JP2019030588A - Tube port and transfusion bag with port member - Google Patents

Abstract

To provide a tube port excellent in steam barrier property, oxygen barrier property, dimension stability and visibility, and a transfusion bag with a tube port comprising the tube port.SOLUTION: There is provided a tube port attached to a transfusion bag, the tube port comprising a cylindrical molded body having a resin layer l which includes polyvinylidene chloride.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a tube port and an infusion bag with a tube port.

  A container (hereinafter, also referred to as “infusion bag”) for storing medicines such as infusion bags is composed of a packaging material (film) provided with a barrier layer and a plug serving as a liquid flow path. As a kind of the plug, the end of the port is a port of a type closed by a closure plug such as an elastic body configured so that the hollow needle can be pierced and liquid does not leak from the pierced gap (hereinafter referred to as a plug). Tube type port (hereinafter referred to as “closed plug type port”), twist-off type connector that twists and opens the upper part, branch type connector, connector with cap, etc. , Also called “tube port”). This plug is required to have various performances from the viewpoint of adhesion to the container, adhesion to the closure plug and connector, from the viewpoint of waste incineration, and from the viewpoint of contact with the chemical solution. There are no measures to improve sex.

  For example, Patent Document 1 discloses an outer layer made of a resin material containing high-density polyethylene and a resin material containing random polypropylene and / or block polypropylene for the purpose of improving heat resistance and adhesion to a polyethylene infusion bag. Although the tube port having an inner layer is disclosed, the polyolefin used in the cited document 1 is easy to permeate gases such as oxygen and carbon dioxide, for example, to easily oxidize drugs and carbon dioxide. It is not necessarily suitable for an application for storing and storing a chemical solution or the like that should suppress the accompanying pH fluctuation. Therefore, even if the overall barrier properties are improved by using an infusion bag made up of a packaging material with a barrier layer, it will eventually be ignored in suppressing the deterioration of the contents due to the low barrier properties of the plugs. It will be impossible.

  In order to solve such a problem, although it is an example of a closed plug type port instead of a tube port, in Patent Document 2, a sheet material including at least one layer that forms a barrier that is essentially impermeable to gas and sealing the same In this case, it is disclosed that a tube that essentially does not allow gas to pass through is used as the stopper.

JP 2012-29895 A JP-T-2004-536630

  The tube port requires close contact (sealability) with various connectors made of materials such as polyolefin and polyvinyl chloride, while a hollow needle can be inserted into the closure port. The material performance required for both is different in that the adhesiveness (sealability) with the elastic body is required. Therefore, the same barrier property is easily achieved also in the tube port disclosed in the cited document 1 just because the barrier plug property disclosed in the cited document 2 shows a temporary barrier property. That is not immediately.

  In addition, in Patent Document 2, the gas to be impervious is substantially only oxygen, and as the oxygen impervious means, ethylene vinyl alcohol copolymer (EVOH) having relatively poor water vapor permeability is used. There is only disclosure. However, as the infusion bag, not only oxygen but also barrier properties such as water vapor can be required, and even with the means disclosed in Patent Document 2, it is difficult to say that sufficient barrier properties are achieved.

  Further, if attention is paid to the peeling of the close contact portion between the tube port and the infusion bag or the connector, it is considered that the dimensional stability of the tube port under high humidity also affects the barrier property. In this respect, the method described in Patent Document 2 using EVOH is inferior in water vapor barrier properties and has a problem in dimensional stability under high humidity. Further, ordinary EVOH has a problem that delamination, whitening, and the like occur when retort sterilization or autoclave sterilization is performed.

  In addition, it is desirable to be able to grasp the defects from the appearance of the tube port when foreign matter is mixed in, when some of the components of the contents are crystallized, or when the connection with the connector is incomplete. Therefore, as the tube port, a tube port having a predetermined barrier property and an excellent visibility inside is desired.

  The present invention has been made in view of the above problems, and is a tube port excellent in water vapor barrier properties and oxygen barrier properties, adhesion between an infusion bag and a connector, and visibility, and a tube provided with the tube port The purpose is to provide a container with a port.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a cylindrical molded body having a predetermined resin layer, and have completed the present invention.

That is, the present invention is as follows.
[1]
A tube port attached to the infusion bag,
Comprising a cylindrical molded body having a resin layer I containing polyvinylidene chloride;
Tube port.
[2]
The water vapor permeability of the cylindrical molded body is 1000 g · μm / m ² · 24 hrs · atm (38 ° C. · 90% RH) or less.
The tube port according to [1].
[3]
The cylindrical molded body has an oxygen permeability of 1000 mL · μm / m ² · 24 hrs · atm (23 ° C. · 65% RH) or less.
The tube port according to [1] or [2].
[4]
The cylindrical molded body has a resin layer II containing polyolefin in the outermost layer,
The tube port according to any one of [1] to [3].
[5]
The cylindrical molded body has, in the innermost layer, a resin layer III containing one or more selected from the group consisting of a thermoplastic elastomer, polypropylene, and ethylene vinyl acetate.
The tube port according to any one of [1] to [4].
[6]
The cylindrical molded body further includes a resin layer IV disposed between the resin layer I and the resin layer II and / or a resin layer V disposed between the resin layer I and the resin layer III. Have
The tube port according to [5].
[7]
An infusion bag with a tube port, comprising: an infusion bag; and the tube port according to any one of [1] to [6] attached to the infusion bag.

  According to the present invention, it is possible to provide a tube port excellent in water vapor barrier properties and oxygen barrier properties, infusion bag and connector adhesion, and visibility, and an infusion bag with a tube port provided with the tube port. .

It is a side view showing the infusion bag with a tube port provided with the tube port of this embodiment. It is sectional drawing which looked at the tube port of this embodiment from the axial direction. It is sectional drawing which shows the aspect of a visibility test.

  Hereinafter, the embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications are possible without departing from the scope of the present invention. It is.

