CZ305291A3 - vacuum vessel for blood - Google Patents

Abstract

A new vacuum blood collection tube is a bottomed tubular body having a sealing part material. The body is made of a material comprising 99-92 wt.% polyethylene terephthalate and 1-8 wt.% poly m-xylylene adipamide contg. 1-100 ppm of a transition metal(s). The tube typically has an outside dia. of 10-16 mm and a length of 60-170 mm. The polyethylene terephthalate is usually prepd. by reacting ethylene terephthalate with terephthalic acid or its ester. Copolymers contg. at least 80% of ethylene terephthalate units are also available. Copolymerising monomers include isophthalic acid, naphthalene dicarboxylic acid, p-oxybenzoic acid derivs. and butane diols. The poly m-xylylene adipamide usually has at least 70% of m-xylyliene diamine and adipic acid units. Copolymerising monomers include p-xylylene diamine and sebacic acid. Tranisiton metals in the form of salts include cobalt acetate and nickel chloride.

Description

The invention relates to a blood vessel in which the internal vacuum changes only slightly over time.

BACKGROUND OF THE INVENTION

Vacuum blood vessels are used for tests and measurements such as biochemical tests, serological tests, haematological tests, blood sugar measurements, blood clotting tests, erythrocyte sedimentation rate tests and bacteriological tests. The blood vessel is generally a tube with one closed and one open end and a rubber stopper closing the open end. Before use, such a tube closed with a rubber stopper is evacuated and the exhausted interior is kept under vacuum so that the necessary amount of blood can be stored in the container between 2 and 20 ml of blood.

Until now, the material of the blood vessel is glass. However, glass is fragile during handling, centrifugation at high speed and similar operations, and has therefore recently been replaced by synthetic resins.

As such synthetic resins for vacuum blood vessels, polyesters, polyethylene, polypropylene and the like are chosen.

Of these, polyester is most commonly used because it is less permeable to gases than other resins. Compared to glass, however, polyester has a higher gas permeability because oxygen and nitrogen gas pass through the wall of the polyester tube. As a result, a vacuum cannot be maintained inside the polyester container during long-term blood storage. Thus, a blood vessel made of commonly used synthetic resins has a higher gas permeability than a glass vessel. Therefore, investigations have been made into packaging material for a vacuum blood vessel made of synthetic resin: for example, a vacuum blood vessel has been vacuum packaged and specific gas has been introduced into the interior of the container and has been found to penetrate into the interior of the container.

SUMMARY OF THE INVENTION

It is an object of the invention to provide a vacuum blood vessel made of synthetic resin so as to have a high gas impermeability and to maintain a vacuum therein for a long time until use.

SUMMARY OF THE INVENTION A vacuum tube-shaped blood vessel with one closed end and one open end is made of a composition comprising 99.5 to 92.0% by weight. % polyethylene terephthalate, 0.5 to 8.0 wt. a polyamide containing an m-xylylene group and 1 to 100 ppm of transition metal based on the total amount of polyethylene terephthalate and a polyamide with an m-xylylene group, and is provided with a closing device to close the open end to maintain vacuum inside the tube.

DETAILED DESCRIPTION OF THE INVENTION

The term closing device means a device for closing the open end of a pipe so as to maintain a vacuum inside the pipe. The locking device can be pierced with a needle. When using a blood vessel according to the invention, the end of the injection needle is inserted into a vein and the other end is plugged into a vacuum vessel. Due to the vacuum in the vial, blood flows from the vein through the needle into the vial. An example of a closure device is, for example, a rubber stopper having sufficient elasticity to be inserted and withdrawn from the pipe and sealing it, a closure device comprising gas-permitting means and a sealing means, and the like.

The term single-ended tube means a tube usable as a vacuum blood vessel. Such a tube may, for example, have an outer diameter of between 10 and 16 mm, a length of from 170 to 170 mm, and a thickness of between 1 and 2 mm.

Polyethylene terephthalate is a commonly used polyester which can be prepared by reacting ethylene glycol and terephthalic acid or an ester thereof, particularly dimethyl terephthalate. Said polyethylene terephthalate comprises polyethylene terephthalate containing repeating groups of ethylene terephthalate in a ratio not falling below 80%. Examples of the copolymerizable component are, for example, isophthalic acid, naphthalenedicarboxylic acid, a p-oxybenzoic acid derivative, butanediol and the like.

