JPH0561934B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION (Technical Field) The present invention relates to reduced pressure blood collection tubes. Specifically, the present invention relates to a vacuum blood collection tube made of synthetic resin that has an extremely high gas barrier, can maintain a high degree of vacuum over a long period of time, has little effect on humidity during storage, and can be provided at low cost. be. (Prior Art) The reduced-pressure blood collection method is widely used because it causes less hemolysis and coagulation, provides samples with less contamination and water evaporation, and simplifies blood collection preparation and equipment management in terms of efficiency. Therefore, the vacuum blood collection tube used in such a vacuum blood collection method consists of a tubular container and a sealing stopper that can be pierced. After puncturing the cap, the other end is punctured into the stopper to communicate with the inside of the sealed container, so that blood flows in due to the negative pressure inside the container and blood is collected. Conventionally, such vacuum blood collection tubes have been made of glass tubular containers, which have no gas permeability and good transparency, and butyl rubber stoppers, which have low gas permeability and can be punctured. Something more was used. However, glass tubular containers have the drawback of being easily damaged during storage, transportation, or use, and being heavy. Therefore, it is possible to use synthetic resin tubular containers as vacuum blood collection tubes that are lightweight, hard to break, and easy to incinerate. Consideration is being given to commercializing the product in combination with nitrogen packaging, etc. However, these materials are more expensive than glass, and their use as disposable products is limited. Furthermore, inorganic coatings, polyvinylidene chloride coatings, polyvinyl alcohol coatings, etc., have been proposed for synthetic resin tubular containers, but these have problems such as discoloration over time, low surface hardness, and high hygroscopicity, and are not practical. has not been standardized. Attempts have also been made to create tubular members by means such as multilayer blow molding, but multilayer blow molded products have poor transparency, are difficult to make thick products, are not recyclable, are expensive, and require a long molding cycle. Currently, there are many problems such as long length, etc., which prevents it from being put into practical use. OBJECT OF THE INVENTION Therefore, the present invention aims to eliminate the drawbacks of the conventional products as described above. That is, an object of the present invention is to provide a novel reduced pressure blood collection tube. A further object of the present invention is to provide a vacuum blood collection tube made of synthetic resin that has extremely high gas barrier properties, can maintain a high degree of vacuum over a long period of time, and can be provided at low cost without problems such as coloring over time. purpose. The above objects include a synthetic resin tubular member that is closed at one end and open at the other end, and a pierceable plug member that seals the open end, and the space formed by both members is kept in a reduced pressure state. In the vacuum blood collection tube, the outer surface of the synthetic resin tubular member is coated with a coating of a hydrolysis reaction product of a mixture of polyvinyl alcohol and an organosilicon compound and a coating of polyvinylidene chloride formed on the upper surface of this coating. This is achieved using a reduced pressure blood collection tube characterized by: The present invention also provides that the weight ratio of polyvinyl alcohol and organosilicon compound (in terms of SiO ₂ ) in the mixture of polyvinyl alcohol and organosilicon compound is
This shows a vacuum blood collection tube with a ratio of 50:50 to 90:10. The invention further provides a vacuum blood collection tube in which the tubular member is made of polystyrene or polypropylene. The present invention further provides a vacuum blood collection tube in which the coating of a hydrolyzate of a mixture of polyvinyl alcohol and an organosilicon compound and the coating of polyvinylidene chloride each have a thickness in the range of 1 to 20 μm. The present invention further provides a vacuum blood collection tube that is stored in a dry state in a packaging container. The present invention also provides a vacuum blood collection tube in which the vacuum blood collection tube is stored in a packaging container under a nitrogen atmosphere. DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail below with reference to the drawings. FIG. 1 is a drawing showing the cross-sectional shape of one embodiment of the reduced pressure blood collection tube of the present invention. As shown in FIG. 1, the reduced pressure blood collection tube 1 of the present invention includes a tubular member 2 made of synthetic resin with one end closed and the other end open, and a pierceable plug with the open end 3 of the tubular member 2 sealed. and a member 4, and maintains a space 5 formed by both members in a reduced pressure state. The outer surface of the synthetic resin tubular member 2 is made of a gas barrier coating 6 made of a hydrolysis reaction product of a mixture of polyvinyl alcohol and an organosilicon compound and polyvinylidene chloride formed on the upper surface of the gas barrier coating 6. It is coated with a moisture-proof coating 7. In FIG. 1, the gas barrier coating 6 and the moisture-proof coating 7 are exaggerated. The synthetic resin constituting the tubular member 2 used in the present invention is not particularly limited, but includes, for example, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polystyrene, polycarbonate, polypropylene, among others, from an economical point of view. Among them, polystyrene and polypropylene are preferred. The tubular member 2 can be obtained by injection molding these synthetic resins into a desired shape. Examples of the material constituting the plug member 4 include butyl rubber, but other materials other than butyl rubber can also be used, as will be described later, to allow the puncture of a blood collection needle during use and to create a space between the blood collection needle and the plug member by puncturing the blood collection needle. Any material having sufficient elasticity to prevent loosening and low gas permeability may be preferably used, such as a blend of thermoplastic elastomer, polyisobutylene, and partially crosslinked butyl rubber. The composition of each component in this formulation is 100 to 100 parts by weight of polyisobutylene per 100 parts by weight of thermoplastic elastomer.
200 parts by weight, preferably 120-150 parts by weight, 100-200 parts by weight of partially crosslinked butyl rubber, preferably 120-200 parts by weight
It is 150 parts by weight. Examples of thermoplastic elastomers include ethylene-propylene rubber, polyester elastomer, nylon elastomer, styrene-isopropylene block copolymer, styrene-butadiene block copolymer, polybutadiene, thermoplastic polyurethane, and hydrogenated styrene-butadiene block copolymer. There are mergers, etc. Polyisobutylene has a molecular weight
15,000 to 200,000, preferably 80,000 to 150,000. Partially crosslinked butyl rubber is obtained by partially crosslinking butyl rubber obtained by copolymerizing isobutylene and a small amount (for example, 0.3 to 3.0 mol%) of isoprene. In the vacuum blood collection tube 1 of the present invention, the gas barrier coating 6 is composed of a hydrolysis reaction product of a mixture of polyvinyl alcohol and an organosilicon compound, as described above. Polyvinyl alcohol is
Although it is a substance with extremely low gas permeability, it is hygroscopic, so if polyvinyl alcohol is used as a gas barrier coating, vacuum blood collection tubes coated with this coating will not only require strict packaging but also be It has poor wettability with lipophilic synthetic resins such as polystyrene and polypropylene, which are typical materials for tubular members, and cannot be firmly adhered to tubular members. On the other hand, while the hydrolysis reaction product of the mixture of polyvinyl alcohol and organosilicon compound constituting the gas barrier coating 6 according to the present invention has excellent gas barrier properties derived from polyvinyl alcohol, it has excellent gas barrier properties due to siloxane bonds. Its water resistance and waterproof properties are improved. This hydrolysis reaction product of a mixture of polyvinyl alcohol and an organosilicon compound can be obtained by hydrolyzing the mixture of polyvinyl alcohol and an organosilicon compound in water in the presence of a catalyst such as an acid or a base as necessary. More specifically, for example, organoalkoxysilane is mixed with polyvinyl alcohol at a concentration of 5 to 10% by weight, then the pH of the solution is adjusted to 1 to 4 with an acid such as hydrochloric acid or acetic acid, and then a transparent homogeneous solution is formed. It is obtained by stirring until the At this time, the mixing ratio of polyvinyl alcohol and organosilicon compound is such that the weight ratio of polyvinyl alcohol and organosilicon compound (calculated as SiO ₂ ) is 50:50 to 50:50.