(Tube port)
The tube port of the present embodiment includes a cylindrical molded body having a resin layer I containing polyvinylidene chloride. In addition, as described above, the “tube port” is an end (hereinafter also referred to as “inner end of the infusion bag”) to which the infusion bag is bonded (welded) among the plugs serving as the flow path of the infusion bag. And an end that is exposed to the outside of the infusion bag and can be connected to various connectors (hereinafter also referred to as a “connector connection end”), and is distinguished from a closure plug-type port. (FIG. 1). For example, in the case where the infusion bag is configured by bonding two films so that the center is a space for liquid retention, the tube port has an infusion bag inner end constituting the infusion bag 2 The inner surface of the film is inserted into the infusion bag so that the outer periphery of the tube port is adhered (welded). When injecting the infusion solution into the infusion bag, the infusion solution can be injected into the infusion bag via the tube port. Moreover, after injection, various connectors can be connected to the connector connection end of the tube port, and high-pressure steam sterilization can be performed. The tube port is a member that seals the infusion bag together with the connector when the infusion bag is not used, and is a member that allows the liquid to communicate with the inside and outside of the infusion bag during use.

  FIG. 1 shows a side view showing an infusion bag with a tube port provided with the tube port of the present embodiment, and FIG. 2 shows a sectional view of the tube port as seen from the axial direction. The tube port 10 of this embodiment is attached to the infusion bag 20 so that the tip (connector connection end) of the infusion bag 20 is partially exposed. A connector 2 is provided in close contact with the inner wall of the tubular molded body 1 at the tip of the tube port 10 exposed from the infusion bag 20. The connector 2 has, for example, a twist-off structure that can be opened by twisting. The tube port 10 of the present embodiment can be used for medical and food (including beverage) infusion bags.

  Since the conventional tube port is inferior in oxygen barrier property and / or water vapor barrier property, even if the infusion bag itself containing the liquid has oxygen barrier property and water vapor barrier property, it has passed through the tube port. There is a problem that oxygen and water vapor deteriorate the contents in the infusion bag, or conversely, components in the contents of the infusion bag diffuse to the outside via the tube port.

  On the other hand, the tube port of this embodiment can prevent deterioration of medicines, foods, etc. in the infusion bag that dislikes the invasion of gas such as oxygen and water vapor by providing a predetermined cylindrical molded body. Can be preserved for a long period of time while maintaining safety and safety, and the components in the contents of the infusion bag can be prevented from escaping to the outside via the tube port. Furthermore, according to the present embodiment, the barrier property can be maintained even if the infusion bag with a tube port from the viewpoint of sterilization is subjected to high-pressure steam sterilization treatment or hot water treatment.

(Cylindrical compact)
By using the cylindrical molded body having the resin layer I, the oxygen barrier property and / or the water vapor barrier property of the tube port can be ensured, the deterioration of the medicine, food, etc. in the infusion bag can be prevented, and hygiene Long-term storage is possible while maintaining safety and safety. Further, it is excellent in dimensional stability under high humidity and excellent in internal visibility (transparency). In the present embodiment, the “resin layer” refers to a cylindrical layer disposed along the side wall of the cylindrical molded body.

  The cylindrical molded body is not particularly limited as long as it has a resin layer I containing polyvinylidene chloride, and may be a single layer structure of the resin layer I, or may be combined with other resin layers as necessary. A multilayer structure may be used. The multilayer structure is not particularly limited. For example, a two-layer structure having an innermost layer and an outermost layer, and a structure of three or more layers having an innermost layer, one or more intermediate layers, and an outermost layer are included. Can be mentioned. In the case of a multilayer structure, the resin layer I may be any of the innermost layer, the intermediate layer, and the outermost layer. FIG. 1 shows a schematic cross-sectional view of a cylindrical molded body having a three-layer structure. In FIG. 1, a resin layer I is disposed in the intermediate layer, a resin layer II described later is disposed in the outermost layer, and a resin layer III described later is disposed in the innermost layer. The layer thicknesses of the resin layer I, the resin layer II, and the resin layer III are h1, h2, and h3, respectively.

  The resin layer other than the resin layer I is not particularly limited. For example, the resin layer II containing a polyolefin (hereinafter also referred to as “PO”) and a thermoplastic elastomer (hereinafter also referred to as “TPE”). , Polypropylene (hereinafter also referred to as “PP”), and resin layer III including one or more selected from the group consisting of ethylene vinyl acetate (hereinafter also referred to as “EVA”), and other resin layers. . The other resin layer is not particularly limited, and examples thereof include a resin layer IV disposed between the resin layer I and the resin layer II, and a resin layer V disposed between the resin layer I and the resin layer III. It is done.

[Resin layer I: Polyvinylidene chloride]
The resin layer I contributes to improvement of the oxygen barrier property and water vapor barrier property of the tube port, dimensional stability under high humidity, and internal visibility. The resin layer I contains polyvinylidene chloride, and is preferably made of polyvinylidene chloride. Examples of the polyvinylidene chloride constituting the resin layer I include a vinylidene chloride homopolymer and a vinylidene chloride copolymer of a vinylidene chloride monomer and a monomer copolymerizable therewith.

  The monomer copolymerizable with the vinylidene chloride monomer (hereinafter sometimes referred to as “comonomer”) is not particularly limited, and examples thereof include vinyl chloride; acrylic acid esters such as methyl acrylate and butyl acrylate. Acrylic acid; methacrylic acid esters such as methyl methacrylate and butyl methacrylate; methacrylic acid; methyl acrylonitrile; vinyl acetate and the like. Among these, acrylic acid ester and methyl acrylonitrile are preferable from the viewpoint of water vapor barrier property, oxygen barrier property and extrusion processability. These copolymerizable monomers may be used alone or in combination of two or more.

  The comonomer content of the vinylidene chloride-acrylic acid ester copolymer, the vinylidene chloride-methacrylic acid ester copolymer, and the vinylidene chloride-methylacrylonitrile copolymer is preferably 1 to 40% by mass, more preferably 1 to 35%. % By mass, more preferably 2 to 25% by mass, still more preferably 2 to 15.5% by mass, still more preferably 4 to 15% by mass, and particularly preferably 5 to 15% by mass. It is. When the comonomer content in the vinylidene chloride copolymer is 1% by mass or more, the melting characteristics during extrusion tend to be further improved. Moreover, when the comonomer content of the vinylidene chloride copolymer is 40% by mass or less, the water vapor barrier property and the oxygen barrier property tend to be further improved.

