JP2023041356A - Medicine packaging sheet, bottom material for press-through package, and press-through package - Google Patents

Abstract

To provide a new medicine packaging sheet capable of enhancing moldability, and capable of suitably molding even a recess part with a small diameter such as a pocket part at a bottom material of PTP, regarding the medicine packaging sheet which includes a polyvinylidene chloride resin layer.SOLUTION: A medicine packaging sheet includes a constitution in which a base material layer (I) whose main component resin is thermoplastic resin, a polyvinylidene chloride resin layer (II) whose main component resin is polyvinylidene chloride resin, and a polyolefin resin layer (III) whose main component resin is polyolefin resin are laminated in this order. A thickness of the base material layer (I) is larger than a thickness of the polyolefin resin layer (III).SELECTED DRAWING: None

Description

The present invention provides a pharmaceutical packaging sheet that can be suitably used to manufacture a packaging material for packaging pharmaceuticals, such as a press-through package (also referred to as "PTP"), and a PTP bottom using the sheet. material and PTP.

2. Description of the Related Art In the field of packaging pharmaceuticals and the like, a press-through package (PTP) is known as a packaging material for packaging pharmaceuticals such as capsules and tablets.
PTP refers to, for example, heating a transparent sheet and then performing air pressure forming, vacuum forming, plug forming, etc. to form a large number of pockets in the sheet surface for storing solids such as capsules and tablets. It is a package in which a foil or film made of a material such as aluminum foil that can be easily torn or opened by hand after storing a capsule or the like in a pocket is pasted together as a cover material and integrated.
With PTP, solid agents and food stored in a pocket of a transparent sheet can be checked with the naked eye before opening. , the contents can be easily taken out.

Polyvinyl chloride resin (hereinafter also referred to as "PVC") has been conventionally used as a raw material for sheets used in PTP because it has good thermoformability, rigidity at room temperature, impact resistance, and transparency. rice field. However, sheets using PVC may not have sufficient moisture resistance, so when packaging contents that require more moisture resistance, polypropylene resin (hereinafter also referred to as "PP") is used as an alternative to PVC. ) has been used (see Patent Document 1).

However, in recent years, there has been a demand for further improvement in moisture resistance, and polyvinylidene chloride resin (PVDC) has attracted attention as a material for pharmaceutical packaging sheets.

Regarding a pharmaceutical packaging sheet using a polyvinylidene chloride resin (PVDC) as a raw material, for example, in Patent Document 2, a polyvinyl chloride resin (A) layer is used as a base material, and at least one surface of the base material is coated with a polyvinyl chloride resin (A) layer. A multilayer sheet for PTP formed by laminating vinylidene chloride-based resin (B) layers, wherein the polyvinylidene chloride-based resin (B) layer includes (B)-1 layer and (B)-2 layer each. At least one set is laminated on the base material, and the thickness ratio of the next set to the set closest to the base material is in the range of 0.3 to 0.75, and A multi-layer sheet for PTP is disclosed wherein the thickness of each of the (B)-1 and (B)-2 layers of the set closest to the substrate is in the range of 7 to 20 μm.

Patent Document 3 describes a layer (I) made of a thermoplastic resin, a layer (II) made of a polyvinylidene chloride resin, and a topcoat layer (III) containing a fibrous substance having a thickness of 0.15 to 5 μm. A multilayer sheet having at least three layers and laminated in the order of (I) / (II) / (III), wherein the static friction coefficient measured in accordance with JIS K7125 with the layers (III) facing each other is A multi-layer sheet for PTP is disclosed, which is characterized by a PTP of less than 0.8.

Japanese Patent No. 4907115 Japanese Patent Application Laid-Open No. 2018-43507 Japanese Patent No. 6589590

Packaging materials for packaging pharmaceuticals are required to have particularly high moisture resistance, that is, water vapor barrier properties. A sheet provided with a layer (referred to as a "polyvinylidene chloride resin layer") is attracting attention as a pharmaceutical packaging sheet.
However, polyvinylidene chloride resin (PVDC) has high crystallinity, is brittle as a material, and is vulnerable to deformation such as bending, and thus has a problem of inferior moldability. Therefore, a single-layer sheet made of a polyvinylidene chloride resin layer is not suitable for molding small-diameter concave portions such as pocket portions in the bottom material of PTP.

Therefore, the present invention relates to a pharmaceutical packaging sheet provided with a polyvinylidene chloride resin layer, which can improve moldability and is suitable even for recesses with a small diameter, such as a pocket part in the bottom material of PTP. To provide a new medical packaging sheet that can be molded.

The present invention comprises a substrate layer (I) containing a thermoplastic resin as a main component resin, a polyvinylidene chloride resin layer (II) containing a polyvinylidene chloride resin as a main component resin, and a polyolefin resin as a main component resin. A pharmaceutical packaging sheet is proposed, which has a structure in which polyolefin resin layers (III) are laminated in this order, and the thickness of the base layer (I) is greater than the thickness of the polyolefin resin layer (III).