When shaping the pipe, it is most preferred that the molecular weight of said polyester polymer be 0.6 to 0.9 as an intrinsic viscosity (> [?]) To form a suitable closed-end pipe. The intrinsic viscosity is the value measured at 25 DEG C. in a solution formed by dissolving 0.25 g of polymer in 100 ml of a mixture containing 3 parts by weight. phenol and 2 parts by wt. 1,1,2,2-tetrachloroethane.

The polyamide containing the m-xylylene group used according to the invention comprises at least one diamine selected from the group consisting of (1) m-xylylenediamine, (2) a mixture of m-xylylenediamine and p-xylylenediamine and (3) a mixture of m-xylylenediamine and hexamethylenediamine, and as the acid component at least one carboxylic acid selected from the group consisting of adipic acid, pimelic acid, corkic acid, azelaic acid, and sebacic acid. According to the invention, poly-m-xylylene adipamide is the most preferred polyamide containing the m-xylylene group. It can be assumed that the polyamide with the m-xylylene group plays an important role in increasing the impermeability of the closed end of the gas pipe.

As transition metal, cobalt, nickel, rhodium and the like can be used. According to the invention, the transition metal is used in the form of a salt. Examples of the transition metal salt are, for example, cobalt acetate, cobalt naphthenate, cobalt stearate, nickel acetylacetonate, nickel chloride, rhodium chloride and the like.

The tube of the invention, produced by mixing a polyamide containing an m-xylylene group and a transition metal salt, absorbs oxygen gas.

The material of the present invention is a blend of polyethylene terephthalate, a polyamide containing an m-xylylene group, and a transition metal salt. All three components may be fed at once or alternatively the components may be premixed and then introduced into the mold.

Since the tube of the invention is formed from a mixture containing a polyamide with an m-xylylene group, the product may be yellowish. Such yellow coloration of the product can be avoided by properly balancing all three components. The yellow color can also be removed by adding up to 4% by weight, based on polyethylene terephthalate, of a substance containing a blue dye or a purple dye, which may be polyethylene terephthalate. This substance contains, for example, 1% dye. It is desirable that the substance containing the blue dye or the purple dye be added to the mixture in the same amount as the polyamide containing the m-xylylene group. Examples of such a dye useful in the present invention are blue # 1 (CI 42090), blue # 2 (CI 73015), blue # 201 (CI 73000), blue # 202 (CI 42052), blue # 203 ( CI 42052), Blue No. 204 (CI 69825), Blue No. 403, Magenta No. 201 (CI 60725), etc.

According to the invention, therefore, in the manufacture of the tube, the polyamide is mixed with the m-xylylene group, the polyester and the transition metal salt to make the tube impermeable to gas and absorb the gaseous oxygen. It is believed that the transition metal salt forms a catalyst to accelerate the absorption capacity. The interior of the evacuated tube can then be kept under vacuum for a long time before use.

According to the invention, 99.5 to 92.0 wt.%, Preferably 99 to 96 wt. and 0.5 to 8.0 wt.%, preferably 1 to 4 wt.% polyethylene terephthalate. polyamide with m-xylylene group. If the ratio of polyamide to the m-xylylene group is greater than 8% by weight, the tube becomes transparent and the cost of the material increases disproportionately. On the other hand, when the amount of polyamide with the m-xylylene group is less than 0.5% by weight, the oxygen absorption is impaired.

As mentioned, the composition for producing a blood vessel according to the invention in the form of a tube should contain 1 to 100 ppm, in particular 2 to 50 ppm, of the transition metal salt. When the amount of salt is greater than 100 ppm, the tube produced is tinted and non-transparent and the cost of the material is high. Conversely, when the amount of salt is less than 1 ppm, the catalytic efficiency accelerating the absorption of oxygen gas deteriorates.

The polymer used to manufacture the closed-end pipe may contain an additive or additives that do not adversely affect its function. Such additives may be, for example, antioxidants, ultraviolet blocking agents, extrusion aids, polymers quality enhancers and the like.