  The comonomer content of the vinylidene chloride-vinyl chloride copolymer is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, still more preferably 1 to 25% by mass, and even more. Preferably it is 4-15 mass%, Most preferably, it is 5-15 mass%. is there. When the comonomer content of the vinylidene chloride copolymer is 1% by mass or more, the melting characteristics at the time of extrusion tend to be further improved. Moreover, when the comonomer content of the vinylidene chloride copolymer is 40% by mass or less, the water vapor barrier property and the oxygen barrier property tend to be further improved.

  The glass transition temperature (Tg) of polyvinylidene chloride is preferably −10 ° C. or higher, more preferably −7 ° C. or higher, and further preferably −2 ° C. or higher. When Tg is −10 ° C. or higher, the stability during extrusion molding tends to be excellent. Further, Tg is preferably 18 ° C. or lower, more preferably 15 ° C. or lower, and further preferably 13 ° C. or lower. When Tg is 18 ° C. or less, the cross-sectional aesthetics at the time of cutting tend to be more excellent.

The weight average molecular weight (Mw) of polyvinylidene chloride is preferably 5 × 10 ^{4 to} 1.5 × 10 ⁵ , more preferably 6 × 10 ^{4 to} 1.3 × 10 ⁵ , and even more preferably 7 ×. 10 ⁴ to 1 × 10 ⁵ . When the weight average molecular weight (Mw) is 5 × 10 ⁴ or more, the melting characteristics at the time of extrusion tend to be further improved. In addition, when the weight average molecular weight (Mw) is 1.5 × 10 ⁵ or less, melt extrusion while maintaining thermal stability tends to be possible. In the present embodiment, the weight average molecular weight (Mw) can be determined by a gel permeation chromatography method (GPC method) using a standard polystyrene calibration curve.

  The thickness of the resin layer I is preferably 5 to 1500 μm, more preferably 10 to 1000 μm, still more preferably 25 to 700 μm, and particularly preferably 50 to 500 μm. When the thickness of the resin layer is within the above range, the cylindrical molded body can be used for more applications.

[Resin layer II: Polyolefin]
The resin layer II is a layer containing polyolefin, preferably a layer made of polyolefin. Although it does not restrict | limit especially as polyolefin, For example, polyethylene-type resin (henceforth "PE"), such as low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-alpha olefin; Polypropylene (henceforth "PP") And cycloolefin polymer (hereinafter also referred to as “COP”). Among these, high-density polyethylene, polypropylene, or cycloolefin polymer is preferable. As resin which comprises the resin layer II, it may be used individually by 1 type, or may use 2 or more types together.

  Although it does not specifically limit as high density polyethylene which comprises the resin layer II, The copolymer which copolymerized with alpha olefins, such as a polyethylene homopolymer and 1-butene, and gave the short branch (SCB) structure is mentioned. . The density of the high density polyethylene is 0.942 to 0.965.

  Although it does not specifically limit as polypropylene which comprises the resin layer II, For example, polypropylene copolymers, such as a polypropylene homopolymer; random polypropylene, a block polypropylene, are mentioned.

  Further, the cycloolefin polymer constituting the resin layer II is not particularly limited, and examples thereof include a polymer containing a monocyclic cycloolefin monomer and / or a norbornene monomer as a monomer. The monocyclic cycloolefin monomer and the norbornene-based monomer may be used alone or in combination of two or more.

  Here, the monocyclic cycloolefin monomer is not particularly limited, and examples thereof include cyclobutene, cyclopentene, cyclooctene, cyclododecene, and 1,5-cyclooctadiene. Further, the norbornene-based monomer is not particularly limited. , Tetracyclics such as phenyltetracyclododecene, pentacyclics such as tricyclopentadiene, and heptacyclics such as tetracyclopentadiene. Monocyclic cycloolefin monomers and norbornene monomers are alkyl-substituted (methyl, ethyl, propyl, butyl-substituted, etc.), alkylidene-substituted (for example, ethylidene-substituted), aryl-substituted (for example, phenyl, tolyl-substituted) And derivatives having a polar group such as an epoxy group, a methacryl group, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a halogen group, an ether bond-containing group, and an ester bond-containing group.

  The thickness of the resin layer II is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 20 μm or less, and even more preferably 10 μm or less. When the thickness of the resin layer II is 100 μm or less, the flexibility of the cylindrical molded body tends to be further improved. In particular, when the thickness is 20 μm or less, the transparency of the cylindrical molded body tends to be further improved. The lower limit of the thickness of the resin layer II is not particularly limited and is 3 μm or more.

  The resin layer II is preferably provided in the outermost layer (outermost layer of the tube port) of the cylindrical molded body. By providing the resin layer II containing polyolefin, particularly high-density polyethylene, polypropylene, or cycloolefin polymer, on the outermost layer of the cylindrical molded body (outermost layer of the tube port), the adhesion with the film constituting the infusion bag is improved. It tends to improve.

[Resin layer III]
The resin layer III is a layer containing at least one selected from the group consisting of a thermoplastic elastomer, polypropylene, and ethylene vinyl acetate. Among these, a thermoplastic elastomer, polypropylene, and ethylene vinyl acetate are preferable, and a thermoplastic elastomer is more preferable.

  The thermoplastic elastomer is not particularly limited. For example, a polystyrene-based thermoplastic elastomer, a polyolefin-based thermoplastic elastomer, a vinyl chloride-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, These copolymer elastomers such as polybutadiene-based thermoplastic elastomers or polystyrene-polyolefin-based thermoplastic elastomers such as hydrogenated styrene-conjugated diene block copolymers may be mentioned. Among these, polyolefin-based thermoplastic elastomers and polystyrene-polyolefin-based thermoplastic elastomers are preferable. By using such a thermoplastic elastomer, the adhesiveness with the film constituting the infusion bag tends to be further improved.

