JP4887343B2 - Multilayer film and packaging container using the multilayer film - Google Patents

Description

  The present invention relates to a multilayer film and a packaging container using the multilayer film.

Conventionally, when injecting, a medicine enclosed in a glass bottle is injected into a syringe. However, in recent years, prefilled syringes (hereinafter referred to as “syringes”) in which a medicine is filled in advance in order to prevent medical accidents such as mixing of medicines have been spreading.
Generally, the syringe body is composed of a resin composition, but the syringe made of such a resin composition is inferior in the protection performance of the drug compared to the conventional glass bottle, and after the syringe is filled with the drug It is sealed and transported and stored in a transparent and visible packaging container such as a blister pack (see Patent Documents 1 to 3).
JP 2007-126913 A Utility Model Registration No. 3112395 JP-A-11-165387

However, blister packs molded from polyethylene-based or polypropylene-based films as disclosed in Patent Document 1 and Patent Document 2 do not have gas barrier properties. Therefore, when the syringe is stored in the blister pack for a long period of time, the medicine in the syringe may be affected by nitrogen oxides, ink, adhesive components, etc. existing in the external environment. Also, volatile components such as moisture in the drug may be lost, and the drug concentration may change.
On the other hand, Patent Document 3 discloses a blister pack molded from a cyclic olefin resin film. However, the cyclic olefin-based resin film is difficult to obtain interlayer adhesion with other resin films, and there is a possibility that delamination may occur due to steam sterilization performed when used as a drug container.

  The present invention has been made in view of the above circumstances, and can be sterilized by steam, has excellent interlayer adhesion, gas barrier properties and transparency, and has excellent handling properties as a packaging container, and uses the multilayer film. It aims at the packaging container obtained by this.

The multilayer film of the present invention includes an inner layer, an adhesive barrier layer provided on the inner layer, a barrier layer provided on the adhesive barrier layer, and an adhesive flexible layer provided on the barrier layer. And an outer layer provided on the adhesive flexible layer, the inner layer is a layer having a thickness of 5 to 80 μm using an olefin resin, and the adhesion barrier layer is 5% by mass or more and 70% by mass. Is a layer having a thickness of 5 to 80 μm and a barrier layer of 70 to 85% by mass using a mixed resin containing a cyclic olefin resin of less than 30% and 95% by mass or less of a styrene elastomer. % Of a cyclic olefin-based resin and a mixed resin containing 15 to 30% by mass of a styrene-based elastomer, a layer having a thickness of 30 to 80 μm and an adhesive flexible layer of 5 to 50% by mass of an olefin Resin and 50-95 mass Formed by using a mixed resin containing the olefin-based elastomer, a thick layer 10～90Myuemu, the outer layer is made using a thermoplastic resin, characterized in that it is a thick layer 50 to 150 [mu] m.
The packaging container of the present invention comprises a container molded with the inner layer of the multilayer film being the inner surface of the container, and a lid.

  The multilayer film of the present invention can be steam sterilized, has excellent interlayer adhesion, gas barrier properties, and transparency, and has excellent handling properties as a packaging container. Moreover, the packaging container of this invention obtained using such a multilayer film of this invention can prevent the modification | denaturation of the chemical | medical agent with which the inside of the syringe was filled, and the change of a chemical | medical solution concentration indirectly.

The present invention will be described in detail below.
FIG. 1 is a schematic cross-sectional view of an embodiment of a multilayer film according to the present invention.
As shown in FIG. 1, the multilayer film 10 of the present invention includes at least an inner layer 15, an adhesive barrier layer 14 provided on the inner layer 15, and a barrier layer 13 provided on the adhesive barrier layer 14. The adhesive flexible layer 12 provided on the barrier layer 13 and the outer layer 11 provided on the adhesive flexible layer 12 are provided.

[Inner layer]
The inner layer 15 is made of an olefin resin.
The olefinic resin is pharmaceutically approved and has a blocking resistance that can withstand sterilization at high temperatures. From the viewpoint of having a blocking resistance, a copolymer of propylene and ethylene, and a copolymer of propylene and α-olefin. Examples thereof include a blend, a copolymer of ethylene and an α-olefin, or a blend of polypropylene and polyethylene, and one or more of these can be used.

