JP5306098B2 - Thermoplastic resin film, and elastomer laminate and rubber plug laminated therewith - Google Patents

Description

  The present invention relates to a thermoplastic resin film, an elastomer laminate laminated with the thermoplastic resin film, and a rubber plug including the laminate.

  The opening of a vial used as a medical container or the like may be capped with a rubber stopper. Moreover, a synthetic resin film may be laminated | stacked on the surface which contacts the contents of a vial among the surfaces of the rubber stopper which plugs the opening part of a vial. This is to prevent components contained in the rubber stopper from being mixed into the contents of the vial or adsorbing the contents on the rubber wire.

  The synthetic resin film laminated on the rubber stopper is often a polyethylene film (see Patent Document 1 or the like) or a fluororesin film such as a tetrafluoroethylene resin film (see Patent Document 2 or the like). . The synthetic resin film laminated on the rubber stopper is required to have stability against the contents of the container, particularly chemical stability; and since the container needs to be sealed, it is required to have a tensile elastic modulus of a certain level or less. . This is because if the laminated film is flexible, it can be brought into close contact with the opening of the container and the sealing performance of the rubber stopper is enhanced. However, the fluororesin film has a problem that it is difficult to incinerate and has a large environmental load.

  In addition, although several methods have been proposed for the production of a rubber stopper laminated with a synthetic resin film (see Patent Documents 3 and 4, etc.), basically, an unvulcanized rubber is used in a predetermined manner. A semi-vulcanized rubber plug is obtained while molding into a shape; a synthetic resin film is laminated and laminated on the semi-vulcanized rubber plug and bonded to obtain a rubber plug with a film of this vulcanization. In order to make it adhere to a rubber stopper, it is required that the synthetic resin film has a high flexibility (shape followability) at the lamination temperature, that is, the storage elastic modulus at the lamination temperature is not more than a certain value. Of course, it is also important to have a melting point above the laminating temperature.

JP-A-4-22362 JP 2002-209975 A JP-A-4-251734 Japanese Patent Laid-Open No. 5-124661

  As described above, various properties are required for the synthetic resin film laminated on the rubber stopper, but no synthetic resin film satisfying these properties has been provided. Accordingly, the present invention provides a rubber plug in which a synthetic resin film is laminated, and is particularly suitable for sealing a medical container. Moreover, the synthetic resin film suitable for it is provided.

1st of this invention is related with the laminated body shown below.
[1] A non-fluorinated thermoplastic resin film (I) having a tensile elastic modulus at 23 ° C. of 1500 Mpa or less and a melting point of 180 ° C. or more, and an elastomer layer (II) mainly composed of an elastomer Laminated body (X).
[2] The laminate (X) according to [1], wherein the thermoplastic resin film (I) has a storage elastic modulus at 160 ° C. of 1.0 × 10 ⁸ Pa or less.
[3] The thermoplastic resin film (I) is at least selected from a structural unit derived from 4-methyl-1-pentene and an α-olefin other than 4-methyl-1-pentene having 2 to 20 carbon atoms. Laminated body (X) as described in [1] or [2] containing the polymer (A) containing the structural unit derived | led-out from 1 type of alpha olefin.
[4] The laminate (X) according to any one of [1] to [3], wherein the thermoplastic resin film (I) further contains a 4-methyl-1-pentene homopolymer (B).
[5] The laminate (X) according to any one of [1] to [4], wherein at least one surface of the thermoplastic resin film (I) is subjected to corona treatment or plasma treatment.
[6] The laminate (X) according to any one of [1] to [5], wherein the water contact angle of at least one surface of the thermoplastic resin film (I) is 100 degrees or less.
[7] The laminate (X) according to any one of [1] to [6], wherein the thermoplastic resin film (I) has an average film thickness of 1 to 300 μm.
[8] The lamination according to any one of [1] to [7], wherein the thermoplastic resin film (I) and the elastomer layer (II) are laminated successively via an adhesive layer (III). Body (X).
[9] The laminate (X) according to any one of [1] to [7], wherein the thermoplastic resin film (I) and the elastomer layer (II) are laminated in contact with each other.

The second of the present invention relates to the rubber plug shown below.
[10] A rubber plug (Y) obtained by processing the laminate (X) according to any one of [1] to [9].