  The content of vinyl acetate in ethylene vinyl acetate is preferably 1 to 35% by mass, more preferably 5 to 30% by mass, and further preferably 10 to 25% by mass with respect to 100% by mass of ethylene vinyl acetate. %, Particularly preferably 15 to 20% by mass. When the content of vinyl acetate is within the above range, the adhesion with the connector tends to be further improved.

  Although it does not specifically limit as polypropylene, For example, polypropylene homopolymer; Polypropylene copolymers, such as a random polypropylene and a block polypropylene, are mentioned.

  The thickness of the resin layer III is preferably 3 to 200 μm, more preferably 3 to 100 μm, still more preferably 3 to 50 μm, still more preferably 3 to 20 μm, still more preferably 3 to 10 μm.

  The resin layer III is preferably provided on the innermost layer (the innermost layer of the tube port) of the cylindrical molded body. By providing the resin layer III containing thermoplastic elastomer, polypropylene, or ethylene vinyl acetate in the innermost layer of the cylindrical molded body (innermost layer of the tube port), the adhesion between the tube port and the connector tends to be further improved. .

[Resin layer IV]
The resin layer IV is a resin layer disposed between the resin layer I and the resin layer II. Although it does not restrict | limit especially as resin which comprises the resin layer IV, For example, a thermoplastic elastomer, polyolefin, and ethylene vinyl acetate are mentioned. Among these, a thermoplastic elastomer and ethylene vinyl acetate are preferable, and a thermoplastic elastomer is more preferable. By using such a resin, the adhesiveness between the resin layer I and the resin layer II tends to be further improved. In addition, the said resin may be used individually by 1 type, or may use 2 or more types together. Further, the resin layer IV is a layer containing the resin, and is preferably a layer made of the resin.

  The thermoplastic elastomer is not particularly limited. For example, a polystyrene-based thermoplastic elastomer, a polyolefin-based thermoplastic elastomer, a vinyl chloride-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, Polybutadiene-based thermoplastic elastomers can be mentioned. Among these, polyolefin-based thermoplastic elastomers are preferable. By using such a thermoplastic elastomer, the adhesiveness between the resin layer I and the resin layer II tends to be further improved.

  The content of vinyl acetate in ethylene vinyl acetate is preferably 1 to 35% by mass, more preferably 5 to 30% by mass, and further preferably 10 to 25% by mass with respect to 100% by mass of ethylene vinyl acetate. %, Particularly preferably 15 to 20% by mass. When the content of vinyl acetate is within the above range, the adhesiveness between the resin layer I and the resin layer II tends to be further improved.

  The thickness of the resin layer IV is preferably 3 to 200 μm, more preferably 5 to 100 μm, and still more preferably 5 to 75 μm.

[Resin layer V]
The resin layer V is a resin layer disposed between the resin layer I and the resin layer III. Although it does not restrict | limit especially as resin which comprises the resin layer V, For example, a thermoplastic elastomer, polyolefin, and ethylene vinyl acetate are mentioned. Among these, a thermoplastic elastomer and ethylene vinyl acetate are preferable, and a thermoplastic elastomer is more preferable. By using such a resin, the adhesiveness between the resin layer I and the resin layer III tends to be further improved. In addition, the said resin may be used individually by 1 type, or may use 2 or more types together. Moreover, the resin layer V is a layer containing the said resin, Preferably it is a layer which consists of said resin.

  The thermoplastic elastomer is not particularly limited. For example, a polystyrene-based thermoplastic elastomer, a polyolefin-based thermoplastic elastomer, a vinyl chloride-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, Polybutadiene-based thermoplastic elastomers can be mentioned. Among these, polyolefin-based thermoplastic elastomers are preferable. By using such a thermoplastic elastomer, the adhesiveness between the resin layer I and the resin layer III tends to be further improved.

  The content of vinyl acetate in ethylene vinyl acetate is preferably 1 to 35% by mass, more preferably 5 to 30% by mass, and further preferably 10 to 25% by mass with respect to 100% by mass of ethylene vinyl acetate. %, Particularly preferably 15 to 20% by mass. When the content of vinyl acetate is within the above range, the adhesion between the resin layer I and the resin layer III tends to be further improved.

  The thickness of the resin layer V is preferably 3 to 200 μm, more preferably 5 to 100 μm, and still more preferably 5 to 75 μm.

(Other additives)
The corner resin layer may contain other additives such as a known plasticizer, heat stabilizer, colorant, organic lubricant, inorganic lubricant, surfactant, and processing aid, as necessary.

  Although it does not specifically limit as a plasticizer, For example, acetyl tributyl citrate, acetylated monoglyceride, dibutyl sebacate etc. are mentioned.

  The heat stabilizer is not particularly limited, and examples thereof include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, epoxy resins, magnesium oxide, hydrotalcite, and the like.

〔Layer structure〕
Although it does not specifically limit as a layer structure of the cylindrical molded object which has a multilayer structure, For example, PVDC / COP, PVDC / PP, PVDC / HDPE, TPE / PVDC, PP / PVDC, EVA / PVDC, TPE / PVDC / COP , PP / PVDC / COP, EVA / PVDC / COP, TPE / PVDC / PP, PP / PVDC / PP, EVA / PVDC / PP, TPE / PVDC / HDPE, PP / PVDC / HDPE, EVA / PVDC / HDPE, TPE / PVDC / TPE / COP, PP / PVDC / TPE / COP, EVA / PVDC / TPE / COP, TPE / PVDC / TPE / PP, PP / PVDC / TPE / PP, EVA / PVDC / TPE / PP, TPE / PVDC / TPE / HDPE, PP / PVDC / TPE / HDP , EVA / PVDC / TPE / HDPE, TPE / PVDC / EVA / COP, PP / PVDC / EVA / COP, EVA / PVDC / EVA / COP, TPE / PVDC / EVA / PP, PP / PVDC / EVA / PP, EVA / PVDC / EVA / PP, TPE / PVDC / EVA / HDPE, PP / PVDC / EVA / HDPE, EVA / PVDC / EVA / HDPE, PP / TPE / PVDC / TPE / COP, EVA / TPE / PVDC / TPE / COP PP / TPE / PVDC / TPE / PP, EVA / TPE / PVDC / TPE / PP, PP / TPE / PVDC / TPE / HDPE, EVA / TPE / PVDC / TPE / HDPE, and the like. The notation “PVDC / PO” indicates that the PVDC layer and the PO layer are laminated from the inside to the outside of the cylindrical molded body.