The present invention also proposes a bottom material for PTP using the sheet for packaging pharmaceuticals.
In such a PTP bottom material, it is preferable that the polyolefin resin layer (III) is arranged so as to form the inner surface of the recess that constitutes the pocket.

The present invention also proposes a PTP comprising the PTP bottom material and a lid material.

Since the pharmaceutical packaging sheet proposed by the present invention includes the polyvinylidene chloride resin layer (II), it can have high moisture resistance, ie, water vapor barrier properties. Further, the polyvinylidene chloride resin layer (II) is sandwiched between a substrate layer (I) containing a thermoplastic resin as a main component resin and a polyolefin resin layer (III) containing a polyolefin resin as a main component resin. Due to the structure, moldability can be improved, and even a recess with a small diameter, such as a pocket portion in the bottom material of PTP, can be suitably molded. Therefore, for example, it is possible to suitably manufacture a PTP bottom material having a concave portion that constitutes a pocket portion.

Next, an example of an embodiment of the invention will be described. However, the present invention is not limited to the embodiments described below.

<<Inventive sheet>>
A sheet according to an example of an embodiment of the present invention (referred to as "the sheet of the present invention") includes a substrate layer (I) containing a thermoplastic resin as a main component resin, a polyvinylidene chloride resin containing a polyvinylidene chloride resin as a main component resin, It has a structure in which a vinylidene resin layer (II) and a polyolefin resin layer (III) containing a polyolefin resin as a main component resin are laminated in this order.
Whereas the substrate layer (I) containing a thermoplastic resin as a main component resin alone does not have sufficient water vapor barrier properties, the provision of the polyvinylidene chloride resin layer (II) can sufficiently improve the water vapor barrier properties.
Further, by laminating the polyolefin resin layer (III) on the back side of the polyvinylidene chloride resin layer (II), moldability and slipperiness can be enhanced.

In this specification, in the sheet of the present invention, the substrate layer (I) side is called the front side, and the opposite side, that is, the polyolefin resin layer (III) side is called the back side.
Further, the “main component resin” of each layer means a resin having the highest mass ratio among the resins constituting each layer, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more of the resin constituting each layer. , 80% by mass or more, 90% by mass or more, or 100% by mass.

The sheet of the present invention may have a structure in which the substrate layer (I), the polyvinylidene chloride resin layer (II) and the polyolefin resin layer (III) are laminated in this order. Between the material layer (I) and the polyvinylidene chloride resin layer (II), between the polyvinylidene chloride resin layer (II) and the polyolefin resin layer (III), on the front side of the substrate layer (I), the polyolefin resin "Another layer" may be provided on the back side of layer (III) or the like.
For example, as described later, an anchor coat layer (B) can be provided between the substrate layer (I) and the polyvinylidene chloride resin layer (II). Moreover, an anchor coat layer (A) can be provided between the polyvinylidene chloride resin layer (II) and the polyolefin resin layer (III). However, it is not limited to these configurations.

<Base material layer (I)>
The substrate layer (I) is a layer containing a thermoplastic resin as a main component.
By having such a substrate layer (I), it is possible to improve moldability even in a sheet having the polyvinylidene chloride resin layer (II).

(Thermoplastic resin)
As the thermoplastic resin which is the main component resin of the substrate layer (I), conventionally known and commonly used resins can be used, and there is no particular limitation. Specifically, polyvinyl chloride resins, polyolefin resins, polystyrene resins, polyamide resins, polyester resins, polycarbonate resins, acrylic resins, fluorine resins such as polychlorotrifluoroethylene, ethylene vinyl alcohol Examples include polyvinyl alcohol-based resins such as copolymers. These thermoplastic resins may be used singly or in combination of two or more.
Among them, in the present invention, polyvinyl chloride-based resins and polyolefin-based resins are preferred from the viewpoint of versatility, and polyolefin-based resins are particularly preferably used from the viewpoint of moisture resistance and environment.

(polyolefin resin)
Examples of the polyolefin resin as the main component resin of the substrate layer (I) include polyethylene resins, polypropylene resins, polybutene resins, poly-4-methylpentene resins, and ethylene/propylene copolymer elastomers. (EPR), ethylene/butene copolymer elastomer (EBR), ethylene/hexene copolymer elastomer (EHR), ethylene/α-olefin copolymer elastomer such as ethylene/octene copolymer elastomer (EOR), etc. can be exemplified by polyolefin resins. Further, the comonomer may be a copolymer consisting of only olefin or a copolymer of olefin and non-olefin comonomer.
Among them, preferred examples of polyolefin resins include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ionomer resin etc. can be mentioned. However, it is not limited to these.
When the main component resin of the substrate layer (I) is a polyolefin resin, it is possible to include resins other than the polyolefin resin, such as polystyrene resins, polyester resins, and polystyrene thermoplastic elastomers. is.