The thickness of the inner layer 15 is 5 to 80 μm, and more preferably 10 to 50 μm. When the thickness is less than 10 μm, it tends to be difficult to ensure a stable sealing property. Here, the sealing property indicates a sealing property with a lid used when a packaging container described later is molded.
On the other hand, if the thickness is larger than 80 μm, the multilayer film tends to be thick and tends to be a multilayer film having poor handling properties. In addition, handling property shows the generation | occurrence | production frequency of the wrinkle and curl at the time of the said multilayer film shaping | molding process.

[Adhesion barrier layer]
The adhesion barrier layer 14 is made of a mixed resin containing a cyclic olefin resin and a styrene elastomer.
The cyclic olefin-based resin is a polyolefin resin having a cyclic structure, and examples thereof include a copolymer of an α-olefin and an alicyclic compound (cyclic olefin) having a double bond. Examples of the α-olefin include ethylene and propylene, and examples of the alicyclic compound include cyclohexane, norbornene, and tetracyclododecene. One or more of these can be used. .
Commercially available products of cyclic olefin resins include “TOPAS (registered trademark)” manufactured by Ticona.
Styrenic elastomers include those with and without hydrogenation. Among them, hydrogenated polystyrene elastomers such as hydrogenated styrene-butadiene elastomer and hydrogenated styrene-isoprene elastomer are flexible, interlayer adhesive, transparent, dispersible in the above cyclic olefin resin, It is excellent in chemical properties and is preferably used in the present invention. These may be used alone or in combination of two or more.

The content rate of cyclic olefin resin in the adhesion barrier layer 14 is 5 mass% or more and less than 70 mass%, and it is especially preferable that it is 60-70 mass%. At this time, the content rate of a styrene-type elastomer is larger than 30 mass%, and is 95 mass% or less, and it is especially preferable that it is 30-40 mass%.
If the content of the cyclic olefin-based resin is 5% by mass or more (the styrene-based elastomer is 95% by mass or less), interlayer adhesion with the inner layer 15 or a barrier layer 13 described later tends to be easily obtained. On the other hand, when the content of the cyclic olefin-based resin is less than 70% by mass (styrene elastomer is greater than 30% by mass), delamination with the inner layer hardly occurs after high-pressure steam sterilization, and the interlayer adhesion tends to be excellent. In particular, when the content of the cyclic olefin is 60% by mass or more (styrene elastomer is 40% by mass or less), the gas barrier performance of the cyclic olefin resin tends to be exhibited, which is preferable.

  The thickness of the adhesion barrier layer 14 is 5 to 80 μm. If the thickness is less than 5 μm, pinholes or the like may occur during film formation, and it is difficult to ensure stable interlayer adhesion. On the other hand, when the thickness is larger than 80 μm, it becomes white due to high-pressure steam sterilization, transparency is lowered, and it becomes difficult to obtain internal visibility, and at the same time, handling property tends to be lowered.

[Barrier layer]
The barrier layer 13 is formed by using a mixed resin containing a cyclic olefin resin and a styrene elastomer.
The cyclic olefin-based resin used for the barrier layer 13 is preferably the same as the cyclic olefin-based resin used for the adhesive barrier layer 14 from the viewpoint of interlayer adhesion. Moreover, it is preferable that the styrene-type elastomer used for the barrier layer 13 is the same as the styrene-type elastomer used for the said adhesion barrier layer 14 from a viewpoint of interlayer adhesiveness.

The content rate of cyclic olefin resin in the barrier layer 13 is 70-85 mass%. At this time, the content rate of a styrene-type elastomer is 15-30 mass%. More preferably, the cyclic olefin resin is 70 to 80% by mass, and the styrene elastomer is 20 to 30% by mass.
When the content of the cyclic olefin resin is less than 70% by mass (the styrene elastomer is more than 30% by mass), the barrier property tends to be difficult to obtain, and whitening occurs due to high-pressure steam sterilization, resulting in decreased transparency. It tends to be difficult to obtain visibility. On the other hand, when the content of the cyclic olefin resin is greater than 85% by mass (styrene elastomer is less than 15% by mass), the flexibility of the entire multilayer film tends to decrease. At this time, there is also a tendency that the interlayer adhesion between the barrier layer and the other layer is lowered, and the multilayer film may cause delamination after high-pressure steam sterilization.

  The thickness of the barrier layer 13 is 30 to 80 μm, and more preferably 40 to 70 μm. When the thickness is less than 30 μm, when molding a packaging container using a multilayer film, the multilayer film is stretched 2 to 10 times, so the barrier layer becomes thin, and the gas barrier property may not be maintained after molding the packaging container There is. On the other hand, when the thickness is larger than 80 μm, the flexibility of the multilayer film tends to be lost, and the handling property tends to be lowered.