[Water vapor permeability]
The water vapor permeability of the resin layer at 38 ° C. and 90% RH is preferably 1000 g · μm / m ² · 24 hrs · atm or less, more preferably 500 g · μm / m ² · 24 hrs · atm or less, and further preferably Is 300 g · μm / m ² · 24 hrs · atm or less, more preferably 200 g · μm / m ² · 24 hrs · atm or less, and even more preferably 100 g · μm / m ² · 24 hrs · atm or less. Particularly preferably, it is 50 g · μm / m ² · 24 hrs · atm or less, and most preferably 25 g · µm / m ² · 24 hrs · atm or less. The lower limit of the water vapor permeability of the cylindrical molded body at 38 ° C. and 90% RH is not particularly limited, and is 0 g · μm / m ² · 24 hrs · atm (detection limit). In the present specification, “RH” means relative humidity.

When the water vapor permeability of the cylindrical molded body at 38 ° C. and 90% RH is 1000 g · μm / m ² · 24 hrs · atm or less, the deterioration of the contents, hygiene and safety tend to be further improved. . The water vapor permeability of the cylindrical molded body at 38 ° C. and 90% RH can be reduced by selecting and using a vinylidene chloride copolymer. Moreover, the water vapor permeability of the cylindrical molded body at 38 ° C. and 90% RH can be measured by the method described in the examples.

[Oxygen permeability]
The oxygen permeability of the resin layer at 23 ° C. and 65% RH is preferably 1000 mL · μm / m ² · 24 hrs · atm or less, more preferably 80 mL · μm / m ² · 24 hrs · atm or less, and further preferably Is 50 mL · μm / m ² · 24 hrs · atm or less, more preferably 45 mL · μm / m ² · 24 hrs · atm or less, and even more preferably 35 mL · μm / m ² · 24 hrs · atm or less. Particularly preferably, it is 30 mL · μm / m ² · 24 hrs · atm or less, and most preferably 25 mL · µm / m ² · 24 hrs · atm or less. The lower limit of the oxygen permeability of the resin layer at 23 ° C. and 65% RH is not particularly limited, and is 0 mL · μm / m ² · 24 hrs · atm (detection limit).

When the oxygen permeability of the cylindrical molded body at 23 ° C. and 65% RH is 1000 mL · μm / m ² · 24 hrs · atm or less, the deterioration of the contents, hygiene and safety tend to be further improved. . In addition, the oxygen permeability of the cylindrical molded body at 23 ° C. and 65% RH can be lowered by selecting and using a vinylidene chloride copolymer. Moreover, the oxygen permeability of the cylindrical molded body at 23 ° C. and 65% RH can be measured by the method described in Examples.

[Oxygen permeability maintenance rate]
The oxygen permeability at 23 ° C. and 65% RH of the cylindrical molded body was divided by the oxygen permeability at a high humidity of 23 ° C. and 90% RH, and the value multiplied by 100 was evaluated as the oxygen permeability maintenance rate. 100% is defined as one having no deterioration in oxygen barrier properties due to humidity. The oxygen permeability maintenance rate is preferably 80 to 100%, more preferably 90 to 100%, and still more preferably 95 to 100%. From the viewpoint of sterilization and disinfection, the contents to be packaged may be enclosed in an infusion bag in a heated state, or the infusion bag in which the contents are enclosed may be heated. Even in such a case, when the oxygen permeability maintenance ratio is within the above range, the barrier property such as oxygen permeability tends to be further suppressed. The oxygen permeability maintenance rate can be improved by selecting and using a vinylidene chloride copolymer.

〔connector〕
Although it does not restrict | limit especially as a material which comprises a connector, For example, olefin resin, such as polyethylene and a polypropylene; The said barrier resin, such as a polyvinyl chloride, is mentioned. Among these, polypropylene is preferable from the viewpoint of adhesion to the inner wall of the cylindrical molded body. The shape of the connector is not particularly limited as long as it can be connected to the tube port, and a commercially available product can be used.

[Method of manufacturing tube port]
The manufacturing method of the tube port of the present embodiment is not particularly limited. For example, a method of forming a cylindrical molded body having a single layer or a multilayer structure and using the cylindrical molded body as it is; a cylinder having a single layer or a multilayer structure There is a method of manufacturing a cylindrical molded body by molding a cylindrical molded body and then injection-molding a resin constituting the outermost layer of the cylindrical molded body around the molded molded body. The latter method is configured such that a tubular molded body is inserted into the tube port.

  Examples of the molding method include extrusion molding, injection molding, blow molding, and the like. Among these, from the viewpoint of easy manufacture of the cylindrical molded body, an extrusion molding process in which the resin is melted and extruded into a cylindrical shape is preferable.

[Infusion bag with tube port]
The infusion bag with a tube port according to this embodiment includes an infusion bag and the tube port attached to the infusion bag. Further, a connector may be provided in the distal end portion of the tube port as necessary.

  Examples of the constituent member of the infusion bag include at least one selected from the group consisting of a laminated film, a laminated film having an aluminum foil layer, and a metal-deposited film. Among these, from the viewpoint of adhesion to the tube port, the innermost layer is preferably a synthetic resin.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited at all by these.

[Preparation of substitute measurement sample for measuring oxygen permeability, water vapor permeability, and oxygen permeability maintenance ratio]
In the measurement of the oxygen permeability, water vapor permeability, and oxygen permeability maintenance rate of the cylindrical molded body, a multilayer film imitating the layer structure (type of resin, stacking order, thickness ratio of each layer) of the cylindrical molded body A substitute measurement sample is prepared, and the oxygen permeability, water vapor permeability, and oxygen permeability of the cylindrical molded body are maintained from the measured values of oxygen permeability, water vapor permeability, and oxygen permeability maintenance rate of the substitute measurement sample. The rate was calculated.

