JPH08183545A - Rubber plug and its manufacture - Google Patents

Abstract

PURPOSE: To provide a rubber plug through which a gas is hard to permeate, and at the same time, which can prevent the content of a container from flowing out from a part where a needle is pierced, and in addition, wherein the rubber plug main body made of rubber does not need to be covered with a plastic layer in order to prevent a gas from permeating such as a conventional rubber plug, and the cost of which can be reduced, and which does not generate the problem of the peeling of a plastic layer. CONSTITUTION: A self sealing rubber layer 2 made of rubber with a favorable self-sealing property is laminated on a gas permeation-preventing rubber layer 1 made of rubber with less gas permeability. A gas is prevented from permeating by the gas permeation-preventing rubber layer 1, and in the meantime, the content of a container from a part which is pierced by a needle can be prevented from flowing out by the self-sealing rubber layer 2. Then, since the two layers 1, 2 are made of rubber, they can be easily combined and integrated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber stopper for sealing the mouth of a container made of glass, plastic or the like, and more particularly to an infusion container, a blood transfusion container, a pharmaceutical container, which is used in the medical field. The present invention relates to a rubber stopper suitable as a rubber stopper for inserting and removing a pointed body such as a needle, such as a rubber stopper for a blood sampling syringe or the like.

[0002]

2. Description of the Related Art Infusion containers, blood transfusion containers, pharmaceutical containers,
For rubber stoppers such as syringes for blood collection, (a) it is difficult for gas to pass in order to prevent gas in the container from flowing out, evaporation of liquid in the container, and ingress of external gas into the container. In addition, (b) it is required that the contents of the container can be prevented from flowing out from a portion such as a needle where the pointed body is pierced. For this reason, conventionally, the rubber stopper main body is made of rubber having a good self-sealing property (sealing property of a penetrating portion when pierced by a pointed body such as a needle), and the surface of the rubber stopper main body is covered with fluorine. A large number of rubber stoppers for preventing gas permeation by coating or laminating a plastic layer such as a system resin or polyethylene (PE) have been developed and used.

[0003]

However, since it is difficult to bond the rubber and the plastic, in the conventional rubber plug, the rubber plug body and the plastic layer are adhered by a method other than the direct bonding. It becomes necessary to integrate them. Therefore, when the outer shell of the rubber stopper is supported by the outer shell support made of plastic, the outer shell support surrounds the plastic layer to bring the plastic layer into close contact with the rubber body (Japanese Patent Laid-Open No. 3-97141).
No.), ultrasonic welding of the outer shell support and the plastic layer laminated on the rubber stopper body (Japanese Patent Application Laid-Open No. 2-1275).
No.) etc., and the structure of the mouth of the container and the manufacturing process are complicated as a whole, and the cost is high.

Further, since the elasticity of rubber cannot be followed by the plastic layer, there is a problem that the plastic layer is likely to be peeled off from the rubber plug main body even if the above measures are taken.

The present invention has been made in view of the above circumstances, and an object of the present invention is to prevent gas from passing therethrough and to allow the contents of the container to flow out from a portion penetrated by a pointed body such as a needle. Moreover, unlike the conventional rubber stoppers, there is no need to take measures to bring the rubber stopper body and the plastic layer into close contact with each other, the structure of the mouth of the container and the manufacturing process can be simplified, and the cost can be reduced. It is an object of the present invention to provide a rubber stopper and a method for manufacturing the same, which does not cause a problem of peeling of layers.

[0006]

A rubber plug of the present invention is a self-sealing rubber layer which is made of a rubber having a small gas permeability and a rubber layer having a good self-sealing property which is laminated on the gas permeability preventing rubber layer. And a seal rubber layer.

The gas permeation preventive rubber layer can be composed of, for example, only butyl rubber (hereinafter referred to as IIR) or rubber containing IIR as a main component, and the self-sealing rubber layer is
For example, it can be composed of only isoprene rubber (hereinafter referred to as IR) or natural rubber (hereinafter referred to as NR), or rubber having IR or NR as a main component.

The first method for producing a rubber stopper according to the present invention comprises a gas permeation-preventing rubber layer obtained by mixing IIR and IR such that IIR is contained in a larger weight ratio than IR.
A layer of self-sealing rubber obtained by mixing IIR and IR in a weight ratio such that IR is contained more than IIR.
The rubber plug is obtained by bringing them into contact with each other in an unvulcanized or vulcanized state and heating and pressurizing them to integrate them.