  In the multilayer film of the present invention, since a resin layer having a barrier property (barrier layer 13 and adhesive barrier layer 14) is continuously present, defects such as fish eyes and pinholes are generated in either layer. Even if the property deteriorates, the minimum barrier property can be maintained in the other layer.

[Adhesive flexible layer]
The adhesive flexible layer 12 is made of a mixed resin containing an olefin resin and an olefin elastomer.
Examples of the olefin resin include block polypropylene, random polypropylene, homopolypropylene, and reactor polypropylene, and one or more of these can be used. Specifically, the same copolymer of propylene and ethylene as that of the inner layer 15, a copolymer of propylene and α-olefin, a copolymer of ethylene and α-olefin, a blend of polypropylene and polyethylene, and the like. It is done.
Reactor polypropylene refers to a propylene copolymer copolymerized by a reactor blend method. Here, the reactor blending method is a polymerization method in which a plurality of types of polymers are continuously produced by performing multi-stage polymerization of two or more stages, instead of completing the polymerization once. The reactor polypropylene resin is excellent in heat resistance, flexibility and transparency, and is preferably used in the present invention.

  Olefin-based elastomers are those in which olefin-based rubbers such as ethylene-propylene-diene copolymer rubber (EPDM) are finely dispersed in crystalline olefin-based polymers such as polyethylene and polypropylene, and these are simply blended. Or a (partial) cross-linked blend composition. In particular, a crosslinked blend composition is preferred. Also, a hydrogenated olefin block copolymer obtained by polymerizing a crystalline olefin polymer block such as polyethylene or polypropylene and an amorphous olefin (co) polymer block containing a diene compound such as butadiene. Are also preferably used. For example, ethylene-ethylene / butylene-ethylene copolymer (CEBC) and the like can be mentioned.

The content of the olefin resin in the adhesive flexible layer 12 is 5 to 50% by mass, preferably 20 to 50% by mass, and more preferably 40 to 50% by mass. At this time, the content rate of an olefin type elastomer is 50-95 mass%, it is preferable that it is 50-80 mass%, and it is more preferable that it is 50-60 mass%.
When the content of the olefin-based resin is less than 5% by mass (the olefin-based elastomer is greater than 95% by mass), film formation tends to be difficult. On the other hand, when the content of the olefin-based resin is larger than 50% by mass (the olefin-based elastomer is less than 50% by mass), the interlayer adhesion with the barrier layer 13 is lost, and delamination may occur after high-pressure steam sterilization. is there.

  The thickness of the adhesive flexible layer 12 is 10 to 90 μm, preferably 20 to 80 μm. When the thickness is less than 10 μm, it tends to be difficult to ensure stable interlayer adhesion. On the other hand, when the thickness is larger than 90 μm, the handling property tends to be lowered because the thickness is too large.

[Outer layer]
The outer layer 11 is made of a thermoplastic resin. In particular, it is preferable to use an olefin resin, a polyester resin, nylon, an adhesive resin for laminating, or the like that can add added value to the multilayer film of the present invention and is excellent in secondary moldability and deep drawability.
Examples of the olefinic resin include polyethylene, polypropylene, and the like, and it is particularly preferable to use polypropylene having a high melting point because the heat resistance of the multilayer film tends to be improved. Furthermore, when polypropylene is used, the environmental load at the time of disposal tends to be small as compared with other resins, which is preferable.
Examples of the polyester-based resin include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. These resins are preferable because they have excellent heat resistance and water vapor barrier properties, and when used for the multilayer film of the present invention, the tensile strength of the multilayer film tends to be improved.
Nylon is preferred because it tends to improve the puncture strength and the like.
Examples of the adhesive resin for laminating include acrylic resin-based adhesives, α-olefin-based adhesives, urethane-based adhesives, etc. When these are provided in the outer layer, aluminum foil or ethylene-vinyl alcohol is further provided on the outer layer. It becomes possible to laminate a layer having a light shielding property and an oxygen barrier property such as a copolymer resin film.

  The thickness of the outer layer 11 is 50 to 150 μm, and more preferably 60 to 100 μm. When the thickness is less than 50 μm, it cannot withstand high-pressure steam sterilization, and the multilayer film may be deformed or broken. On the other hand, when the thickness exceeds 150 μm, it is difficult to obtain flexibility as a packaging container when the packaging container is molded using a multilayer film.