(other ingredients)
The substrate layer (I) contains components other than resins, such as heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, antibacterial/antifungal agents, antistatic agents, lubricants, pigments, dyes, and other additives. It is also possible to contain

(melting point)
The melting point of the substrate layer (I) measured by DSC measurement is preferably 50° C. or higher, especially 80° C. or higher, especially 100° C. or higher, from the viewpoint of maintaining the pocket shape when used as a PTP. is more preferable. On the other hand, the temperature is preferably 200° C. or lower, more preferably 180° C. or lower, and more preferably 170° C. or lower, from the viewpoint of ease of molding without requiring a high temperature during molding.

In the present invention, the "melting point measured by DSC measurement" is the one with the larger peak height when two or more endothermic peaks are observed in the DSC curve measured by a differential scanning calorimeter (DSC). The temperature of the endothermic peak of is adopted as the melting point. The same applies to melting points other than the substrate layer (I).
Moreover, when two or more endothermic peaks are observed because the substrate layer (I) has a multi-layer structure or the like, each peak is preferably within the above range.

(stretched/unstretched)
When the substrate layer is obtained in the form of a film, the substrate layer (I) may be a non-stretched film or a uniaxially or biaxially stretched film. Among them, it is preferable to use a non-stretched film from the viewpoint of facilitating opening by pushing the pocket portion.

(thickness)
The thickness of the substrate layer (I) is preferably greater than the thickness of the polyolefin resin layer (III). By making the polyolefin resin (III) thinner than the substrate layer (I), it is possible to contribute to the thinning of the entire film while maintaining moldability.
The thickness of the substrate layer (I) is preferably 100 μm or more, more preferably 150 μm or more, and more preferably 200 μm or more, from the viewpoint of sheet processability and practicality. From the viewpoint of ease of unsealing, the thickness is preferably 400 μm or less, more preferably 350 μm or less, and more preferably 300 μm or less.

(multilayer structure)
The substrate layer (I) may have a single-layer structure containing a thermoplastic resin as a main component resin, or may have a multilayer structure consisting of two or more layers containing a thermoplastic resin as a main component resin.
In the case of a multilayer structure, a plurality of layers containing a single thermoplastic resin as the main component resin may be laminated, or a plurality of layers containing two or more different thermoplastic resins as the main component resin. It may be formed by lamination.

In particular, when the substrate layer (I) is a layer containing a polyolefin-based resin as a main component resin, from the viewpoint of moldability, a layer containing a polypropylene-based resin as a main component/a layer containing a polyethylene-based resin as a main component/ It is preferable to have a three-layer structure of a layer containing a polypropylene-based resin as a main component resin.

Moreover, in the case of the laminated structure, not only the laminated structure consisting only of the virgin layer but also the laminated structure in which at least one layer is a recycled layer may be used. Here, the virgin layer refers to a layer formed from resin as a virgin material, and refers to a layer formed from resin obtained by recycling waste resin generated during molding.
Also, the reproduction layer is preferably a repro layer. Here, the ribbed layer is preferably a layer formed from a resin obtained by recycling burrs generated during molding of the container.

<Anchor coat layer (B)>
Between the substrate layer (I) and the polyvinylidene chloride resin layer (II), if necessary, for example, in order to increase the adhesion between the substrate layer (I) and the polyvinylidene chloride resin layer (II) , an anchor coat layer (B) can be interposed.

Especially when the substrate layer (I) has a three-layer structure of a layer containing a polypropylene-based resin as a main component resin/a layer containing a polyethylene-based resin as a main component resin/a layer containing a polypropylene-based resin as a main component resin, From the viewpoint of enhancing the adhesion between the substrate layer (I) and the polyvinylidene chloride resin layer (II), the main component resin of the anchor coat layer (B) is a compound containing a hydroxyl group and a compound containing an isocyanate group. It is preferable that the resin is

As the compound containing a hydroxyl group, a polyol having two or more hydroxyl groups is preferable. Among them, acrylic polyols, aromatic polyester polyols, aromatic polycarboxylic acids, and the like are preferable from the viewpoint of reactivity with isocyanate compounds. Among these, acrylic polyols are preferable because of their excellent transparency.

On the other hand, the isocyanate group-containing compound preferably acts mainly as a cross-linking agent or a curing agent, as long as it has at least two isocyanate groups (-N=C=O) in the molecule. Examples of monomeric isocyanates include aromatic isocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), bisisocyanatomethylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate. Aliphatic isocyanates such as (H12MDI), xylene diisocyanate (XDI), araliphatic isocyanates such as tetramethylxylylene diisocyanate (TMXDI), and the like can be mentioned. Polymers or derivatives of these monomeric isocyanates can also be used. Examples of the polymer or derivative include a trimer isocyanurate type, an adduct type reacted with 1,1,1-trimethylolpropane, and a biuret type.
The isocyanate compound may be arbitrarily selected from the above monomeric isocyanates, their polymers, derivatives, and the like, and may be used singly or in combination of two or more.