In the second method for producing a rubber stopper according to the present invention, the surface of a vulcanized self-sealing rubber layer made of only IR or rubber having IR as a main component is subjected to a chlorination treatment, and this chlorination is carried out. The treated self-sealing rubber layer is brought into contact with an unvulcanized gas permeation-preventing rubber layer made of a rubber containing halogen, bromine or iodine and containing only IIR or IIR as a main component, and heated and pressurized. The rubber plug is obtained by combining and integrating.

Further, in the method for producing a rubber plug according to the third aspect of the present invention, the surface of a vulcanized self-sealing rubber layer made of only IR or rubber having IR as a main component is subjected to a roughening treatment, and this roughening treatment is performed. By contacting an unvulcanized gas permeation-preventing rubber layer made of IIR alone or a rubber containing IIR as a main component with the self-sealing rubber layer that has been subjected to the surface treatment, and heating and pressurizing the rubber layer to bond and integrate them, The rubber plug is obtained.

[0011]

In the rubber stopper of the present invention, the gas permeation preventing rubber layer prevents gas permeation, while the self-sealing rubber layer prevents the contents of the container from flowing out from the portion penetrated by the pointed body such as the needle. it can. Since the gas permeation preventive rubber layer and the self-sealing rubber layer are rubbers, they can be bonded to each other as in the method of manufacturing the rubber stopper according to the first, second and third aspects of the present invention. Therefore, unlike the conventional rubber stopper, there is no need to take measures to bring the rubber stopper body and the plastic layer into close contact with each other, the structure of the container mouth portion and the manufacturing process can be simplified, and the cost can be reduced.
Moreover, the problem of peeling of the plastic layer does not occur.

[0012]

【Example】

<< Embodiment of Laminated Structure of Rubber Plug >> FIG. 1 shows a first embodiment of a laminated structure of a rubber plug according to the present invention. It has a gas permeation preventive rubber layer 1 made of rubber having a small gas permeability and a good self-sealing property. The self-sealing rubber layer 2 made of rubber is laminated on the entire rubber plug, and the self-sealing rubber layer 2 is provided on the outer surface (top surface) side and the gas permeation prevention rubber layer 1 is provided on the inner surface (lower surface) side.

FIG. 2 shows a second embodiment of the laminated structure of the rubber stopper according to the present invention. As in the case of the first embodiment of FIG. 1, the gas permeation preventing rubber layer 1 and the self-sealing rubber layer 2 are made of rubber. Although laminated over the entire stopper, contrary to the case of the first embodiment, a gas permeation preventive rubber layer 1 is provided on the outer surface side and a self-sealing rubber layer 2 is provided on the inner surface side.

FIG. 3 shows a third embodiment of the laminated structure of the rubber stopper according to the present invention. The rubber stopper has a three-layer structure as a whole, and a self-sealing rubber layer 2 is provided between two gas permeation preventing rubber layers 1. It is sandwiched.

FIG. 4 shows a fourth embodiment of the laminated structure of the rubber stopper according to the present invention. As in the case of the third embodiment of FIG. 3, the entire rubber stopper has a three-layer structure. Contrary to the case of the third embodiment, the gas permeation preventive rubber layer 1 is sandwiched between the two self-sealing rubber layers 2.

FIGS. 5 and 6 show a fifth embodiment of the laminated structure of the rubber stopper according to the present invention, in which the gas permeation preventing rubber layer 1 and the self-sealing rubber layer 2 are laminated only on a part of the rubber stopper. Has become. That is, the circular self-sealing rubber layer 2 having a diameter smaller than the entire diameter of the rubber stopper is provided only on a part of the rubber stopper.
The self-sealing rubber layer 2 is provided on the outer surface side, the inner surface side, and the lateral side of the (in other words, the gas permeation prevention rubber layer 1
(The self-sealing rubber layer 2 is embedded inside). On the outer surface of the gas permeation preventive rubber layer 1 directly above the self-sealing rubber layer 2, there is provided a circular unevenness 3 indicating a position where a pointed body such as a needle is pierced.

FIGS. 7 and 8 show a sixth embodiment of the laminated structure of the rubber stopper of the present invention. As in the case of the fifth embodiment of FIGS. 5 and 6, only a part of the rubber stopper is gas. Although the self-sealing rubber layer 2 is embedded inside the gas permeation-preventing rubber layer 1 so that the permeation-preventing rubber layer 1 and the self-sealing rubber layer 2 are laminated, in the present embodiment, the self-sealing rubber layer 2 is separated into three. Is provided. On the outer surface of the gas permeation preventive rubber layer 1 directly above the self-sealing rubber layer 2, there is provided a circular unevenness 3 indicating a position where a pointed body such as a needle is pierced.

