Multilayer sheet and press-through pack using same

Abstract

To provide a multi-layer sheet having oxygen barrier property and moisture-proof property, which is rich in moldability and capable of maintaining a gas barrier property function, and PTP in which the multi-layer sheet is used.SOLUTION: There is provided a multilayer sheet in which a first polyolefin sealant layer 1, a first water vapor barrier adhesive layer 2, an oxygen gas barrier base material 3, a second water vapor barrier adhesive layer 4, and a second polyolefin sealant layer 5 are laminated in this order, in which the oxygen gas barrier base material is made of a polyglycolic acid resin, and the first and second water vapor barrier adhesives are a reaction product of a polyepoxy resin and a polyamine resin, a thickness of the oxygen barrier base material is 5 μm or more and 60 μm or less, and a thickness of the water vapor barrier adhesive layer is 1.0 μm or more and 3.8 μm or less, and a thickness of each of the first and second polyolefin sealant layers is 30 μm or more and 400 μm or less.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a multilayer sheet for packaging and a press-through pack (hereinafter referred to as PTP) using the same. [Background technology]

[0002] In PTP, a storage section or small container is created in a shape that is the size of the contents by hot vacuum forming, hot pressure air forming, hot vacuum pressure air forming, etc. using a PTP base material made of a plastic film or sheet, and then it is filled with food, pharmaceutical tablets, glass ampoules, etc., and the opening is covered and sealed with another flexible or thin rigid plastic sheet or aluminum foil.

[0003] On the other hand, since pharmaceutical preparations such as tablets, troches, and capsules are generally highly hygroscopic, transparent molding base sheets with high water vapor barrier properties are required for PTP base materials. Furthermore, in recent years, the drugs contained in the contents have become more sophisticated, and additional functions such as oxygen barrier properties are being required for PTP packaging materials.

[0004] Examples of polymer films that can be used for PTP applications and have oxygen permeability and water vapor permeability, that is, gas barrier properties and moisture resistance, include the resin multilayer sheets described in Patent Documents 1, 2 and 3. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2008 / 156039 [Patent Document 2] JP 2014-68770 A [Patent Document 3] JP 2019-150987 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, the oxygen barrier property and moisture resistance of these proposed resin sheets for forming press-through packages are not sufficient. For example, the laminated film described in Patent Document 1 has an oxygen permeability of 15 ml / m 2 ·day·atm or less, water vapor permeability is 1.0g / m 2 The packaging sheet described in Patent Document 2 has an oxygen absorbing layer and a moisture-proof layer in addition to the oxygen barrier layer, and has an oxygen permeability of 2.0 ml / m 2 ·day·atm or less, water vapor permeability is 100g / m 2 The laminate described in Patent Document 3 lists polyvinyl chloride, aluminum-deposited PET film, and silica-deposited PET film as the water vapor barrier layer, but there are concerns that the depth of the storage part of the PTP may be insufficient when it is molded, and that cracks may occur in the barrier layer, resulting in a significant decrease in barrier function.

[0007] The problem that the present invention aims to solve is to provide a multilayer sheet having oxygen barrier properties and moisture resistance, which is highly formable and can maintain its gas barrier function, and a PTP using the same. [Means for solving the problem]

[0008] In order to solve the above problems, the present invention according to claim 1 provides a multilayer sheet in which a first polyolefin sealant layer, a first water vapor barrier adhesive layer, an oxygen gas barrier substrate, a second water vapor barrier adhesive layer, and a second polyolefin sealant layer are laminated in this order, the oxygen gas barrier substrate being made of a polyglycolic acid resin, the first water vapor barrier adhesive and the second water vapor barrier adhesive being made of a polyepoxy resin and a polyamide resin. the oxygen barrier substrate has a thickness of 5 μm or more and 60 μm or less, the water vapor barrier adhesive layer has a thickness of 1.0 μm or more and 3.8 μm or less, and the first polyolefin-based sealant layer and the second polyolefin-based sealant layer each have a thickness of 30 μm or more and 400 μm or less.