<Polyvinylidene chloride resin layer (II))>
The polyvinylidene chloride-based resin layer (II) is a layer containing polyvinylidene chloride-based resin as a main component resin.
By providing the polyvinylidene chloride resin layer (II), the sheet of the present invention can have excellent moisture resistance and transparency.

(polyvinylidene chloride resin)
Specific examples of polyvinylidene chloride-based resins include vinylidene chloride polymers and copolymers of vinylidene chloride monomers and various copolymerizable monomers.
Specific examples of the copolymerizable monomer include unsaturated carboxylic acids such as vinyl chloride, acrylic acid, methacrylic acid, fumaric acid, and maleic acid; aromatic vinyl compounds such as α-methylstyrene and vinyltoluene; (Meth) acrylic acid esters such as methyl acid, ethyl (meth) acrylate, and hydroxyethyl (meth) acrylate, glycidyl acrylate methacrylate, (meth) acrylamide, N-methylol (meth) acrylamide, etc. Meth)acrylamide may be mentioned. These may be used alone or in combination of two or more.

The method for producing the polyvinylidene chloride resin is not particularly limited. A conventionally known method such as an emulsion polymerization method can be employed. Commercially available polyvinylidene chloride resins include, for example, "Saran Latex" series manufactured by Asahi Kasei Corporation.

The polyvinylidene chloride-based resin layer (II) is a single layer composed of a layer containing a polyvinylidene chloride-based resin as a main component resin, and has two or more layers containing a polyvinylidene chloride-based resin as a main component resin. It may be multiple layers.
When the polyvinylidene chloride resin layer (II) is laminated in multiple layers, a plurality of layers having a single polyvinylidene chloride resin as the main component resin may be laminated, or two or more different polyvinylidene chloride resins may be laminated. A plurality of layers containing the main component resin may be laminated.

(other ingredients)
Polyvinylidene chloride-based resin layer (II) contains resins other than polyvinylidene chloride-based resins, such as polyolefin-based resins, polystyrene-based resins, polyester-based resins, and resins such as polyolefin-based or polystyrene-based thermoplastic elastomers. It is possible.
In addition, the polyvinylidene chloride resin layer (II) contains components other than resins, such as heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, antibacterial/antifungal agents, antistatic agents, lubricants, pigments, and dyes. It is also possible to contain additives such as

(melting point)
The melting point of the polyvinylidene chloride resin layer (II) measured by DSC measurement is preferably 100° C. or higher, more preferably 110° C. or higher, and more preferably 120° C. or higher, from the viewpoint of barrier properties. preferable. On the other hand, from the viewpoint of moldability, the temperature is preferably 200° C. or lower, more preferably 190° C. or lower, and more preferably 180° C. or lower.

The melting point of the substrate layer (I) (in the case of a multilayer structure, the melting point of the layer located closest to the polyvinylidene chloride resin layer (II)) and the melting point of the polyvinylidene chloride resin layer (II) From the viewpoint of preventing cracking of the polyvinylidene chloride resin layer (II) during molding and preventing fusion of the substrate layer (I) during molding, the temperature is preferably 50°C or less, especially 40°C or less, and especially 30°C. More preferably: Although the lower limit of the melting point difference is not particularly limited, it is generally 1°C or more.

(thickness)
If the thickness of the polyvinylidene chloride resin layer (II) is increased, the moisture-proof performance is improved, but the moldability is lowered. It is preferably 2 μm or more and 90 μm or less, and more preferably 3 μm or more and 60 μm or less.

<Anchor coat layer (A)>
Between the polyvinylidene chloride-based resin layer (II) and the polyolefin-based resin layer (III), if necessary, for example, the adhesion between the polyvinylidene chloride-based resin layer (II) and the polyolefin-based resin layer (III) is increased. Therefore, an anchor coat layer (A) can be interposed.

As will be described later, particularly when the main component resin of the polyolefin resin layer (III) is a polypropylene copolymer, the main component resin of the anchor coat layer (A) is, for example, a polyvinylidene chloride resin layer ( From the viewpoint of increasing the adhesion between II) and the polyolefin resin layer (III), it is preferably a polyester resin, a polyurethane resin, or both.

<Polyolefin resin layer (III)>
The polyolefin-based resin layer (III) is a layer containing a polyolefin-based resin as a main component resin.
Although the polyvinylidene chloride resin layer (II) has excellent water vapor barrier properties, it has poor moldability and slipperiness. By this, moldability and slipperiness can be improved. Therefore, for example, when the sheet of the present invention is used as a bottom material in a PTP, if the polyolefin resin layer (III) is arranged to form the inner surface of the recess that constitutes the pocket, the moldability of the recess is improved. and improve tablet slipperiness.

(polyolefin resin)
Examples of the polyolefin-based resin that is the main component resin of the polyolefin-based resin layer (III) include polyethylene-based resin, polypropylene-based resin, polybutene-based resin, poly-4-methylpentene-based resin, and ethylene/propylene copolymer. Ethylene/α-olefin copolymer elastomers such as elastomers (EPR), ethylene/butene copolymer elastomers (EBR), ethylene/hexene copolymer elastomers (EHR), ethylene/octene copolymer elastomers (EOR), etc. Known polyolefin resins can be mentioned. Further, the comonomer may be a copolymer consisting of only olefin or a copolymer of olefin and non-olefin comonomer.