A ratio of 90:10 is desirable. That is, if the ratio of polyvinyl alcohol is too low, there is a risk that the gas barrier properties of the film will be lowered, while if it is too high, problems will arise in the waterproof property of the film. In addition, as an organosilicon compound, the general formula R ¹ _a R ² _b Si(OR ³ ) _4-(a+b) () (in the formula, R ¹ and R ² are C ₁ to C ₁₀ alkyl, aryl, An alkyl halide, an aryl halide, an alkenyl, or an organic group having an epoxy group, a (meth)acryloxy group, a mercapto group, an amino group or a cyano group, which is bonded to silicon through a Si-C bond, and R ³ is _C1 to _C6
is an alkyl group, alkoxyalkyl group or acyl group, a and b are 0 to 2, and a+b
is 2 or less. ) Examples include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxylane,
Ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxy silane,
γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3
-trifluoropropyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, γ-
Glycidoxypropyltriethoxysilane, γ-
(β-glycidoxyethoxy)propyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
-Epoxycyclohexyl)ethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane , N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, trialkoxy or triacyloxysilanes such as β-cyanoethyltriethoxysilane, methyldimethoxysilane,
Phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyl phenyldimethoxysilane, γ-Glycidoxypropylphenyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxylan, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane Ethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, etc. Alkoxysilanes or diacyloxysilanes and tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, n-propyl silicate, iso-propyl silicate, n-butyl silicate, sec-butyl silicate, t-butyl silicate, etc. It can be used alone or in combination of two or more. Formation of the gas barrier film 6 of a hydrolysis reaction product of a mixture of polyvinyl alcohol and an organosilicon compound on the outer surface of the synthetic resin tubular member 2 involves applying the hydrolysis reaction product solution prepared as described above to the synthetic resin tubular member 2. After coating the external surface by means such as dipping, spraying, or brushing, the coating solution is dried at 50 to 90°C. The thickness of the formed gas barrier film 6 is 1 μm or more, preferably 6 μm or more.
It is assumed to be 12μm. That is, if it is less than 1 μm, there is a risk that sufficient gas barrier properties may not be exhibited. In addition, in order to increase the bondability between the synthetic resin constituting the tubular member 2 and the hydrolysis reaction product of the mixture of polyvinyl alcohol and organosilicon compound constituting the gas barrier coating 6, a known primer such as isocyanate may be used. It is also effective to coat the tubular member 2 in advance, or to activate the surface of the tubular member 2 in advance by a method such as plasma treatment, corona discharge treatment, or ozone gas treatment. In the vacuum blood collection tube 1 of the present invention, a moisture-proof coating is further applied to the upper surface of the gas barrier coating 6 formed on the outer surface of the synthetic resin tubular member 2 and made of a hydrolyzate of a mixture of polyvinyl alcohol and an organosilicon compound as described above. 7 has been applied. This is because the gas barrier properties of a film made of a hydrolysis reaction product of a mixture of polyvinyl alcohol and an organosilicon compound are affected by humidity, so the upper surface is further covered with a moisture-proof film 7, and the vacuum blood collection tube 1 is exposed to high humidity. It maintains the desired gas barrier properties even when placed in a certain location. As the material for this moisture-proof coating 7, polyvinylidene chloride is used because it has good bonding properties with the gas barrier coating 6, has high gas barrier properties, and is non-hygroscopic. To form the moisture-proof coating 7 of polyvinylidene chloride, after coating the synthetic resin tubular member 2 with the gas barrier coating 6 described above, polyvinylidene latex is applied to the gas barrier coating 6. immersion into the tubular member 2 formed in the
Apply by spraying, brushing, etc., and apply for 40 minutes.
This can be done by drying the coated latex at a temperature of ~80°C. As the polyvinylidene chloride latex, commercially available latex with a concentration of 10 to 100% by weight can be used. As mentioned above, since the hydrolysis reaction product of the mixture of polyvinyl alcohol and organosilicon compound constituting the gas barrier coating 6 has water resistance, an aqueous latex can be used in coating polyvinylidene chloride, and an organic solvent can be used. Since no gas is used, there is little risk of adverse effects on the formed gas barrier film 6. The thickness of the moisture-proof film 7 of polyvinylidene chloride formed in this way is 0.5 μm or more, preferably 3 to 6 μm.