[0009] A second aspect of the present invention relates to the multilayer sheet according to the first aspect, wherein the weight average molecular weight (Mw) of the polyglycolic acid resin is 50,000 or more and 800,000 or less.

[0010] The invention according to claim 3 of the present invention is a press-through pack using the multilayer sheet according to any one of claims 1 and 2. Effect of the Invention

[0011] It is possible to provide a multilayer sheet having oxygen gas barrier properties and moisture resistance, which is highly formable and capable of maintaining its barrier function, and a PTP package using the same. [Brief description of the drawings]

[0012] [Figure 1] 1 is a schematic cross-sectional view showing an example of a configuration of a multilayer sheet according to an embodiment of the present invention. [Diagram 2] 1 is a schematic cross-sectional view showing an example of the configuration of a PTP using a multilayer sheet according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, an embodiment of the present invention will be described in detail.

[0014] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a multilayer sheet according to an embodiment of the present invention.

[0015] [Multi-layer sheet composition] The multilayer sheet 10 of this embodiment is a multilayer sheet in which a first polyolefin substrate 1, a first water vapor barrier adhesive layer 2, an oxygen gas barrier substrate 3, a second water vapor barrier adhesive layer 4, and a second polyolefin substrate 5 are laminated in this order.

[0016] (Oxygen gas barrier substrate) The oxygen gas barrier substrate 3 is a substrate that imparts oxygen gas barrier properties and strength as a package to the multilayer sheet 10 according to this embodiment. As a substrate having oxygen gas barrier properties and strength as a substrate, a substrate containing polyglycolic acid (PGA) resin in the range of 95% by mass to 100% by mass can be used.

[0017] When the proportion of the polyglycolic acid resin contained in the oxygen gas barrier substrate 3 is within the above range, the multilayer sheet of the present invention can be provided with sufficient oxygen gas barrier properties when used as a PTP packaging material. In particular, when the oxygen gas barrier substrate is made of 100% polyglycolic acid resin, the oxygen permeability is 0.2 to 0.7 ml / m 2 This is preferable because it provides high oxygen gas barrier properties of the order of 1.5-day-atm.

[0018] The weight average molecular weight (Mw) of the polyglycolic acid resin contained in the oxygen gas barrier substrate 3 is preferably in the range of 50,000 to 800,000, more preferably in the range of 100,000 to 500,000. If the weight average molecular weight (Mw) of the polyglycolic acid resin is in the above numerical range, it is possible to impart sufficient gas barrier properties. The weight average molecular weight (Mw) of the polyglycolic acid resin in this embodiment is a value measured by GPC measurement using hexafluoroisopropanol solvent. When the molecular weight increases, the free volume when the molecules are assembled becomes smaller, and the cohesive force between the molecules becomes stronger. The interaction between the molecules becomes stronger, the ease of movement of the molecules decreases, and when gas molecules flow in, it becomes difficult to push the molecular chains apart, so the barrier properties are improved.

[0019] The thickness of the oxygen gas barrier substrate 3 is preferably in the range of 5 μm to 60 μm, more preferably in the range of 10 μm to 40 μm, from the viewpoint of film-forming properties and formability of the pocket portion for inserting tablets or the like of the PTP. If the thickness of the oxygen gas barrier substrate 3 is in the above-mentioned numerical range, it is possible to impart sufficient gas barrier properties and transparency for use to the PTP or the like processed using the multilayer sheet 10, and uniform film formation becomes easy. Furthermore, if the thickness of the oxygen gas barrier substrate 3 is thinner than 3 μm, it becomes difficult to form a uniform film. On the other hand, if the thickness of the barrier layer 1 is thicker than 60 μm, transparency is lost.

[0020] In addition to the polyglycolic acid resin, the oxygen gas barrier substrate 3 may contain additives such as modifiers, processing aids, and colorant masterbatches for resins, depending on the application. If the oxygen gas barrier substrate 3 contains these resins, it is possible to improve the processing suitability and impart various functions.