FIGS. 9 and 10 show a seventh embodiment of the laminated structure of the rubber stopper of the present invention. As in the case of the fifth embodiment of FIGS. 5 and 6, only a part of the rubber stopper is gas. Although the self-sealing rubber layer 2 is embedded in the gas permeation-preventing rubber layer 1 so that the permeation-preventing rubber layer 1 and the self-sealing rubber layer 2 are laminated, in the present embodiment, the self-sealing rubber layer 2 is used.
The outer surface of the gas permeation preventive rubber layer 1 is not covered, and the outer surface of the gas permeation preventive rubber layer 1 and the outer surface of the self-sealing rubber layer 2 are flush with each other. It is exposed to the outside.

FIGS. 11 and 12 show an eighth embodiment of the laminated structure of the rubber stopper of the present invention. As in the case of the seventh embodiment of FIGS. 9 and 11, the gas permeation preventive rubber layer 1 is self-sealed. Although the seal rubber layer 2 is buried, in this embodiment, the self-seal rubber layer 2 is provided separately in three layers.

In the rubber stoppers of the above-mentioned respective embodiments, the gas permeation preventive rubber layer 1 prevents the permeation of gas, while the self-sealing rubber layer 2 allows the contents of the container to be penetrated by a pointed body such as a needle. Can be prevented (when the gas permeation preventive rubber layer 1 and the self-sealing rubber layer 2 are laminated only in a part of the rubber plug as in the embodiment of FIGS. A pointed body such as a needle shall be pierced in the portion where the layer 2 exists).

Since the gas permeation preventing rubber layer 1 and the self-sealing rubber layer 2 are rubbers, they can be joined to each other by a method which will be described later, so that a rubber stopper like a conventional rubber stopper is used. No measures are required to bring the main body and the plastic layer into close contact, the structure of the mouth of the container and the manufacturing process can be simplified, and the cost can be reduced.
Moreover, the problem of peeling of the plastic layer does not occur.

When the gas permeation preventing rubber layer 1 and the self-sealing rubber layer 2 are laminated only on a part of the rubber plug as in the embodiment of FIGS. 5 to 12, the apex is formed by means other than providing the unevenness 3. Needless to say, it is possible to indicate the position of piercing. For example, when the outer surface of the gas permeation preventive rubber layer 1 is exposed to the outside as in the embodiments of FIGS. 9 to 12, instead of providing the unevenness 3, the gas permeation preventive rubber layer 1 is provided.
The position where the pointed body such as a needle is pierced may be indicated by changing the color of the self-sealing rubber layer 2.

The gas permeation preventive rubber layer 1 is made of, for example, II.
It can be composed of only R or rubber containing IIR as a main component,
The self-sealing rubber layer 2 is, for example, only IR or NR,
Alternatively, it can be made of rubber having IR or NR as a main component.

When the gas permeation preventive rubber layer 1 is composed of only IIR or rubber containing IIR as a main component,
The thickness of the gas permeation preventing rubber layer 1 is preferably 2 mm or more in order to sufficiently prevent gas permeation. Also,
When the self-sealing rubber layer 2 is made of only IR or rubber containing IR as a main component, the thickness of the self-sealing rubber layer 2 is preferably 1 mm or more in order to obtain sufficient self-sealing property.

Further, while the gas permeation preventive rubber layer 1 is composed of only IIR or rubber containing IIR as a main component,
When the self-sealing rubber layer 2 is composed of only IR or NR or rubber containing IR or NR as a main component,
In order to reduce the amount of eluate when the rubber stopper comes into contact with the liquid in the container, the gas permeation preventive rubber layer 1 has a rubber stopper as in the embodiments of FIGS. 1, 3, and 5 to 12. It is preferable to configure the inner surface. However, when the amount of eluate can be suppressed below the allowable value, the self-sealing rubber layer 2 may constitute the inner surface of the rubber plug as in the embodiment of FIGS. 2 and 4.

As a structure for mounting the rubber stopper of the present invention on the container, the rubber stopper may be directly mounted on the mouth of the container, or may be indirectly attached to the mouth of the container via an outer shell support or the like. It may be attached to the.

<< Method of Joining Gas Permeation Prevention Rubber Layer 1 and Self-Sealing Rubber Layer 2 >> The gas permeation prevention rubber layer 1 and the self-sealing rubber layer 2 can be joined, for example, as follows.