[Other layers]
In the multilayer film 10 of the present invention, a transparent vapor deposition film or the like can be provided on the outer layer 11 in addition to the aluminum foil and the ethylene-vinyl alcohol copolymer resin film. In addition, various additives such as an ultraviolet absorber and an oxygen absorber can be added to the resin layer closer to the outer layer 11 than the barrier layer 13 within a range that does not impair the spirit of the present invention.

[Manufacture of multilayer films]
The multilayer film 10 can be molded by employing a known method such as a co-extrusion inflation method or a co-extrusion T-die method.

[Manufacture of packaging containers]
The packaging container of the present invention includes a container molded from the multilayer film 10 and a lid. An example of the packaging container of the present invention is shown in FIG. A packaging container 20 shown in FIG. 2 has a container 21 formed from the multilayer film 10 and a lid 22.
The lid 22 is preferably made of a material having gas barrier properties such as an aluminum foil, a polyethylene terephthalate film, a laminated film obtained by thermally laminating an olefin resin film and an aluminum foil, or a film obtained by thinning the multilayer film of the present invention.

In order to mold the packaging container 20 of the present invention, the multilayer film 10 is first molded into the shape of the container 21. At this time, methods such as press molding, membrane press molding, vacuum molding, pressure molding, and vacuum / pressure molding can be used.
Next, a stored item 24 such as a syringe is stored in the container 21, and thereafter the opening of the container 21 is covered with a lid 22, and the flange portion 23 of the container 21 and the peripheral portion of the lid 22 are heat-sealed to form a packaging container. Get 20.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. Further, various physical properties in each example and comparative example are measured by the following methods.

[Interlayer adhesion]
A strip of 25 mm × 150 mm was cut out from the multilayer film before and after high-pressure steam sterilization at 121 ° C. for 20 minutes, and a biaxially stretched PET film of the same size was adhered to both surfaces as a sample. Using a tensile tester, the PET film adhered to both surfaces of the sample is gripped with a chuck, peeled 180 ° at a speed of 300 mm / min at room temperature, and the following values were obtained by measuring the tensile stress and visually observing the peeled surface. Judged by criteria.
A: Maximum tensile stress of 1 kgf / 25 mm or more, and the peeling surface is agglomerated and peeled.
X: The maximum tensile stress is less than 1 kgf / 25 mm, or the peeling surface is peeled off at the interface.
―: Measurement not possible

[Gas barrier properties]
The multilayer film was heat-sealed in a bag shape, and acetic acid was sealed inside, and further sealed in an aluminum bag. After leaving at room temperature for 1 month, the aluminum bag was opened, the presence or absence of acetic acid odor was confirmed by a sensory test, and judged according to the following criteria.
○: The acetic acid odor was not felt.
×: A stimulating odor of acetic acid was felt.

[transparency]
The light transmittance (450 nm) of the multilayer film after steam sterilization at 121 ° C. for 20 minutes was measured and judged according to the following criteria.
○: 450 nm light transmittance is 70% or more ×: 450 nm light transmittance is less than 70% −: Measurement not possible

[Handling]
Five samples of 200 × 200 mm were collected from the obtained multilayer film, visually observed for wrinkles and curls, and evaluated according to the following criteria.
○: Wrinkles and curls are not observed in all samples.
X: Wrinkles and curling were observed.

[Sealability]
A sample was cut from a multilayer film into a 25 mm × 150 mm strip and the inner layers of the two strips were welded (200 ° C., 3.5 sec) with a heat sealer. Using a tensile tester, the sample was peeled 180 ° at a normal temperature of 300 mm / min, and the measured value of the tensile stress and visual observation of the peeled surface were used for the determination based on the following criteria.
A: Maximum tensile stress of 1 kgf / 25 mm or more, and the peeling surface is agglomerated and peeled.
X: The maximum tensile stress is less than 1 kgf / 25 mm, or the peeling surface is peeled off at the interface.