[0021] (Water vapor barrier adhesive layer) The first water vapor barrier adhesive layer 2 and the second water vapor barrier adhesive layer 4 according to the present invention may be made of the same material or different materials. The first water vapor barrier adhesive layer 2 and the second water vapor barrier adhesive layer 4 are layers containing at least an epoxy adhesive as a water vapor barrier adhesive. More specifically, they are layers containing a polymerization reaction product of a polyepoxy resin and a polyamine resin. For example, a gas barrier adhesive Maxive (manufactured by Mitsubishi Gas Chemical Company, Inc.) can be used.

[0022] The thickness of the first water vapor barrier adhesive layer 2 and the second water vapor barrier adhesive layer 4 is preferably 1.0 μm or more and 3.8 μm or less. If the thickness of the first water vapor barrier adhesive layer 2 and the second water vapor barrier adhesive layer 4 is within the above numerical range, they can be reliably bonded, and the water vapor permeability is 0.19 to 0.4 g / m 2 It also has high moisture resistance of about 1000m / day atm.

[0023] (Polyolefin sealant layer) The first polyolefin sealant 1 and the second polyolefin sealant layer 5 according to the present invention may be made of the same material or different materials.

[0024] The first polyolefin sealant layer 1 and the second polyolefin sealant layer 5 are preferably layers containing at least one resin selected from polypropylene (PP) resin, low density polyethylene (LDPE) resin, and linear low density polyethylene resin (LLDPE) in a range of 50% by mass to 100% by mass. If the ratio of the resin contained in the first polyolefin sealant layer 1 and the second polyolefin sealant layer 5 is within the above numerical range, it is possible to impart sufficient impact resistance for use to a PTP or the like processed using the multilayer sheet 10 including the first polyolefin sealant layer 1 and the second polyolefin sealant layer 5.

[0025] The first polyolefin-based sealant layer 1 and the second polyolefin-based sealant layer 5 have a water vapor permeability of 0 g / m2 or less, as measured by a test method conforming to JIS-K7129. 2 ·day or more 1.0g / m 2 If the water vapor permeabilities of the first and second polyolefin sealant layers 1, 5 are within the above-mentioned range, the polyglycolic acid resin contained in the oxygen gas barrier substrate 3 is hydrolyzed by water vapor that has permeated the first polyolefin sealant layer 1 and the second polyolefin sealant layer 5 during storage of the multilayer sheet 10 or during use of a PTP or the like processed using the multilayer sheet 10. This makes it possible to reduce the occurrence of leakage, thereby making it possible to maintain the gas barrier properties imparted to the oxygen gas barrier substrate 3.

[0026] The thickness of each of the first polyolefin sealant layer 1 and the second polyolefin sealant layer 5 is preferably within the range of 30 μm to 400 μm. If the thickness of the first and second sealant layers is within the above range, it is possible to impart sufficient impact resistance for use (thickness and toughness that can protect the contents without crushing the blister pack) to the PTP or the like using the multilayer sheet of the present invention.

[0027] The ratio of the thickness of the oxygen gas barrier substrate to the thickness of each of the first and second sealant layers (thickness of the oxygen gas barrier substrate:thickness of the first (second) polyolefin sealant layer 1 (5)) is preferably within the range of 1:2 to 1:10. If it is within the above range, it is 0.2 to 1.0 ml / m, which is sufficient for use in PTPs and the like processed using the multilayer sheet of the present invention. 2 ·day·atm oxygen gas barrier property of 0.1~0.2g / m 2 It is possible to provide moisture resistance for 10 days.

[0028] As described above, the multilayer sheet 10 according to this embodiment has high impact resistance and low water vapor permeability because the first and second polyolefin sealant layers 1, 5 contain PP resin, LDPE resin, LLDPE resin, etc. For this reason, the multilayer sheet 10 can be widely used for various applications such as food packaging, blister packs and PTPs for daily necessities such as electrical appliances and cosmetics.

[0029] [Performance of multi-layer sheet] The multilayer sheet 10 of the present invention has an oxygen permeability of 3.0 ml / m2 as measured by a test method in accordance with JIS-K7126. 2 Furthermore, it is preferable that the water vapor permeability measured by the test method conforming to JIS-K2129 is within the range of 0.5 g / m 2 It is preferable that the moisture resistance is within the range of 1000 MPa or less per day 1000 MPa. The multilayer sheet 10 can impart sufficient gas barrier properties and moisture resistance to PTPs and the like processed using the multilayer sheet 10.