  The substitute measurement film for the cylindrical molded body has a layer composition ratio similar to that of the cylindrical molded body using a direct inflation apparatus and a co-extrusion multilayer die, and the thickness of the layer is 1 / of that of the cylindrical molded body. It was obtained by forming a multilayer film having a thickness of 10. Hereinafter, the substitute measurement film refers to a film having the same layer composition ratio as that of the cylindrical molded body and having a layer thickness of 1/10 of that of the cylindrical molded body.

The oxygen permeability and water vapor permeability per thickness of the substitute measurement film are measured, and the oxygen permeability and water vapor permeability per 1 μm thickness are obtained by multiplying the obtained measurement value by the thickness of the substitute measurement film. It was. Since it can be evaluated that the barrier property is higher as the various transmittances per 1 μm thickness are smaller, the various barrier properties when the thickness of the cylindrical molded body is evaluated by comparing the various transmittances per 1 μm thickness. Is possible.
Permeation per 1 μm thickness = Transparency of substitute measurement film × Thickness of substitute measurement film

[Oxygen permeability (OTR)]
The oxygen transmission rate (OTR) was measured according to ASTM D-3985. Specifically, using a Mocon OX-TRAN 2/20, a substitute measurement sample having a predetermined thickness was measured under the conditions of 23 ° C. and 65% RH. The obtained measured value was multiplied by the thickness of the cylindrical molded body to obtain oxygen permeability per 1 μm thickness (rounded off after the decimal point). The unit of oxygen permeability (mL · μm / m ² · 24 hrs · atm) represents the oxygen permeability per 1 μm thickness.

[Water vapor transmission rate (WVTR)]
The water vapor transmission rate (WVTR) was measured according to ASTM F-372. Specifically, a substitute measurement sample having a predetermined thickness was measured under the conditions of 38 ° C. and 90% RH using Mocon PERMATRAN-W398. The obtained measured value was multiplied by the thickness of the cylindrical molded body to obtain the water vapor permeability per 1 μm thickness (rounded off to the nearest decimal point). The unit of water vapor transmission rate (g · μm / m ² · 24 hrs · atm) indicates the water vapor transmission rate per 1 μm thickness.

[Oxygen permeability maintenance rate]
The oxygen permeability maintenance rate was measured according to ASTM D-3985. Specifically, using a Mocon OX-TRAN 2/20, a substitute measurement sample having a predetermined thickness was measured under the conditions of 23 ° C. and 65% RH and 23 ° C. and 90% RH. The obtained measured value was multiplied by the thickness of the cylindrical molded body to obtain oxygen permeability per 1 μm thickness (rounded off after the decimal point). Then, maintain the oxygen permeability by dividing the oxygen permeability under the conditions of 23 ° C. and 65% RH by the oxygen permeability under the conditions of 23 ° C. and 90% RH (rounded off to the nearest decimal place) and multiplying by 100%. Got the rate.

[Glass transition temperature (Tg)]
Measurements were made using a Diamond DSC from PerkinElmer. Each resin used in Examples and Comparative Examples was made into a sample of 5 mg to 10 mg and set in a device. From the endothermic curve when the sample was heated from −50 ° C. to 190 ° C., the midpoint glass transition temperature was determined according to JIS K-7121. In addition, raising / lowering temperature was performed at the speed | rate of 10 degree-C / min.

〔Visibility〕
Autoclave sterilization was performed on the tube ports obtained in Examples and Comparative Examples under the conditions of 121 ° C., 0.2 MPa, and 20 minutes. After the treatment, moisture on the inside was wiped off, and a square of 1 mm in width and length was written on the inside of the tube with a black oil-based pen, and this was regarded as a foreign substance. 10 tube ports with foreign objects on the inside are shown to 100 panelists, respectively, and are cylindrical from the direction A in FIG. 3 (the direction opposite to the radial direction of the part marked with a square mark simulating foreign objects). The molded body was observed, and an evaluation was made on whether or not foreign matter was observed in the tube port, and a sensory test score of 0 to 2 points was obtained.
2 points: The foreign matter in the tube port can be clearly recognized. 1 point: The foreign matter in the tube port can be recognized (although it is blurred).
0 point: Cannot recognize the presence of foreign matter in the tube port

The first decimal place of the average value of 1000 sensory test scores was rounded off to give an evaluation score. Based on the obtained evaluation points, visibility was evaluated according to the following criteria.
A: Average value of sensory test score is 1.5 or more B: Average value of sensory test score is 0.5 or more and less than 1.5 C: Average value of sensory test score is less than 0.5

[Adhesion 1; Evaluation of Adhesion between Infusion Bag Body and Tube Port]
The peel strength at the welded portion between the film of the infusion bag body and the tube port was measured. Specifically, after the high-pressure steam sterilization treatment, the infusion bag main body and the tube port welded portion are cut into a strip shape having a width of 5 mm in the width direction of the infusion bag, and in accordance with JIS Z 0238, 23 ± 2 ° C., relative A peel test was performed under the conditions of humidity 50 ± 5% and peel speed of 300 mm / min, and 90 ° peel strength (N / 5 mm) was measured.

[Adhesion 2; Evaluation of adhesion between tube port and connector]
After inserting the connector into the tube port and subjecting it to high-pressure steam sterilization, cut the tube port together with the connector, and peel off the contact part between the connector and the tube port. And evaluated.
A: The connector cannot be removed from the tube port. Peeling was a cohesive failure, and tube pieces were seen on the peeled surface.
B: The connector cannot be removed from the tube port. The peeling was interfacial peeling, and the peeled surface was smooth.
C: The connector can be removed from the tube port.

[Method of manufacturing infusion bag with tube port]
Using the cylindrical molded body obtained in Examples and Comparative Examples as a tube port, a polypropylene twist-off spike port (manufactured by Maruji) was inserted as a connector into the tube port and plugged. . The stopper was attached to an infusion bag whose innermost layer was made of polypropylene (Nippon Polypropylene Co., Ltd. Novatec PP EA-9), heat sealed, and autoclaved at 121 ° C. for 20 minutes.