In the following examples and comparative examples, resins used for molding the multilayer film are shown below.
The melt flow rate is expressed as MFR, the glass transition temperature is expressed as Tg, and the melting point is expressed as MP.
Resin (A): Cyclic olefin-based resin “TOPAS (manufactured by Ticona)” (Tg 80 ° C., density 1.02 g / cm ³ , melt flow rate (MFR) 3.5 g / 10 mim (260 ° C.))
Resin (B): Hydrogenated styrene-butadiene elastomer (Tg 80 ° C., density 0.89 g / cm ³ , MFR 3.5 g / 10 min (230 ° C.))
Resin (C): Linear low density polyethylene resin (MP 115 ° C., density 0.921 g / cm ³ , MFR 2.5 g / 10 min (190 ° C.))
Resin (D): Propylene-α-olefin resin “Zeras 7023 (manufactured by Mitsubishi Chemical)” (density 0.89 g / cm ³ , MFR 2 g / 10 min (230 ° C.))
Resin (E): Reactor polypropylene (MP 144 ° C., density 0.885 g / cm ³ , MFR 2.5 g / 10 min (230 ° C.))
Resin (F): ethylene-ethylene-butylene-ethylene block copolymer (Tg-52 ° C., density 0.88 g / cm ³ , MFR 2.5 g / 10 min (230 ° C.))
Resin (G): Polypropylene resin (MP 160 ° C., density 0.89 g / cm ³ , MFR 2.6 g / 10 min (230 ° C.))
Resin (H): Nylon resin “5023FDX21 (manufactured by Ube Industries)” (MP196 ° C.)
Resin (I): Polyester resin (polybutylene terephthalate resin)
Resin (J): Adhesive resin for laminating (α-olefin maleic anhydride adhesive)

[Example 1]
The resin having the blending ratio shown in Table 1 is used for each of the inner layer, the adhesive barrier layer, the barrier layer, the adhesive flexible layer and the outer layer, melted using an extruder, and the thickness of each layer is shown in Table 1 using an inflation device. A multilayer film was molded to the indicated thickness, and each evaluation was performed. The results are shown in Table 1.

[Examples 2 to 5, Comparative Examples 1 to 8]
A multilayer film was molded in the same manner as in Example 1, and each evaluation was performed. The results are shown in Table 1.

[Comparative Example 9]
The resin having the blending ratio shown in Table 2 is used for the inner layer, the adhesive barrier layer, the barrier layer, the adhesive flexible layer and the outer layer, melted using an extruder, and the thickness of each layer is shown in Table 2 using an inflation device. A multilayer film was molded to the indicated thickness, and each evaluation was performed. The results are shown in Table 2.

[Comparative Examples 10 to 18]
A multilayer film was molded in the same manner as in Comparative Example 9, and each evaluation was performed. The results are shown in Table 2.

From Examples 1 to 5 in Table 1, according to the resin structure of the multilayer film of the present invention, even when sterilized by high-pressure steam, it has excellent interlayer adhesion, has transparency without whitening, It can be said that a multilayer film having excellent gas barrier properties can be obtained.
From Example 2 in Table 2, if the thickness of each layer of the multilayer film is the thickness of the multilayer film of the present invention, not only interlayer adhesion, gas barrier properties and transparency, but also handling properties as packaging containers and packaging It can be said that the sealing property with the lid when molding the container is also excellent.

  The multilayer film of the present invention can form a packaging container for packaging pharmaceuticals, prefilled syringes, etc., and can be used as a blister pack or the like.

It is a schematic diagram of the cross section of the multilayer film of this invention. It is a schematic diagram of the cross section of the packaging container of this invention.

Explanation of symbols

10: multilayer film 11: outer layer, 12: adhesive flexible layer, 13: barrier layer, 14: adhesive barrier layer, 15: inner layer 20: packaging container

Claims (2)

An inner layer, an adhesive barrier layer provided on the inner layer, a barrier layer provided on the adhesive barrier layer, an adhesive flexible layer provided on the barrier layer, and an adhesive flexible layer And an outer layer provided on the
The inner layer is a layer having a thickness of 5 to 80 μm using an olefin resin,
The adhesion barrier layer is formed of a mixed resin containing a cyclic olefin resin of 5% by mass or more and less than 70% by mass and a styrene elastomer of greater than 30% by mass and 95% by mass or less, and having a thickness of 5 to 80 μm. Layer,
The barrier layer is a layer having a thickness of 30 to 80 μm, comprising a mixed resin containing 70 to 85% by mass of a cyclic olefin resin and 15 to 30% by mass of a styrene elastomer.
The adhesive flexible layer is a layer having a thickness of 10 to 90 μm formed using a mixed resin containing 5 to 50% by mass of an olefinic resin and 50 to 95% by mass of an olefinic elastomer,
A multilayer film in which the outer layer is a layer having a thickness of 50 to 150 μm, using a thermoplastic resin.   A packaging container comprising a container molded so that the inner layer of the multilayer film according to claim 1 becomes an inner surface of the container, and a lid.

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