3rd of this invention is related with the container shown below.
[11] A container having a container main body having at least one opening, and the rubber stopper (Y) according to [10] that seals the opening.
[12] A medical container having a container main body having at least one opening, and the rubber stopper (Y) according to [10] that seals the opening.
[13] An infusion container having a container main body having at least one opening and the rubber stopper (Y) according to [10] which seals the opening.
[14] The container according to any one of [11] to [13], wherein the container body is made of glass.

  The rubber stopper laminated with the resin film (I) of the present invention can seal the opening of the container. In particular, if the resin film (I) is a polymer containing a structural unit derived from 4-methyl-1-pentene having high chemical resistance, contamination of the contents of the container is suppressed. Therefore, the rubber stopper of the present invention can be preferably used as a stopper of a medical container that contains a medicine.

It is a figure which shows the example of a rubber stopper, FIG. 1A is a perspective view, FIG. 1B is sectional drawing, FIG. 1C is sectional drawing of the rubber stopper provided with the tube. It is a figure which shows an example of the preparation process of a rubber stopper.

1. Thermoplastic resin film (I)
The thermoplastic resin film (I) is mainly laminated on the surface of an elastomer resin (rubber material). As will be described later, since the resin film (I) may be laminated on an elastomer resin molded into a predetermined shape, the resin film (I) is required to have high flexibility at the lamination temperature. The laminating temperature is often 160 ° C. or higher. Therefore, the storage modulus at 160 ° C. of the resin film (I) is more it is not more than 1.0 × ¹⁰ 8 Pa and preferably, 1.0 × 10 ⁷ or more 1.0 × ¹⁰ 8 Pa or less preferable.

  Of course, the resin film (I) needs to have a melting point equal to or higher than the lamination temperature so as not to melt at the lamination temperature, preferably has a melting point equal to or higher than 180 ° C., and more preferably equal to or higher than 215 ° C. It has a melting point of 245 ° C. or lower.

  On the other hand, the resin film (I) can be laminated on a rubber stopper. Since the rubber stopper seals the opening of the container by the elasticity of rubber, it is preferable that the laminated film does not reduce the elasticity of the rubber. Therefore, the film (I) is required to have “elongation” of a certain level or more. “Elongation above a certain level” means that the tensile modulus at 23 ° C. is 1500 MPa or less, and preferably 600 MPa or more and 1300 MPa or less.

  The thermoplastic resin film (I) may satisfy the above characteristics, but preferably does not contain a fluorine resin. Fluorine resins are difficult to incinerate and have a large environmental impact. Therefore, it is particularly unsuitable for rubber plugs for disposable use, such as rubber plugs for medical containers. Examples of the fluororesin include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), and the like.

  The thermoplastic resin film (I) more preferably contains a copolymer of 4-methyl-1-pentene and another α-olefin. The other α-olefin is an olefin having 2 to 20 carbon atoms and includes ethylene. When the copolymerization ratio of other olefins is increased, the tensile elastic modulus is lowered to obtain “elongation”, and the storage elastic modulus at the lamination temperature tends to be lowered. Furthermore, the thermoplastic resin film (I) of the present invention may contain a homopolymer of 4-methyl-1-pentene together with the copolymer. When a homopolymer is contained, the melting point of the resin increases.

  A resin film containing a copolymer of 4-methyl-1-pentene and another α-olefin can be obtained by extruding a resin composition. Moreover, you may extend | stretch an extrusion-molded film as needed.

  A polymer containing a structural unit derived from 4-methyl-1-pentene generally has high releasability and low frictional resistance. Therefore, the rubber stopper laminated with the film containing the polymer is easy to remove from the opening. A polymer containing a structural unit derived from 4-methyl-1-pentene has high chemical resistance. Therefore, a rubber stopper in which a film containing the polymer is laminated is also suitably used as a stopper for a container that contains a medicine. That is, it is used as a stopper for containers for medicines and infusions.

  The thermoplastic resin film (I) of the present invention may contain other optional components. Examples of optional components include polyolefins, particularly polybutene.

  The average film thickness of the thermoplastic resin film (I) is preferably 1 to 300 μm. The thinner the thermoplastic resin film, the more difficult it is to reduce the elasticity of the elastomer resin to be laminated, and the sealing performance as a rubber plug can be improved. On the other hand, if the film is too thin, handling when laminating to the elastomer resin becomes difficult.

  It is preferable that the wettability of at least one surface of the thermoplastic resin film (I) of the present invention, that is, the “surface in contact with the rubber material” is not less than a certain value, that is, has a surface free energy not greater than a certain value. When the wettability is high, the film can be firmly bonded when the film is laminated on the elastomer resin. The wettability being above a certain level means that the water contact angle is 100 degrees or less, for example. In order to improve the wettability of the surface of the film (I), the surface may be subjected to corona treatment or plasma treatment. The corona treatment can be performed with reference to JP-A-4-22362.