[0030] In addition, in this embodiment, the multilayer sheet 10 including both the first outer layer 3 and the second outer layer 5 has been described, but the multilayer sheet according to the present invention is not limited to this. For example, any multilayer sheet including at least one of the first outer layer 3 or the second outer layer 5 can solve the problem of the present application.

[0031] [Uses of multi-layer sheets] The multilayer sheet 10 according to the present embodiment can be used in the packaging of medicines, cosmetics, electrical appliances, daily necessities, etc., and in particular can be used as PTP packaging when packaging solid drugs.

[0032] A known method can be used to form a PTP package from a multilayer sheet, and a contact heating plate is used to heat the portion of the multilayer sheet that will become a pocket when a blister pack is formed. The heated multilayer sheet is then subjected to plug-assisted pressure molding using a plug in a molding die to form a pocket, which can be combined with a lid material to form a PTP package.

[0033] [Manufacturing method of multilayer sheet] An example of a method for producing the multilayer sheet 10 according to this embodiment will be briefly described below. The oxygen gas barrier substrate 3 according to this embodiment can be produced in the form of a film by melt extrusion molding a polyglycolic acid resin in a normal extrusion device. The first and second polyolefin sealant layers according to this embodiment can be produced in the form of a film by melt extrusion molding a specified polyolefin resin in an extrusion device. This polyolefin The polyolefin sealant film and the oxygen barrier substrate made of the polyglycolic acid resin can be laminated with a water vapor barrier adhesive. Alternatively, a specific polyolefin resin can be extrusion laminated onto the oxygen barrier substrate made of the polyglycolic acid resin, with the water vapor barrier adhesive as an anchor coating agent. The multilayer sheet of the present invention can be produced by sequentially laminating polyolefin sealant layers onto both sides of the oxygen barrier substrate made of polyglycolic acid. The film made of polyglycolic acid resin and polyolefin may be surface-treated by corona treatment, ozone treatment, atmospheric pressure plasma treatment, or the like, as necessary.

[0034] [Composition of PTP packaging] Fig. 2 is a cross-sectional schematic diagram showing an example of the configuration of a PTP multilayer sheet according to an embodiment of the present invention. A PTP package is composed of a base material 7 forming a storage section 8 for storing tablets, capsules, etc., and a sealing member 6 for sealing the PTP package. The multilayer sheet according to the present invention can be used as both the base material 7 and the sealing member 6 of the PTP package, and Fig. 2 shows both as multilayer sheets according to the present invention.

[0035] When the multilayer sheet of the present invention is used as the base material of a PTP package, the sealing member is not particularly limited, and may be, for example, a metal foil such as an aluminum foil coated with a heat seal coating agent or a biaxially stretched polyethylene terephthalate film (VM-PET film) on which a metal oxide is vapor-deposited. The pharmaceutical packaging sheet of the present invention may also be used. The contents such as pharmaceuticals are contained in the storage section of the PTP. After the contents are contained in the storage section, the sealing member is sealed to the PTP, and the storage section is sealed.

[0036] In addition, when the multilayer sheet of the present invention is used as a sealing member of PTP packaging, the storage member is not particularly limited, but for example, SUMILITE CEL-R111B or CEL-R161A (manufactured by Sumitomo Bakelite Co., Ltd.) can be used. A multilayer sheet laminated with aluminum foil can also be used. The drug packaging sheet of the present invention can also be used.