I) The gas permeation preventive rubber layer 1 is composed of IIR and I
R is composed of a rubber mixed so that IIR is contained in a larger weight ratio than IR, while the self-sealing rubber layer 2 is composed of IIR and IR in a larger weight ratio than IR than IR. The gas permeation preventive rubber layer 1 and the self-sealing rubber layer 2 are brought into contact with each other in an unvulcanized state or in a vulcanized state to bond them by heating and pressing. Integrate. In this case, in order to satisfactorily bond the two layers 1 and 2, the IR contained in the gas permeation prevention rubber layer 1 and the self-sealing rubber layer 2
It is preferable that the IIRs contained in each are 5% or more.

Ii) While the self-sealing rubber layer 2 is composed of only IR or rubber containing IR as a main component,
The gas permeation preventive rubber layer 1 is composed of a rubber containing halogen, bromine or iodine and containing only IIR or IIR as a main component. Vulcanized self-sealing rubber layer 2
The surface of is subjected to a chlorination treatment, and the vulcanized self-sealing rubber layer 2 is brought into contact with the unvulcanized gas permeation preventive rubber layer 1 to heat and pressurize them for integration.

Iii) The self-sealing rubber layer 2 is composed of only IR or rubber containing IR as a main component, while the gas permeation preventing rubber layer 1 is composed of only IIR or IIR.
It is composed of rubber containing as a main component. The surface of the vulcanized self-sealing rubber layer 2 is roughened by plasma treatment or the like, and the unvulcanized gas permeation prevention rubber layer 1 is brought into contact with the roughened self-sealing rubber layer 2. Heat and pressurize to combine and integrate.

FIG. 13 shows an embodiment of a manufacturing method for efficiently producing the rubber stoppers of the first and second embodiments of FIGS. 1 and 2. Unvulcanized IIR1 'and IR2' are rolled by rolls 4, 5 or screws to form a gas permeation preventive rubber layer 1 and a self-sealing rubber layer 2, respectively. These gas permeation preventive rubber layer 1 and self-sealing rubber layer 2 are overlapped with each other and passed through a roll 6 to be crimped to each other, cut by a cutter 7 which moves up and down to an appropriate size, charged in a mold 8 and pressed and heated to join the two layers 1 and 2 together. At the same time, it is vulcanized. afterwards,
If necessary, it is further processed into a predetermined shape by punching or the like to obtain a rubber plug having a desired shape.

In the present invention, it goes without saying that the gas permeation preventive rubber layer 1 and the self-sealing rubber layer 2 may be joined by a method other than the method described above.

<< Formulation Examples and Test Results of Gas Permeation Prevention Rubber Layer and Self-sealing Rubber Layer >>

[Table 1]

[Table 2]

[Table 3]

[Table 4] Table 1 shows an example of IIR formulation in the present invention, and Table 2 shows an example of IR formulation in the present invention. Further, Table 3 shows that the rubber plugs of the first embodiment of FIG. 1 were produced by changing the mixing ratio of IIR and IR of the above-mentioned composition variously, and the coring property (the pointed body such as the needle was changed to the rubber plug) for them was prepared. When pierced, whether the rubber breaks and fragments are generated), self-sealing property,
The results of tests for elution physical properties and gas permeability are shown, and Table 4 shows the results of similar tests performed for the second example of FIG. 2 (thicknesses of the gas permeation prevention rubber layer 1 and the self-sealing rubber layer 2). Both are 5 mm).

The presence / absence of treatment in Tables 3 and 4 indicates the presence / absence of chlorination treatment. That is, in the case of “with” the chlorination treatment, the surface of the vulcanized self-sealing rubber layer 2 is chlorinated, and the chlorinated self-sealing rubber layer 2 contains halogen, bromine or chlorine. The unvulcanized self-sealing rubber layer 2 is brought into contact and heated and pressed to bond and integrate, while chlorination treatment is “none”.
In this case, the surface of the self-sealing rubber layer 2 is not subjected to chlorination treatment, but the unvulcanized self-sealing rubber layer 2 is brought into contact with the surface of the self-sealing rubber layer 2 to heat and pressurize them for integration.

Here, when the gas permeation preventive rubber layer 1 and the self-sealing rubber layer 2 are IIR only (that is, IIR is 100%) and IR only (that is, IR is 100%), the chlorination treatment is not performed. Therefore, the gas permeation preventive rubber layer 1 and the self-sealing rubber layer 2 cannot be joined well.

Further, in Tables 3 and 4, ◯ means good. Regarding the gas permeability, when the N ₂ gas permeability is 100 when the IR is 100%, the case where the N ₂ gas permeability index is 9 or less is good (◯).

As shown in Tables 3 and 4, good results were obtained in all of the mixing ratios in terms of self-sealing property, elution property, and gas permeability.