  Moreover, the adhesive layer may be laminated | stacked on one side of the thermoplastic resin film of this invention. Adhesion is enhanced by laminating to the elastomer resin through the adhesive layer. Examples of the adhesive constituting the adhesive layer include a silicone-based adhesive, an epoxy-based adhesive, an acrylic pressure-sensitive adhesive, and the like.

2. Rubber plug The rubber plug of the present invention is characterized in that the thermoplastic resin film (I) is laminated on a part or all of the surface thereof. The thermoplastic resin film (I) may be laminated on the entire surface of the rubber stopper, but it is preferable that the film (I) is laminated on at least a surface that may come into contact with the substance contained in the container. . Furthermore, it is preferable that the film (I) is also laminated on the surface that comes into contact with the container when the stopper is plugged.

  Although FIG. 1 shows an example of the rubber plug of the present invention, the shape of the rubber plug is not limited to this. FIG. 1A is a perspective view of the rubber plug 10, and FIG. 1B is a cross-sectional view of the rubber plug 10. The rubber plug 10 shown in FIG. 1 has a head 20 and a leg 30. The container can be sealed with the rubber stopper 10 by inserting the leg 30 into the opening of the container. Moreover, as shown in FIG. 1C, a tube 50 that passes through the head 20 and passes through the hollow portion formed by the leg 30 can be arranged to extract the contents stored in the container. In particular, in the case of a rubber stopper for an infusion container, it is preferable to provide a tube 50 as shown in FIG. 1C.

  As shown in FIG. 1B, a thermoplastic resin film 40 is laminated on the surface of the rubber plug 10 on the side where the legs 30 are disposed. The film 40 prevents the contents of the container from coming into direct contact with the elastomer resin.

  Examples of the elastomer resin constituting the rubber plug body include butyl rubber, halogenated butyl rubber, butadiene rubber, styrene butadiene rubber, isoprene rubber, isobutylene isoprene rubber, ethylene propylene rubber, silicon rubber, etc. Natural rubber may be used. Moreover, various compounding agents may be contained in the elastomer resin. Examples of the compounding agent include organic peroxides, vulcanizing agents (organic sulfur donating vulcanizing agents, sulfur and the like), vulcanization accelerators, vulcanizing aids, reinforcing agents, processing aids, and the like.

Manufacturing method of rubber plug The manufacturing process of the rubber plug of the present invention is not particularly limited. For example, a step of setting an unvulcanized elastomer resin sheet in a mold (FIG. 2A), and molding the elastomer resin sheet into a predetermined shape And a step of semi-vulcanizing (FIGS. 2B to C), a step of placing a thermoplastic resin film on the elastomer resin sheet molded into a predetermined shape (FIG. 2D), and an elastomer molded into a predetermined shape A step of bonding a thermoplastic resin film to the resin sheet by thermocompression bonding (FIG. 2E) and a step of separating the rubber plugs from the elastomer resin sheet are included.

  As described above, the resin constituting the elastomer resin sheet includes synthetic rubber or natural rubber. Examples of the rubber include butyl rubber, halogenated butyl rubber, butadiene rubber, isoprene rubber, ethylene propylene rubber, silicon rubber and the like, and the rubber material may contain various fillers.

  The elastomer resin sheet is primarily molded into a desired shape using a mold. The desired shape is set according to the shape of the rubber plug, but may be the shape shown in FIG. 1, for example. The elastomer resin sheet set in the mold is preferably an unvulcanized rubber sheet. By molding the unvulcanized rubber with a mold, it is possible to prevent bubbles from being contained in the molded product.

  For example, as shown in FIG. 2, a mold composed of a lower mold 100 and an upper mold 110 is prepared. The cavity of the lower mold 100 is flat and forms the head 20 side in FIG. 1; the cavity of the upper mold 110 molds the legs 30 side. An unvulcanized elastomer resin sheet 120 is set on the lower mold 100 (FIG. 2A), and the upper mold 110 is stacked and heated under pressure to be semi-vulcanized (FIG. 2B), and the upper mold 110 is removed and the mold is opened. (FIG. 2C).