[0037] The depth of the storage portion, which corresponds to the pocket of the PTP packaging, may be 3 mm or more, 3.5 mm or more, 4.0 mm or more, 4.5 mm or more, 5.0 mm or more, or 5.5 mm or more, or may be 10 mm or less, 9.5 mm or less, 9.0 mm or less, 8.5 mm or less, 8.0 mm or less, 7.5 mm or less, or 7.0 mm or less. EXAMPLES

[0038] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0039] Example 1 A 20 μm thick substrate was prepared by melt extrusion of polyglycolic acid resin (Kuredux100R35; polyglycolic acid resin 95% by mass or more, weight average molecular weight (Mw) 200,000 to 250,000) constituting the oxygen gas barrier substrate. In addition, a 30 μm thick polypropylene sealant film was similarly obtained using polypropylene (Novatec TMPP MA3H manufactured by Japan Polypropylene Corporation) as the polyolefin. Next, the polypropylene sealant film was dry laminated on both sides of the polyglycolic acid resin substrate using Maxive (main agent M-100, curing agent C-93) manufactured by Mitsubishi Gas Chemical Company, Inc. as the water vapor barrier adhesive, to obtain a multilayer sheet. The thickness of the water vapor barrier adhesive was 2 μm.

[0040] (Examples 2 to 15) (Comparative Examples 1 to 4) The thickness of the oxygen gas barrier substrate, the thickness of the water vapor barrier adhesive layer, and the material and thickness of the polyolefin-based sealant layer are as shown in Table 1, and Examples 2 to 15 and Comparative Example 1 are prepared in the same manner as in Example 1. Comparative Examples 1 to 4 were produced. The details of the polyolefin materials are as follows.

[0041] PP: Novatec PP Density: 0.9g / cm 3 MFR: 9.5g / 10min LDPE: Suntech L1850K Density: 0.918g / cm3 MFR: 6.8g / 10min LLDPE: Nipolon ZF260 Density: 0.936g / cm 3 MFR: 2.0g / 10min (evaluation) <Oxygen permeability> The oxygen permeability of the PTP film was measured in accordance with the test method of JIS K7126B, as in Patent Document 1, using an oxygen permeability tester (OX-TRAN 2 / 20 manufactured by Mocon Co., Ltd.), with a test temperature of 40°C, test humidity of 75% RH before permeation (oxygen side) and 0% RH after permeation (nitrogen side), and a permeation area of ​​50 cm. 2 The test gas was 100% oxygen. 1.0ml / m 2 ·day·atm or less is preferable. <Moisture resistance (water vapor permeability)> The water vapor permeability of the PTP film was measured based on JIS K7129, as in Patent Document 2. 0.5g / m 2 It is preferable that the time is 10-24 hours or less.

[0042] [Table 1] [Explanation of symbols]

[0043] 1. First polyolefin sealant layer 2. First water vapor barrier adhesive layer 3. Oxygen gas barrier substrate 4...Second water vapor barrier adhesive layer 5. Second polyolefin sealant layer 6...Sealing member 7...Bottom material 8. Storage area 10. Multi-layer sheet

Claims

1. A multilayer sheet comprising a first polyolefin sealant layer, a first water vapor barrier adhesive layer, an oxygen gas barrier substrate, a second water vapor barrier adhesive layer, and a second polyolefin sealant layer laminated in this order, the oxygen gas barrier substrate is made of a polyglycolic acid resin, the first water vapor barrier adhesive and the second water vapor barrier adhesive are reaction products of a polyepoxy resin and a polyamine resin, The oxygen gas barrier substrate has a thickness of 20 μm or more and 60 μm or less, the thickness of each of the first water vapor barrier adhesive layer and the second water vapor barrier adhesive layer is 1.0 μm or more and 3.8 μm or less; The first polyolefin sealant layer and the second polyolefin sealant layer each have a thickness of 30 μm or more and 400 μm or less, each of the first polyolefin-based sealant layer and the second polyolefin-based sealant layer is made of polypropylene or polyethylene; The oxygen permeability of the multilayer sheet is 2.23 ml / m 2 ·day ·atm or less; The multilayer sheet has a water vapor permeability of 0.41 g / m 2 ·day·atm or less.

2. 2. The multilayer sheet according to claim 1, wherein the weight average molecular weight (Mw) of the polyglycolic acid resin is 50,000 or more and 800,000 or less.

3. A press-through pack using the multilayer sheet according to any one of claims 1 and 2.

Images