Among them, a preferable polyolefin resin is a polypropylene copolymer composed of a copolymer of propylene and another copolymerizable comonomer.
Among them, those mainly composed of propylene and copolymerized with a small amount of one or more comonomers copolymerizable therewith are more preferable. In particular, when the polyolefin resin layer (III) is formed by coating, it is preferable that the propylene component is contained in a high ratio in order to obtain a high melting point. Specifically, the composition ratio of the propylene unit is preferably 60% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, and more preferably 95% by mass or more.
The copolymer of propylene and another copolymerizable comonomer may be a random copolymer or a block copolymer.

Comonomers to be copolymerized with propylene can be, for example, ethylene and α-olefins having 4 to 20 carbon atoms. Specific examples of α-olefins include the following. 1-butene, 2-methyl-1-propene (above C4); 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene (above C5); 1-hexene, 2-ethyl-1- butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene (above C6); 1-heptene, 2-methyl-1-hexene, 2,3-dimethyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-3-ethyl-1-butene (above C7); 1-octene, 5-methyl-1-heptene, 2-ethyl-1-hexene, 3,3-dimethyl-1-hexene, 2-methyl-3-ethyl-1-pentene, 2,3,4-trimethyl-1-pentene, 2-propyl-1-pentene, 2,3-diethyl-1-butene (above C8); 1-nonene (C9); 1-decene (C10); 1-undecene (C11); 1-dodecene (C12); 1-tridecene (C13); 1-tetradecene (C14); 1-pentadecene (C15); 1-hexadecene (C16); 1-heptadecene (C17); can be mentioned.

Among them, preferred polypropylene-based copolymers include propylene/ethylene copolymers and propylene/1-butene copolymers. Among them, a propylene-ethylene random copolymer (RPP) is preferable. RPP is a random copolymer with 50 mol % or more propylene units and 50 mol % or less ethylene units.

The most preferable polyolefin resin as the main component resin of the polyolefin resin layer (III) is a propylene/ethylene copolymer, that is, a propylene unit and an ethylene unit as monomer components, from the viewpoint of moldability and slipperiness. From the viewpoint of obtaining a high melting point, the composition ratio of the propylene unit is preferably 60% by mass or more, more preferably 75% by mass or more, and more preferably 90% by mass or more. More preferably, it is 95% by mass or more, most preferably.

The polyolefin resin, which is the main component resin of the polyolefin resin layer (III), is acid-modified by introducing an acid component such as maleic anhydride into the structure while maintaining the melting point within the above range from the viewpoint of improving adhesion. preferably.

(other ingredients)
The polyolefin-based resin layer (III) can contain resins other than the polyolefin-based resins, such as polystyrene-based resins, polyester-based resins, and polystyrene-based thermoplastic elastomers.
In addition, the polyolefin resin layer (III) contains components other than resin, such as heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, antibacterial/antifungal agents, antistatic agents, lubricants, pigments, dyes, etc. It is also possible to contain additives.

(melting point)
The melting point of the polyolefin resin layer (III) in DSC measurement is preferably 130° C. or higher.
When the sheet of the present invention is used as a bottom material in PTP, and the polyolefin resin layer (III) is arranged so as to form the inner surface of the recess forming the pocket portion and PTP is formed, the recess is formed as described later. In order to do so, the melting point of the polyolefin resin layer (III) is preferably 130° C. or higher from the viewpoint of enhancing releasability from the plug when pressed by the plug and suppressing dents on the bottom surface of the recess. , preferably 135° C. or higher, more preferably 140° C. or higher, and more preferably 145° C. or higher.
However, if the melting point is too high, a high temperature is required during PTP molding, and as a result, the polyvinylidene chloride resin layer (II) may deteriorate, so the melting point is preferably 200 ° C. or less. , especially 190°C or less, more preferably 180°C or less.

(coating layer/laminate layer)
The polyolefin resin layer (III) may be formed by coating a resin composition for forming the polyolefin resin layer (III), and the polyolefin resin layer (III) is It may be formed by laminating a film comprising the polyolefin resin layer (III).

When the polyolefin-based resin layer (III) is formed by laminating a film, the film may be an unstretched film containing the polyolefin-based resin as a main component resin, or a uniaxially or biaxially stretched film. good. Among them, it is preferable to use a non-stretched film from the viewpoint of improving the sealability with the lid material. For example, unstretched polypropylene (CPP) can be mentioned.