As described above, vulcanization is performed when the unvulcanized elastomer resin sheet 120 is formed into a desired shape, but it is preferable that the unvulcanized elastomer resin sheet 120 be kept in a semi-vulcanized state without being completely vulcanized. This is because the elastomer resin sheet 120 and the thermoplastic resin film 130 are sufficiently bonded in the next step. The conditions for semi-vulcanization should be set as appropriate depending on the composition and thickness of the elastomer resin and are not particularly limited. For example, the mold temperature is 130 ° C. to 190 ° C., and the molding pressure is 50 to 300 kg. / cm ² .

  The thermoplastic resin film 130 is set on the elastomer resin sheet 120 formed into a desired shape (FIG. 2D). The thermoplastic resin film 130 is the above-described resin film (I). The resin film 130 is set on the surface of the elastomer resin sheet 120 on which legs are formed by the upper mold 110. When the surface of the resin film 130 is subjected to corona treatment or plasma treatment, the treated surface and the elastomer resin sheet 120 are set in contact with each other; or an adhesive layer is laminated on the surface of the resin film 130. If it is, the adhesive layer and the elastomer resin sheet 120 are set in contact with each other.

  When the resin film 130 is set, the upper mold is again stacked and heated under pressure (FIG. 2E). At this time, the resin film 130 is laminated and adhered to the elastomer resin sheet 120. Further, by this pressure heating, the semi-vulcanized elastomer resin sheet 120 is completely vulcanized (main vulcanization). The conditions for this vulcanization should be appropriately set according to the conditions of the elastomer resin sheet 120 and the resin film 130; the mold temperature is a temperature at which the vulcanization of the elastomer resin sheet 120 proceeds. In addition, it is necessary that the temperature be equal to or lower than the melting point of the resin film 130, and the temperature is preferably such that the storage elastic modulus of the resin film 130 is sufficiently lowered. This is because the resin film 130 adheres to the elastomer resin sheet. The normal mold temperature is 160 ° C. or higher and below the melting point of the resin film 130.

  After laminating the resin film 130, the upper mold 110 is removed (FIG. 2F), and the laminated sheet 140 is isolated. Then, a rubber stopper is obtained by separating the laminated sheet 140 into individual pieces. The resulting rubber plug is shown, for example, in FIG. The elastomer sheet 120 in FIG. 2 comprises the head 20 and the leg 30 in FIG. 1; the resin film 40 in FIG. 2 comprises the resin film 130 in FIG.

3. Container The rubber stopper in which the resin film (I) of the present invention is laminated can seal the container with good airtightness. The container may be a glass container or a resin container, but is generally used as a sealing stopper for a glass container. In addition, when the resin film (I) laminated on the rubber stopper of the present invention is a polymer containing a structural unit derived from 4-methyl-1-pentene, the chemical resistance is high. It is suitably used for sealing stoppers. This is because there is little influence on the contents and the safety is high.

  The contents of the medical container are various pharmaceuticals, which may be solid or liquid, and may be an injection solution, a tablet, an infusion solution, or the like. An infusion is an aqueous solution that is administered subcutaneously, intravascularly, intraperitoneally, and the like, and includes various pharmaceutical ingredients, nutritional ingredients, and the like. When the infusion container is sealed with the rubber stopper of the present invention, a tube such as a hollow needle can be passed through the rubber stopper and the infusion can be taken out through the tube.

The following three types of poly-4-methylpentene-1 were prepared. Each was formed into a film using a cast film molding machine with a T-die (cylinder temperature 280 ° C., chill roll temperature 60 ° C.) to obtain a cast film having a thickness of 50 μm.
A: TPX RT18 (Mitsui Chemicals)
B: TPX MX004 (Mitsui Chemicals)
C: TPX MX002O (Mitsui Chemicals)

  In addition, a PTFE film (manufactured by Dupont) and a PET film (manufactured by Eastman) were prepared.

  The surface of each film was subjected to corona treatment with a corona treatment machine under the conditions of normal temperature, 400 W, and take-up speed of 5 m / min.

The following items were measured or evaluated for each film. These results are shown in Table 1.
Melting point measurement: Each film was heated from room temperature at 10 ° C./min by differential scanning calorimetry (DSC), and the temperature at the peak top of the obtained melting peak was defined as the melting point.
Measurement of elastic modulus at room temperature (23 ° C.) A test piece was cut out from each film, and a tensile test was performed at 50 mm / min in accordance with JIS K 6301-2 to measure the elastic modulus at room temperature.
Measurement of storage elastic modulus: A test piece was cut out from each film, heated at a rate of 3 Hz / min from −80 ° C. to 260 ° C. at a frequency of 1 Hz in a solid viscoelasticity measuring device in a tensile mode, and the storage elastic modulus was determined. It was measured. The E ′ at 160 ° C. of the obtained chart was read.
Measurement of water contact angle: A drop of distilled water was dropped on the corona-treated surface of each film at room temperature. The droplet contact angle was measured using a single-liquid interface analysis system.
Environmental: x having a halogen atom in the molecular structure and ◯ a resin composed of C, H, O atoms that can be incinerated.