Here, in Tables 3 and 4, the amount of IR in the self-sealing rubber layer 2 and the gas permeation preventing rubber layer 1
Even when the amount of IIR in each is less than 80% (formulation examples 5 and 6), good results are obtained,
In order to further improve the gas permeability of the gas permeation prevention rubber layer 1 and the self-sealing property of the self-sealing rubber layer 2, the amount of IR of the self-sealing rubber layer 2 and the amount of IIR of the gas permeation prevention rubber layer 1 are 80% respectively. The above is preferable.

The rubber stopper according to the present invention can be applied to containers other than an infusion container, a blood transfusion container, a pharmaceutical container, and a blood sampling syringe.

[0040]

As described above, according to the present invention, it is difficult for gas to pass therethrough, and it is possible to prevent the contents of the container from flowing out from a portion penetrated by a pointed body such as a needle, and moreover, unlike the conventional rubber stopper. Rubber that does not require any measures to bring the rubber stopper body and the plastic layer into close contact with each other, simplifies the structure of the mouth of the container and the manufacturing process, reduces costs, and does not cause the problem of peeling the plastic layer. An excellent effect such as obtaining a stopper can be obtained.

[Brief description of drawings]

FIG. 1 is a sectional view showing a first embodiment of a laminated structure of a rubber plug of the present invention.

FIG. 2 is a cross-sectional view showing a second embodiment of the laminated structure of the rubber plug of the present invention.

FIG. 3 is a sectional view showing a third embodiment of the laminated structure of the rubber plug of the present invention.

FIG. 4 is a sectional view showing a fourth embodiment of the laminated structure of the rubber plug of the present invention.

FIG. 5 is a plan view showing a fifth embodiment of the laminated structure of the rubber plug of the present invention.

6 is a cross-sectional view taken along line VI-VI in FIG.

FIG. 7 is a plan view showing a sixth embodiment of the laminated structure of the rubber plug of the present invention.

8 is a cross-sectional view taken along the line VIII-VIII in FIG.

FIG. 9 is a plan view showing a seventh embodiment of the laminated structure of the rubber plug of the present invention.

10 is a cross-sectional view taken along line XX of FIG.

FIG. 11 is a plan view showing an eighth embodiment of the laminated structure of the rubber plug of the present invention.

12 is a sectional view taken along line XII-XII in FIG.

FIG. 13 is a cross-sectional view showing an embodiment of the method for manufacturing the rubber plug of the first embodiment and the second embodiment.

[Explanation of symbols]

 1 Gas permeation prevention rubber layer 2 Self-sealing rubber layer

Claims (5)

[Claims] 1. A rubber plug comprising a gas permeation preventive rubber layer made of rubber having low gas permeability and a self-sealing rubber layer made of rubber having good self-sealing property, which is laminated on the gas permeation preventive rubber layer. 2. The gas permeation preventive rubber layer is composed of butyl rubber alone or a rubber containing butyl rubber as a main component.
2. The self-sealing rubber layer is made of isoprene rubber alone or rubber containing isoprene rubber as a main component.
The rubber stopper described. 3. A gas permeation-preventing rubber layer formed by mixing butyl rubber and isoprene rubber in a weight ratio such that butyl rubber is contained more than isoprene rubber, and butyl rubber and isoprene rubber are in a weight ratio of isoprene rubber. And a layer of self-sealing rubber formed by mixing so as to be contained in a larger amount than butyl rubber, respectively, in contact with each other in an unvulcanized state or in a state where one of them is vulcanized, and heated and pressurized to bond and integrate them. Item 3. A method for producing a rubber plug, which is used to obtain the rubber plug according to Item 2. 4. The surface of a vulcanized self-sealing rubber layer composed of isoprene rubber alone or a rubber mainly containing isoprene rubber is chlorinated, and the self-sealing rubber layer subjected to the chlorination treatment is treated with halogen, The rubber according to claim 2, wherein an unvulcanized gas permeation-preventing rubber layer made of butyl rubber alone or a rubber containing butyl rubber as a main component, which contains bromine or chlorine, is brought into contact with the rubber layer to heat and pressurize them to integrate them. A method for producing a rubber stopper for obtaining a stopper. 5. A surface of a vulcanized self-sealing rubber layer made of only isoprene rubber or a rubber containing isoprene rubber as a main component is roughened, and the surface of the self-sealing rubber layer is roughened. 3. A rubber stopper for obtaining a rubber stopper according to claim 2, wherein an unvulcanized gas-permeation-preventing rubber layer made of butyl rubber alone or a rubber containing butyl rubber as a main component is brought into contact with the rubber layer to heat and pressurize the rubber layer to integrate them. Method.