(thickness)
As described above, from the viewpoint of thinning, the thickness of the polyolefin resin layer (III) is preferably smaller than the thickness of the substrate layer (I).
The thickness of the polyolefin-based resin layer (III) is preferably 0.1 μm to 100 μm from the viewpoint of moldability, workability, and economy, and is preferably 0.3 μm or more or 70 μm or less, especially 0.5 μm or more or 70 μm or less. It is more preferably 50 μm or less.
When the polyolefin resin layer (III) is formed by coating, the thickness of the polyolefin (III) is preferably 0.1 μm to 30 μm, especially 0.3 μm or more or 20 μm or less, especially 0.5 μm or more or It is more preferably 10 μm or less.
When the polyolefin resin layer (III) is formed by lamination, the thickness of the polyolefin (III) is preferably 1 μm to 100 μm, more preferably 3 μm or more or 70 μm or less, and more preferably 5 μm or more or 50 μm or less. More preferred.

<Thickness of the sheet of the present invention>
The thickness of the sheet of the present invention is preferably 100 μm to 700 μm, more preferably 150 μm or more or 500 μm or less, and more preferably 200 μm or more or 400 μm or less.

From the viewpoint of moisture resistance, the thickness of the polyvinylidene chloride resin layer (II) is preferably 1% or more, especially 2% or more, and especially 3% or more of the thickness of the substrate layer (I). It is more preferable to have On the other hand, from the viewpoint of moldability, the thickness is preferably 70% or less, more preferably 60% or less, and more preferably 50% or less of the thickness of the base layer (I).

The thickness of the polyolefin-based resin layer (III) is preferably smaller than the thickness of the substrate layer (I), as described above. From this point of view, it is preferably 50% or less, more preferably 30% or less, more preferably 15% or less of the thickness of the substrate layer (I). On the other hand, from the viewpoint of ensuring moldability, it is preferably 0.1% or more, more preferably 0.2% or more, and more preferably 0.3% or more of the thickness of the base layer (I). .

From the viewpoint of moldability, the thickness of the polyolefin resin layer (III) is preferably 1% or more of the thickness of the polyvinylidene chloride resin layer (II). % or more is more preferable. On the other hand, from the standpoint of workability and economy, the thickness is preferably 500% or less, more preferably 400% or less, more preferably 300% or less, of the thickness of the polyvinylidene chloride resin layer (II).
When the polyolefin resin layer (III) is formed by coating, the thickness of the polyolefin (III) is preferably 1% or more and 100% or less of the thickness of the polyvinylidene chloride resin layer (II). .5% or more or 50% or less, more preferably 2% or more or 25% or less.
When the polyolefin resin layer (III) is laminated and formed, the thickness of the polyolefin (III) is preferably 25% or more and 500% or less of the thickness of the polyvinylidene chloride resin layer (II). 50% or more or 400% or less, more preferably 75% or more or 300% or less.

(Production method)
The method for producing the sheet of the present invention is not particularly limited.
For example, a resin composition forming each layer may be prepared and laminated by a method such as coating, coextrusion, extrusion lamination, heat lamination, or dry lamination.
For example, in the case of co-extrusion, the resin compositions forming each layer are melt-mixed in separate extruders, etc., laminated and extruded using a feed block or multi-manifold die, etc., and rapidly cooled and solidified by cast rolls. should be
In the case of lamination, it can be produced by stacking sheets made of a resin composition forming each layer and passing them through heated lamination rolls to laminate under pressure.

Furthermore, if necessary, the film can be uniaxially or biaxially stretched using a roll method, a tenter method, a tubular method, or the like.

(Use of the sheet of the present invention)
Since the sheet of the present invention is excellent in formability, it can be suitably used as, for example, a bottom material for PTP.
PTP (press-through package) is defined as "consisting of a sheet-shaped bottom material with a recess (pocket) for inserting a tablet or capsule and a sheet-shaped cover material that seals the recess, and the recess is pushed open to release the tablet. It is a packaging material that can be taken out.

The PTP bottom material can be formed with recesses that form pocket portions.
In this case, the inner diameter and depth of the recess are not particularly limited, but are, for example, 5 to 20 mm in diameter and 1 to 10 mm in depth, and a typical example is approximately 9 mm in diameter and approximately 4 mm in depth.
Then, it is preferable that the polyolefin-based resin layer (III) is positioned inside the concave portion, that is, on the side that contacts the medicine, and then molded. In other words, it is preferable that the polyolefin-based resin layer (III) is arranged so as to form the inner surface of the recess that constitutes the pocket.

A PTP can be formed by combining a bottom material for PTP formed from the sheet of the present invention and a lid material.

As the lid material, conventionally known materials such as materials generally used for PTP, such as aluminum foil and film, can be used. The contents of the PTP are not particularly limited as long as they can be stored in the pocket, such as tablets and capsules.

For example, when manufacturing a bottom material for PTP, the sheet of the present invention may be heated and softened and then subjected to various molding methods such as plug molding, air pressure molding and vacuum molding.
In particular, the sheet of the present invention is particularly useful in a molding method using a plug because of its good plug releasability. Among molding methods using plugs, air-assisted plug molding that combines air assist and plug molding as preforming, and plug pressure molding that assists moldability by raising and lowering the plug at appropriate timing during injection of compressed air. method is preferred. Among these, the air-assisted plug molding method is more preferable from the viewpoint of wall thickness control.