That is, if it is less than 0.5 μm, the moisture-proofing effect cannot be substantially exhibited. Furthermore, in the reduced pressure blood collection tube 1 of the present invention, the degree of vacuum in the space 5 formed by the tubular member 2 and the plug member 4 is set to a degree of vacuum corresponding to the amount of blood to be collected; Anticoagulants such as heparin and EDTA are added to the space as necessary. The vacuum blood collection tube 1 of the present invention is usually stored in a packaging bag or packaging container until it is used, but it is preferably stored in a dry state. That is, by being stored in a dry state, the gas barrier properties of the gas barrier film 6 made of a hydrolysis reaction product of a mixture of polyvinyl alcohol and an organosilicon compound are maintained high, and the rate of decrease in the amount of blood collected from the blood collection tube over time is reduced. This is because it can be suppressed. Preservation in a dry state can be carried out by including a moisture absorbent in the packaging or using a moisture-proof packaging container. Furthermore, it is preferable that the vacuum blood collection tube 1 is stored in a nitrogen gas atmosphere. This is because the permeability of nitrogen gas to the material constituting the vacuum blood collection tube is lower than that of air. The reduced pressure blood collection tube 1 having the above configuration is used in the following manner. That is, as shown in FIG. 2, the vacuum blood collection tube 1 is opened in a blood collection tube holder 11 that is closed at one end and opened at the other end, and has a blood collection needle 10 screwed into the screw hole 9 of the closed end 8. Insert from part 12. This blood collection needle 10 includes, for example, a blood vessel piercing part 10a and a plug puncturing part 10b, and the plug puncturing part 10b is wrapped with a luer adapter 13 made of synthetic resin. Next, when the blood vessel piercing portion 10a of the blood collection needle 10 is pierced into a blood vessel, for example a vein, and the reduced pressure blood collection tube 1 is pressed and inserted into the closed end 8 of the blood collection tube holder 11, as shown in FIG. The puncture part 10b punctures the luer adapter 13 and the stopper member 4, and the tip thereof reaches the internal space 5 of the blood collection tube 1, so that the blood vessel and the internal space 5 communicate with each other, and due to the negative pressure in the internal space 5, Blood within the blood vessel flows into the internal space 5 of the blood collection tube 1 in an amount corresponding to the degree of reduced pressure. Next, the blood vessel piercing portion 10a of the blood sampling needle 10
Blood collection is completed by removing the tube from the blood vessel. The present invention will be described in more detail below based on Examples. Example Polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) having a degree of polymerization of approximately 2000 was dissolved in water under heating to prepare an 8% by weight aqueous solution. Tetraethoxysilane (Wako Pure Chemical Industries, Ltd.) was added to 100 g of this polyvinyl alcohol aqueous solution.
After adding 8.3 g of HC Co., Ltd., a 1N HC aqueous solution was gradually added dropwise to adjust the pH to 3.0, and stirring was continued until a clear homogeneous solution was obtained. On the other hand, a tube with an inner diameter of about 13 mm, a length of about 10 cm, and an inner volume of 13 ml was made of polystyrene (GP, Denki Kagaku Kogyo).
Co., Ltd.) as a raw material by injection molding. The tube was then subjected to ozone treatment to activate the surface. The outer surface of this tube was coated with the homogeneous solution obtained above by dipping, and then dried with hot air at 80° C. for 4 minutes to form a gas barrier coating on the outer surface of the tube. The average thickness of this gas barrier coating was 8.1 μm. After forming a gas barrier film, polyvinylidene chloride latex (DO-818, Kureha Chemical Industry Co., Ltd.)
Co., Ltd.) was further coated on the tube by dipping, and dried at 63° C. for 2 minutes using an infrared heater to form a moisture-proof coating on the upper surface of the gas barrier coating. The average thickness of this moisture-proof coating is 6.0μm
It was hot. A vacuum blood collection tube was prepared by combining the coated tube with a general butyl rubber stopper and sealing it under reduced pressure so that the amount of blood to be collected was approximately 10 c.c. In addition, 7.5 mg of ethylenediamine triethylamine sodium salt (EDTA-2Na) was added as an anticoagulant to the inside of the vacuum blood collection tube. Changes over time in the amount of blood collected using the vacuum blood collection tube thus prepared were investigated.
