to form a metal oxide film via a polar group containing oxygen and / or nitrogen as described above,
After the plug is housed in the plasma CVD reactor and evacuated to a predetermined degree of reduced pressure, instead of suddenly introducing a raw material gas for forming a metal oxide film, first, oxygen,
A plasma reaction may be caused by introducing nitrogen, hydrogen, or air containing these. In the first step, a polar group containing oxygen and / or nitrogen, for example, an amino group, a carbonyl group, and other ozonides are introduced into the surface of the plug.
Then, as a second step, a source gas for forming a metal oxide film is introduced, and a metal oxide film may be formed by a plasma reaction.

When the introduction of steam is added after the first step and before the second step, the ozonide is hydrolyzed to form a polar group such as a hydroxyl group or a carbonyl group.

In the plug for a vacuum sample collection container according to the present invention, the metal oxide film is made of an oxide of one or more metal elements selected from the group consisting of silicon, aluminum, magnesium, titanium and zirconium. Is preferred. By being composed of the metal oxide as described above, the metal oxide coating has excellent gas barrier properties and adhesion to the plug, so the obtained plug for a vacuum sample collection container is: The degree of decompression of the sample collection container can be maintained for a long period of time. Among them, silicon is more preferable because the reactive gas is easily available.

In the above-mentioned metal oxide film, the purity of the metal oxide does not need to be 100%, but may partially include the structure as a metal hydroxide. Further, the metal oxide film does not need to be formed on the entire surface of the stopper, and when fitted to the sample collection tube, the surface facing the inside and the surface facing the outside of the tube are not required. What is necessary is just to form continuously on at least one surface.

Further, when the metal oxide film is formed by the plasma CVD method as described above when manufacturing the plug for a vacuum sample collection container of the present invention, the plug may be formed during the metal oxide film formation reaction. It is preferable to keep stirring the plug body in the plasma CVD reaction chamber capable of accommodating many bodies.

When forming a metal oxide film by the plasma CVD method, if a large number of plugs are accommodated in a pile at one time in the reaction vessel in order to increase production efficiency, not only the influence of the unevenness of the plug shape but also the influence of the unevenness of the plug shape is obtained. As a result of the overlapping of the plugs, the degree of exposure of each plug surface to the plasma gas is not constant, and the formed metal oxide film tends to be uneven, but the specimen is agitated during the film formation reaction. By continuing,
Since the surface of the plug is uniformly exposed to the plasma gas, a substantially continuous film can be formed on the surface of the plug, and a plug for a vacuum sample collection container having excellent gas barrier properties can be efficiently produced. Can be. The method for manufacturing the above-described plug for a vacuum sample collection container is also one of the present invention.

Since the plug for a vacuum sample collection container of the present invention has the above-described configuration, it has a high gas barrier property and can maintain a reduced pressure in the sample collection container for a long period of time. Also, it has excellent needle tube piercing property and needle hole sealing property.
Furthermore, it is excellent in productivity and can be made detachable.

[0028]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 (Preparation of Sample) A plug having the shape shown in FIG. 1 was prepared by using polyethylene (PE) for the grip portion 10, and styrene for fitting the needle tube piercing portion 20 and the sample collection tube to styrene. It was prepared by a two-material injection molding method using a / butadiene / styrene (SBS) thermoplastic elastomer. In FIG. 1, (a)
Is a schematic view of the prepared plug viewed from above, (b) is a schematic view of the plug viewed from the front, (c) is a plug of (a) of FIG.
FIG. 4D is a schematic cross-sectional view when cut at −A ′, and FIG. 4D is a schematic view of the plug viewed from below.

Subsequently, the plasma C
By the VD method, as a first step, air was subjected to a plasma reaction to introduce a polar group into the plug body surface. Thereafter, as a second step, hexamethyldisiloxane and oxygen were introduced as a reaction gas and argon was introduced as a carrier gas to form a silicon oxide film on the entire surface of the plug. The obtained plug for a vacuum sample collection container was stoppered under reduced pressure into a 7 mL hard glass test tube to prepare two vacuum sample collection containers for collecting 6 mL.

(Evaluation) One of the prepared vacuum sample collection containers was subjected to 3
The water heated to 0 ° C. was sucked, and the initial suction water amount was measured. The remaining one was aged at 55 ° C. for 10 days, and the amount of inhaled water after the aged was measured in the same manner. The results are shown in Table 1.

Comparative Example 1 (Preparation of Sample) Two vacuum sample collection containers were prepared in the same manner as in Example 1 except that the silicon oxide film was not formed by the plasma CVD method. Further, evaluation was performed in the same manner as in Example 1 using the obtained vacuum sample collection container. The results are shown in Table 1.

[0033]

[Table 1]

From Table 1, it can be seen that the vacuum sample collection container using the stopper of Example 1 having a silicon oxide film formed on the surface by plasma CVD has a high gas barrier property. The reduced pressure was maintained, and the temporal change in the amount of suction water was suppressed. On the other hand, in the vacuum sample collection container using the stopper of Comparative Example 1 in which the silicon oxide film was not formed, the pressure change in the container was not maintained, and the temporal change in the amount of suction water was large.

[0035]

As described above, the plug for a vacuum sample collection container of the present invention has the above-described structure, so that it is excellent in productivity and can sufficiently maintain the degree of reduced pressure in the sample collection container for a long period of time. It is excellent in needle tube penetration and needle hole sealing.

[Brief description of the drawings]

FIG. 1A is a schematic view showing a shape of an upper surface of a plug manufactured in an example of the present invention. (B) It is a schematic diagram which shows the shape of the front of the plug produced in the Example of this invention. (C) A- of the plug produced in the example of the present invention
It is a schematic diagram which shows the cross section in A '. (D) It is a schematic diagram which shows the shape of the bottom surface of the plug produced in the Example of this invention.

[Explanation of symbols]

 10 gripping part 20 piercing part 30 fitting part (fitting surface)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G01N 33/48 A61B 5/14 300E F-term (Reference) 2G045 AA01 CA25 HA04 HB02 HB20 3E084 AB01 CA01 CB04 CC03 CC04 CC05 DA01 DC03 DC04 DC05 EC01 EC03 EC04 EC05 EC09 FA09 GA08 GB12 4C038 TA01 UD01 UD03 4F073 AA17 BA19 BA20 CA01 CA02 CA62 CA63 CA69 CA72 4K030 BA01 BA22 BA42 BA43 BA44 BA46 CA07 CA11 DA02 FA01 GA09 LA01 LA11

Claims (5)

[Claims] 1. A plug for a vacuum sample collection container capable of hermetically sealing an open end of a sample collection tube so that the inside of the sample collection tube can be maintained in a reduced pressure state. A plug for a vacuum sample collection container, comprising an oxide film formed thereon. 2. The metal oxide film is formed by introducing a polar group containing oxygen and / or nitrogen into the plug body surface in advance.
The plug for a vacuum sample collection container according to claim 1, wherein the plug is formed. 3. The metal oxide film according to claim 1, wherein the metal oxide film comprises at least one metal element oxide selected from the group consisting of silicon, aluminum, magnesium, titanium and zirconium. Of a vacuum sample collection container. 4. The plug for a vacuum sample collection container according to claim 1, wherein the plug can be detachably fitted to an open end of the sample collection tube. 5. The vacuum according to claim 1, wherein the plug is continuously stirred in a plasma CVD reaction chamber capable of accommodating a large number of plugs during a reaction for forming a metal oxide film. A method for producing a plug for a sample collection container.