In addition to the above-mentioned thermoforming, the surface, back surface or both surfaces of the sheet are coated with aluminum foil, aluminum vapor deposition film, plastic film (for example, biaxially oriented polypropylene film, polyamide film, ethylene-vinyl alcohol copolymer film, polyvinylidene chloride film. ), etc., can be stacked. It is also possible to form a composite sheet by laminating an aluminum foil or the above-described various films on the front surface, back surface, or both surfaces of the sheet, and then thermoforming the composite sheet.

Further, for the purpose of enhancing the design property and secondary workability of the product, the surface of the sheet may be subjected to processing such as embossing and matting. In this case, even if a mirror-like sheet is first created and then processed with an embossing roll or matte roll, the cast roll should be changed to an embossing roll or matte roll during extrusion molding. may As long as it does not impair the gist of the present invention, the surface of the sheet may be coated with an antistatic agent, silicone, wax, etc., a surface protective sheet may be used to form a film for the purpose of preventing scratches, or a printed layer may be provided. is also possible. Any means known at present can be employed as means for forming the printed layer.

<Explanation of terms>
In this specification, when expressed as "X to Y" (X and Y are arbitrary numbers), unless otherwise specified, "X or more and Y or less" and "preferably larger than X" or "preferably Y It also includes the meaning of "less than".
In addition, when expressed as "X or more" (X is an arbitrary number) or "Y or less" (Y is an arbitrary number), "preferably larger than X" or "preferably less than Y" It also includes intent.

The invention is further illustrated by the following examples. The examples are not intended to limit the invention in any way.

<raw materials>
(Base material layer (I) forming raw material)
・Thermoplastic resin base material: Two types of three-layer structure of "polypropylene layer / polyethylene layer / polypropylene layer", total thickness 250 μm, each layer thickness ratio 1: 4: 1, unstretched film The polypropylene layer (polypropylene resin is the main component The melting point of the resin layer) is 160°C
The melting point of the polyethylene layer (layer containing polyethylene resin as the main component resin) is 127°C.

(Anchor coat layer (B) forming raw material)
Anchor coating agent 1: Coating liquid containing acrylic polyol and a trimer of hexamethylene diisocyanate (isocyanurate type) at a mass ratio of 10:1.5

(Polyvinylidene chloride resin layer (II) forming raw material)
・PVDC latex dispersion liquid: Melting point 131°C, saran latex L574A (manufactured by Asahi Kasei Corporation)

(Anchor coat layer (A) forming raw material)
・Anchor coating agent 2: Coating liquid whose main component resin is a saturated copolymer polyester resin composed of terephthalic acid/isophthalic acid/ethylene glycol/diethylene glycol/neopentyl glycol components ・Anchor coating agent 3: Aliphatic ester polyol as a main component Coating liquid for resin

(Polyolefin resin layer (III) forming raw material)
・ Unstretched polypropylene (CPP) film: thickness 20 μm
Polyolefin resin coating agent 1 (PO coating agent 1): Coating liquid containing modified polypropylene resin (mass ratio PP: PE = 98: 2) as a main component resin Polyolefin resin coating agent 2 (PO coating agent 2): Coating liquid containing modified polypropylene resin (mass ratio PP:PE = 99:1) as main component resin Polyolefin resin Coating agent 3 (PO coating agent 3): Coating liquid containing polyethylene elastomer as main component resin Polyolefin system Resin coating agent 4 (PO coating agent 4): Coating liquid containing low-density polyethylene (LDPE) as a main component resin

<Example 1>
The above thermoplastic resin substrate was used as the substrate (I), and one surface thereof was coated with the above anchor coating agent 1 and dried at 80° C. for 1 minute to form an anchor coat layer (B) having a thickness of 1 μm.
The above PVDC latex dispersion was applied to the anchor coat layer (B) side and dried at 80° C. for 1 minute to form a polyvinylidene chloride resin layer (II) having a thickness of 10 μm.
The anchor coat agent 2 was applied to the polyvinylidene chloride resin layer (II) side and dried at 80° C. for 1 minute to form an anchor coat layer (A) having a thickness of 1 μm.
The above PO coating agent 1 was applied to the anchor coat layer (A) side and dried at 80° C. for 1 minute to form a polyolefin resin layer (III) having a thickness of 1 μm.
By the above operations, a laminate having a configuration of polyolefin resin substrate (I)/anchor coat layer (B)/polyvinylidene chloride resin layer (II)/anchor coat layer (A)/polyolefin resin layer (III) A sheet (sample) was obtained.
Table 1 shows the melting point of the PO coating agent 1 as the melting point of the polyolefin resin layer (III), as well as the coating film evaluation and molding machine processability of Example 1.

<Example 2>
A laminate sheet (sample) was prepared in the same manner as in Example 1, except that the PO coating agent 2 was used instead of the PO coating agent 1 in Example 1.
Table 1 shows the melting point of the PO coating agent 2 as the melting point of the polyolefin resin layer (III), as well as the coating film evaluation and molding machine processability of Example 2.