[Example 1]
From inside, thermoplastic elastomer (TPE-A; manufactured by Mitsubishi Chemical Corporation, product name: Zelas MC721AP) as resin layer III, and vinylidene chloride copolymer (PVDC-A; vinylidene chloride (VDC) / methyl acrylate) as resin layer I (MA) = 96/4 (mass%), weight average molecular weight 8 × 10 ⁴ , Tg = 5 ° C., manufactured by Asahi Kasei Corporation, TPE-A as resin layer IV, cycloolefin polymer (COP; Japan as resin layer II) Zeon Co., Ltd., ZEONOR 1020R and Nippon Zeon Co., Ltd., ZEONEX 690R (equal mixture of ZEONEEX 690R) are formed in the order of layers, and are continuously extruded in a cylindrical shape using a melt extrusion equipment equipped with a coextrusion multilayer cylindrical die did. Thereafter, the inner diameter was adjusted to 6 mm in a cold water tank equipped with an outer diameter sizing device to obtain a cylindrical molded body having a four-layer structure having a thickness of 700 μm. Moreover, the substitute measurement film of thickness 70micrometer was obtained using the same resin.

[Example 2]
As a resin constituting the resin layer I, instead of the PVDC-A resin, a vinylidene chloride copolymer (PVDC-B; vinylidene chloride (VDC) / methyl acrylate (MA) = 92/8 (mass%), weight average molecular weight Except for using 8 × 10 ⁴ , Tg = 13 ° C., manufactured by Asahi Kasei Co., Ltd.), a cylindrical molded body having a four-layer structure with an inner diameter of 6 mm and a thickness of 700 μm, and a thickness of 70 μm, as in Example 1. A substitute measurement film was obtained.

Example 3
As a resin constituting the resin layer I, instead of the PVDC-A resin, a vinylidene chloride copolymer (PVDC-C; vinylidene chloride (VDC) / vinyl chloride (VC) = 89/11 (mass%), and weight In the same manner as in Example 1 except that an average molecular weight of 8 × 10 ⁴ , Tg = −7 ° C., manufactured by Asahi Kasei Co., Ltd. was used, A substitute measurement film having a thickness of 70 μm was obtained.

Example 4
As a resin constituting the resin layer I, instead of the PVDC-A resin, a vinylidene chloride copolymer (PVDC-D; vinylidene chloride (VDC) / methyl acrylate (MA) = 90/10 (mass%), and weight Except for using an average molecular weight of 8 × 10 ⁴ , Tg = 14 ° C., manufactured by Asahi Kasei Co., Ltd.), and a cylindrical molded body having a four-layer structure with an inner diameter of 6 mm and a thickness of 700 μm, and a thickness, as in Example 1. A substitute measurement film of 70 μm was obtained.

Example 5
As a resin constituting the resin layer I, instead of the PVDC-A resin, a vinylidene chloride copolymer (PVDC-E; vinylidene chloride (VDC) / vinyl chloride (VC) = 95/5 (mass%), weight average molecular weight 8 × 10 ⁴ , Tg = −8 ° C., manufactured by Asahi Kasei Co., Ltd.) In the same manner as in Example 1, a cylindrical molded body having a four-layer structure with an inner diameter of 6 mm and a thickness of 700 μm, and a thickness of 70 μm A substitute measurement film was obtained.

Example 6
As resin constituting the resin layer III, in place of TPE-A resin, ethylene vinyl acetate (EVA; manufactured by Asahi Kasei Co., Ltd., product name Suntec-EVA EF1522) was used in the same manner as in Example 1, A cylindrical molded body having a four-layer structure having a diameter of 6 mm and a thickness of 700 μm, and a substitute measurement film having a thickness of 70 μm were obtained.

Example 7
As a resin constituting the resin layer III, a polypropylene polymer (PP; manufactured by Nippon Polypro Co., Ltd., product name: Novatec PP EA-9) is used instead of the TPE-A resin as a resin constituting the resin layer III. Except having used TPE-A, it carried out similarly to Example 1, and obtained the cylindrical molded object which consists of a 5-layer structure with an inner diameter of 6 mm and a thickness of 700 micrometers, and the substitute measurement film of thickness 70 micrometers.

Example 8
As a resin constituting the resin layer III, a thermoplastic elastomer (TPE-B: manufactured by Mitsubishi Chemical Corporation, product name: Zelas 719) is used instead of the TPE-A resin, and as a resin constituting the resin layer V, TPE- Except for using the A resin, a cylindrical molded body having a five-layer structure having an inner diameter of 6 mm and a thickness of 700 μm and a substitute measurement film having a thickness of 70 μm were obtained in the same manner as in Example 1.

Example 9
The inner diameter of the resin layer II was the same as in Example 1 except that high-density polyethylene (HDPE; manufactured by Asahi Kasei Corporation, product name: Suntech-HD B770) was used instead of the COP resin. A tubular molded body having a four-layer structure of 6 mm and a thickness of 700 μm, and a substitute measurement film having a thickness of 70 μm were obtained.

Example 10
As in Example 1, except that HDPE resin was used instead of the COP resin as the resin constituting the resin layer II, and EVA was used instead of the TPE-A resin as the resin constituting the resin layer IV. Thus, a cylindrical molded body having a four-layer structure having an inner diameter of 6 mm and a thickness of 700 μm, and a substitute measurement film having a thickness of 70 μm were obtained.

Example 11
As resin constituting the resin layer II, in place of the COP resin, a polypropylene polymer (PP; manufactured by Nippon Polypro Co., Ltd., product name: Novatec PP EA-9) was used in the same manner as in Example 1. A cylindrical molded body having a four-layer structure having an inner diameter of 6 mm and a thickness of 700 μm, and a substitute measurement film having a thickness of 70 μm were obtained.