The vacuum blood collection tubes were stored under three conditions: unpackaged, stored in a dry state, and stored in a dry nitrogen atmosphere (all at room temperature). In addition, in consideration of the leakage of gas remaining in the polystyrene during molding into the vacuum blood collection tube internal space, the amount of blood collected after aging at 60°C for 3 days was set as the initial value, and the amount of blood collected over time was determined from this initial value. The rate of change is expressed as a percentage. If the blood sample amount changed by 10% or more, tracking of changes over time was stopped. The results obtained are shown in Table 1. Comparative Example 1 For comparison, a vacuum blood collection tube prepared in the same manner as in the example was used, except that no polyvinylidene chloride coating was formed, and changes over time in the amount of blood collected were examined in the same manner as in the example. The results are shown in Table 1. Comparative Example 2 A reduced pressure blood collection tube was prepared using a polystyrene tube similar to that used in Example 1 without any coating, and the change in the amount of blood collected over time was examined in the same manner as in Example 1. The results are shown in Table 1.

[Table] Effects of the Invention As described above, the present invention includes a synthetic resin tubular member with one end closed and the other end open, and a pierceable plug member with the open end sealed. In a vacuum blood collection tube that maintains a vacuum state in the space formed, the outer surface of the synthetic resin tubular member is covered with a coating of a hydrolysis reaction product of a mixture of polyvinyl alcohol and an organosilicon compound, and a polyester film formed on the upper surface of this coating. Because it is coated with a film of vinylidene chloride, the degree of vacuum inside the blood collection tube is maintained stably over a long period of time, and the amount of blood collected over time does not change much.
In particular, even if the storage condition is not dry, the change in the amount of blood collected over time is kept low, and the product is inexpensive, making it an extremely excellent vacuum blood collection tube. Further, in the vacuum blood collection tube of the present invention, the weight ratio of polyvinyl alcohol and organosilicon compound (SiO ₂ equivalent) in the mixture of polyvinyl alcohol and organosilicon compound is 50:50 to 90:10, and the vacuum blood collection tube is in a dry state. If the blood is stored in a packaging container under a nitrogen gas atmosphere, the amount of blood collected will change less over time. Furthermore, it is more economically advantageous if the tubular member is made of polystyrene or polypropylene.

[Brief explanation of the drawing]

FIG. 1 is a drawing showing the cross-sectional shape of one embodiment of the reduced pressure blood collection tube of the present invention, and FIGS.
The figure is a sectional view showing how the blood collection tube is used. DESCRIPTION OF SYMBOLS 1... Decompression blood collection tube, 2... Tubular member, 4... Plug member, 6... Gas barrier coating, 7... Moisture-proof coating.

Claims (1)

[Claims] 1. A synthetic resin tubular member with one end closed and the other end open, and a pierceable plug member with the open end sealed, and the space formed by both members is reduced in pressure. In the vacuum blood collection tube, the outer surface of the synthetic resin tubular member is coated with a coating of a hydrolysis reaction product of a mixture of polyvinyl alcohol and an organosilicon compound, and a coating of polyvinylidene chloride formed on the top surface of this coating. A vacuum blood collection tube characterized by: 2 The weight ratio of polyvinyl alcohol and organosilicon compound (in terms of SiO ₂ ) in the mixture of polyvinyl alcohol and organosilicon compound is 50:50 to 90:
10. The reduced pressure blood collection tube according to claim 1. 3. The vacuum blood collection tube according to claim 1 or 2, wherein the tubular member is made of polystyrene or polypropylene. 4. The film according to any one of claims 1 to 3, wherein the film of a hydrolyzate of a mixture of polyvinyl alcohol and an organosilicon compound and the film of polyvinylidene chloride each have a thickness in the range of 1 to 20 μm. Vacuum blood collection tube. 5. Claims 1 to 4, wherein the vacuum blood collection tube is stored in a packaging container in a dry state.
The reduced pressure blood collection tube according to any of paragraphs. 6 Claim 1, in which the vacuum blood collection tube is stored in a packaging container under a nitrogen gas atmosphere
The reduced pressure blood collection tube according to any one of Items 1 to 5.