Preparation of Laminate with Elastomer Eight unvulcanized butadiene rubbers were placed in a 2 cmφ, 1 cm high mold. Semi-crosslinking was carried out by heating at 160 ° C. and 1 MPa for 30 minutes. Thereafter, the mold was once opened, and each of the above films was inserted so that the corona-treated surface and the rubber surface were in contact with each other, and further crosslinked for 30 minutes under the same conditions. The molded product was taken out to obtain a laminate of each film and butadiene rubber.

Follow-up evaluation: The shape of the film and rubber at the convex part of the laminate was visually confirmed, and a part not following was evaluated as Δ, and a part following completely was evaluated as ○.
Adhesive strength evaluation: The film was peeled off from the end of the laminate, and the case where even a part was peeled was evaluated as Δ, and the case where no peeling occurred was evaluated as ○.

  The laminated body using any film had sufficient adhesive strength. However, poly-4-methylpentene-1 system A films and PET films having an elastic modulus at room temperature of 1900 MPa have poor followability during lamination. Moreover, the film of PTFE which is a fluorine resin is inferior in environmental property. On the other hand, both the 1300 MPa and 880 MPa poly-4-methylpentene-1 B and C resin films were evaluated well.

DESCRIPTION OF SYMBOLS 10 Rubber plug 20 Head 30 Leg 40 Thermoplastic resin film 50 Tube 100 Lower mold 110 Upper mold 120 Elastomer resin sheet 130 Thermoplastic resin film 140 Laminated sheet

Claims (12)

Setting an unvulcanized elastomer resin sheet in a mold;
Molding the elastomer resin sheet into a predetermined shape and semi-vulcanizing;
On the elastomeric resin sheet, the tensile modulus at 23 ° C. is not more than 1500M P a, and a melting point of 180 ° C. or more, constitutional units having 2 to 20 carbon atoms derived from 4-methyl-1-pentene A non-fluorinated thermoplastic resin film (I) containing a polymer (A) containing a structural unit derived from at least one α-olefin selected from α-olefins other than 4-methyl-1-pentene is disposed. And steps to
Bonding the elastomer resin sheet and the thermoplastic resin film (I) by thermocompression bonding;
A method for producing a rubber plug. The method for producing a rubber plug according to claim 1, wherein the thermoplastic resin film (I) has a storage elastic modulus at 160 ° C. of 1.0 × 10 ⁸ Pa or less. The method for producing a rubber plug according to claim 1 or 2 , wherein the thermoplastic resin film (I) further contains a 4-methyl-1-pentene homopolymer (B). The method for producing a rubber plug according to any one of claims 1 to 3 , wherein at least one surface of the thermoplastic resin film (I) is subjected to corona treatment or plasma treatment. The method for producing a rubber plug according to any one of claims 1 to 4 , wherein a water contact angle of at least one surface of the thermoplastic resin film (I) is 100 degrees or less. The method for producing a rubber plug according to any one of claims 1 to 5 , wherein an average film thickness of the thermoplastic resin film (I) is 1 to 300 µm. Placing the thermoplastic resin film (I) is, the thermoplastic resin film (I) and the elastomeric resin sheet, the so that stacked via an adhesive layer (III), wherein on the elastomeric resin sheet The manufacturing method of the rubber stopper as described in any one of Claims 1-6 which is a step which arrange | positions contact bonding layer (III) and the said thermoplastic resin film (I). Rubber stopper, which is produced by the method of claim 1-7 rubber stopper according to any one of (Y). A container comprising: a container body having at least one opening; and the rubber stopper (Y) according to claim 8 for sealing the opening. The medical container which has a container main body which has at least 1 opening part, and the rubber stopper (Y) of Claim 8 which seals the said opening part. An infusion container comprising: a container body having at least one opening; and the rubber stopper (Y) according to claim 8 that seals the opening, and a tube passes through the rubber stopper (Y). . The container according to any one of claims 9 to 11 , wherein the container body is made of glass.

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