The invention will be illustrated by the following examples, comparative example and test examples, wherein all parts are by weight unless otherwise indicated. However, the invention is not limited to these examples and various modifications and modifications may be made therein.

Examples 1 to 10 and Comparative Examples 1 to 3

Using the materials summarized in Table 1, tubes with one closed and one open end were prepared, for an internal content of 5 ml. The tubes had a wall thickness of 1.3 mm, a length of 75 mm and an inner diameter of 10.8 mm. Each tube was tightly stoppered with a butyl rubber rubber stopper.

Ten containers were made for each group. In Table 1, polyethylene terephthalate, poly-m-xylylene group poly-m-xylylene adipamide and blue anthraquinone dye were used as the polyester.

Table 1

Number weight ratio polyester / polyamide with m-xylylene group / blue dye substance cobalt concentration (ppm) Ex 100/1/0 23 Ex 2 100/1/0 5 Ex 3 100/1/2 5 4 100/2/0 10 Ex 5 100/2/0 5 Ex 6 100/2/0 1 pr. 7 100/4/0 100 ALIGN! Ex 8 100/4/0 20 May Ex 9 100/4/0 10 eg 10 100/4/0 2 Porovn.př. 1 100/0/0 0 Porovn.př. 2 100/4/0 0 Porovn.př. 3 100/0/2 0 Test Example 1

Ten vessels from each group were used to measure the internal pressure.

The pressure inside each of the containers made according to Examples 1 to 10 and Comparative Examples 1 to 3 was reduced to 460 mm Hg of mercury (300 mm Hg bag) to form a vacuum blood vessel.

The internal pressure in each of the vacuum vessels was measured at 50 ° C every three weeks, that is, immediately after closure, weeks, 6 weeks, 9 weeks, 12 weeks and 15 weeks thereafter. If we consider the internal pressure to be 100% immediately after closure, the percentage of retention related to the degree of vacuum was calculated from the measured value. The results are shown in Table 2.

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Test Example 2

In the same manner as in Test Example 1, the internal pressure in the vacuum blood vessel was measured except that the internal pressure in the vessel was reduced to 310 mm Hg (450 mm Hg bag).

If we consider the internal pressure to be 100% immediately after closing the container, the percent retention related to the degree of vacuum was calculated from the measured value. The results are summarized in Table 3.

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Test Example 3

In the same manner as in Test Example 1, the internal pressure in the blood vessel was measured except that the pressure inside the vessel was reduced to 30 mm Hg (730 mm Hg bag).

If we consider the internal pressure to be 100% immediately after closing the container, the percent retention related to the degree of vacuum was calculated from the measured value. The results are shown in Table 4.

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In test examples 1-3, a temperature of 50 ° C was used, which is a relatively high value compared to room temperature; such a high temperature was chosen because the observation period, ie 15 weeks, is relatively short as the permeability observation period.

As can be seen from the results in Tables 2 to 4, the higher the cobalt concentration, the faster the oxygen gas is absorbed. Also, the higher the polyamide content with the m-xylylene group, the faster the absorption of oxygen gas.

There are differences between the results of Tables 2 to 4. Their reason is that there is a different amount of oxygen gas to be absorbed due to the different degree of vacuum. The better the blood vessel is depleted, the smaller the amount of ky contained in it is.

No effect on gas impermeability was observed in containers where a blue dye substance was used as a constituent.

In addition to the components indicated in the examples, the comparative examples and the test examples, other additives may be used to achieve substantially the same results.

Claims (3)

PATENT CLAIMS Vacuum container for blood, characterized in that it consists of a tube with one closed and one open end, which is made of a mixture containing 99.5 to 92.0% by weight. polyethylene terephthalate, 0.5 to 8.0 wt. polyamide with m-xylylene group and 1 to 10 ppm of transition metal based on the weight of polyethylene terephthalate and polyamide with m-xylylene group; Vacuum container according to claim 1, characterized in that the polyamide with the m-xylylene group is poly-m-xylylene adipamide. Vacuum container according to claim 1 or 2, characterized in that the mixture comprises a blue dye or a purple dye.