[Example 12]
Except that the thickness of the resin layer I made of PVDC-A resin was set to 100 μm, a cylindrical molded body having a four-layer structure with an inner diameter of 6 mm and a thickness of 500 μm, and a substitute measurement of a thickness of 50 μm, as in Example 1. Got the film

Example 13
Except that the thickness of the resin layer I made of PVDC-A resin was set to 500 μm, a cylindrical molded body having a four-layer structure with an inner diameter of 6 mm and a thickness of 900 μm, and a substitute measurement of a thickness of 90 μm, as in Example 1. Got the film

Example 14
Except that the thickness of the resin layer II made of COP resin was 50 μm, a cylindrical molded body having a four-layer structure with an inner diameter of 6 mm and a thickness of 650 μm and a substitute measurement film with a thickness of 65 μm were obtained in the same manner as in Example 1. It was.

Example 15
Except that the thickness of the resin layer II made of COP resin is 20 μm, a cylindrical molded body having a four-layer structure with an inner diameter of 6 mm and a thickness of 620 μm and a substitute measurement film with a thickness of 62 μm are obtained in the same manner as in Example 1. It was.

Example 16
Except that the thickness of the resin layer II made of COP resin was 10 μm, a cylindrical molded body having a four-layer structure having an inner diameter of 6 mm and a thickness of 610 μm and a substitute measurement film having a thickness of 61 μm were obtained in the same manner as in Example 1. It was.

Example 17
Except that the thickness of the resin layer III made of TPE-A resin was set to 150 μm, a cylindrical molded body having a four-layer structure having an inner diameter of 6 mm and a thickness of 600 μm, and a substitute measurement film having a thickness of 60 μm, as in Example 1. Got.

Example 18
Except that the thickness of the resin layer III made of TPE-A resin was set to 100 μm, a cylindrical molded body having a four-layer structure having an inner diameter of 6 mm and a thickness of 550 μm, and a substitute measurement film having a thickness of 55 μm, as in Example 1. Got.

Example 19
Except that the thickness of the resin layer III made of TPE-A resin was set to 70 μm, a cylindrical molded body having a four-layer structure having an inner diameter of 6 mm and a thickness of 520 μm, and a substitute measurement film having a thickness of 53 μm, as in Example 1. Got.

Example 20
Except that the thickness of the resin layer III made of TPE-A resin was set to 60 μm, a cylindrical molded body having a four-layer structure having an inner diameter of 6 mm and a thickness of 510 μm, and a substitute measurement film having a thickness of 51 μm, as in Example 1. Got.

Example 21
Except that the resin layer IV was not provided, a cylindrical molded body having a three-layer structure having an inner diameter of 6 mm and a thickness of 600 μm and a substitute measurement film having a thickness of 60 μm were obtained in the same manner as in Example 1.

[Example 22]
A cylinder having a three-layer structure with an inner diameter of 6 mm and a thickness of 600 μm, as in Example 1, except that the resin layer IV was not provided and that the resin constituting the resin layer III was replaced with EVA instead of TPE-A. And a substitute measuring film having a thickness of 60 μm were used.

[Comparative Example 1]
As resin which comprises the resin layer I, it replaced with PVDC-A resin and carried out similarly to Example 1 except having used the ethylene vinyl alcohol copolymer (EVOH; the Kuraray Co., Ltd. product name: Eval L171B). A cylindrical molded body having a four-layer structure having an inner diameter of 6 mm and a thickness of 700 μm, and a substitute measurement film having a thickness of 70 μm were obtained.

[Comparative Example 2]
As the resin constituting the resin layer I, in place of the PVDC-A resin, MXD6 polyamide resin (PA; manufactured by Mitsubishi Gas Chemical Co., Ltd., product name S6007) was used. A tubular molded body having a four-layer structure of 6 mm and a thickness of 700 μm, and a substitute measurement film having a thickness of 70 μm were obtained.

[Comparative Example 3]
As a resin constituting the resin layer III, low-density polyethylene (LDPE: manufactured by Asahi Kasei Corporation, product name: Suntech-LD M2203) is used instead of the TPE-A resin, and as the resin constituting the resin layer V, the TPE-A is used. In the same manner as in Example 1 except that EVOH was used instead of PVDC-A as a resin constituting the resin layer I, a cylindrical molded body having a five-layer structure with an inner diameter of 6 mm and a thickness of 700 μm, A substitute measurement film having a thickness of 70 μm was obtained.

[Comparative Example 4]
The resin layer II was replaced with a COP resin instead of an LDPE resin, and the resin layer I was replaced with a PVDC-A resin instead of an EVOH resin as in Example 1. Thus, a cylindrical molded body having a four-layer structure having an inner diameter of 6 mm and a thickness of 700 μm, and a substitute measurement film having a thickness of 70 μm were obtained.

  In Comparative Example 1 using EVOH, the oxygen permeability maintenance rate is low, the layer dimensions change during moisture absorption, the phenomenon of delamination between layers, and the adhesion with the infusion bag and the connector is reduced. A decrease in visibility was observed.

  The tube port of the present invention has industrial applicability as a tube port used for an infusion bag.

Claims (7)

A tube port attached to the infusion bag,
Comprising a cylindrical molded body having a resin layer I containing polyvinylidene chloride;
Tube port. The water vapor permeability of the cylindrical molded body is 1000 g · μm / m ² · 24 hrs · atm (38 ° C. · 90% RH) or less.
The tube port according to claim 1. The cylindrical molded body has an oxygen permeability of 1000 mL · μm / m ² · 24 hrs · atm (23 ° C. · 65% RH) or less.
The tube port according to claim 1 or 2. The cylindrical molded body has a resin layer II containing polyolefin in the outermost layer,
The tube port according to any one of claims 1 to 3. The cylindrical molded body has, in the innermost layer, a resin layer III containing one or more selected from the group consisting of a thermoplastic elastomer, polypropylene, and ethylene vinyl acetate.
The tube port according to any one of claims 1 to 4. The cylindrical molded body further includes a resin layer IV disposed between the resin layer I and the resin layer II and / or a resin layer V disposed between the resin layer I and the resin layer III. Have
The tube port according to claim 5.   An infusion bag with a tube port, comprising: an infusion bag; and the tube port according to claim 1 attached to the infusion bag.