<Example 3>
In Example 1, after the polyvinylidene chloride resin layer (II) was provided, the anchor coating agent 3 was applied to the CPP film and dried at 80° C. for 1 minute to form an anchor coating layer (A) having a thickness of 5 μm. established.
The surface of the anchor coat layer (A) and the surface of the polyvinylidene chloride resin layer (II) were laminated to prepare a laminated sheet (sample).
Table 1 shows the melting point of the CPP film as the melting point of the polyolefin resin layer (III), as well as the lamination strength and processability of Example 3 with a molding machine.

<Example 4>
A laminated sheet (sample) was prepared in the same manner as in Example 1, except that PO coating agent 3 was used instead of PO coating agent 1.
Table 1 shows the melting point of the PO coating agent 3 as the melting point of the polyolefin resin layer (III), as well as the coating film evaluation and molding machine processability of Example 4.

<Example 5>
A laminated sheet (sample) was prepared in the same manner as in Example 1, except that the PO coating agent 4 was used instead of the PO coating agent 1 in Example 1.
Table 1 shows the melting point of the PO coating agent 4 as the melting point of the polyolefin resin layer (III), as well as the coating film evaluation and molding machine processability of Example 5.

<Comparative Example 1>
A laminated sheet (sample) was produced in the same manner as in Example 1, except that the anchor coat layer (A) and the polyolefin resin layer (III) were not provided.
Table 1 shows the molding machine processability of Comparative Example 1.

<Measurement and evaluation method>
(1) Melting point PO coating agents 1 to 4 were dried at 80°C to obtain solidified products. The obtained solidified product or CPP film is measured by a DSC measuring device (NETZSCH DSC204F1) in a method conforming to JIS K7121 (2012), with a measurement temperature range of -50 to 200 ° C. and a heating rate of 10 ° C./min. The melting point was determined by measuring under the conditions.

(2) Coating film evaluation PO coating agents 1 to 4 used in Examples and Comparative Examples were polychlorinated by a method based on the crosscut method (crosscut test method) of JIS K5600-5-6 (1999). Adhesion between the vinylidene resin layer (II) and the polyolefin resin layer (III) was evaluated.
Specifically, using a cutter knife, 11 cuts reaching the polyvinylidene chloride resin layer (II) were made on the polyolefin resin layer (III) to form 100 grids. The distance between cuts was 1 mm.
Cellotape (registered trademark) was pressed against the grid portion, the edge of the tape was peeled off at an angle of 45°, and the number of detached grids was counted.

(3) Laminate strength The laminated sheet (sample) of Example 3 was cut into strips with a width of 15 mm and a length of 6 cm, the ends were partially peeled off, and a tensile tester ("STA-1150" manufactured by Orientec Co., Ltd.) was applied. was used to measure the laminate strength by peeling the CPP film 180° at a speed of 300 mm/min.

(4) Molding machine processability Using a PTP molding machine (FBP-300E (manufactured by CKD)), PTP molding was performed on the laminated sheets (samples) produced in Examples and Comparative Examples by the air-assisted plug molding method. bottom. That is, after heating and softening the laminated sheets (samples) produced in Examples and Comparative Examples, they were sandwiched between an upper mold and a lower mold, and air-assisted from above and raised and lowered by a convex plug from the bottom. , a sheet heating temperature of 126° C., a pocket size of Φ10 mm, and a depth of 4.5 mm. After that, a 20 μm-thick aluminum foil was sealed on the sheet surface on which the concave portions were formed to produce a press-through package.

Evaluation was made according to the following criteria.
"Good": Molding could be performed smoothly without any trouble, and the finished press-through package had a good appearance.
"Fair": After molding, when the convex plug was removed from the concave portion, a slight trace of the plug remained on the sheet surface, but the concave portion was normally formed and there was no practical problem.
"X": During the molding process, the bottom of the recess was dented, or the recess was fused to the plug and was pulled and deformed when the plug was separated, resulting in a phenomenon in which a normal recess was not formed. This caused problems with the shape of the resulting press-through package molding.

(Results/Discussion)
From the results of the above examples and the results of the tests conducted so far by the present invention, a configuration in which the polyvinylidene chloride resin layer (II) is sandwiched between the substrate layer (I) and the polyolefin resin layer (III) It has been found that, since it is provided, the moldability can be improved, and even a concave portion with a small diameter, such as a pocket portion in the bottom material of a PTP, can be suitably molded.
In addition, by setting the melting point of the polyolefin resin layer (III) to 130° C. or higher in DSC measurement, the PTP moldability can be improved. It was also found that the releasability from the mold can be improved to suppress the depression of the bottom surface of the recess.
Further, from the results of coating film evaluation or lamination strength in Examples 1 to 5, it was found that there is practically no problem with the adhesion between the polyvinylidene chloride layer (II) and the polyolefin resin layer (III).

Claims (12)

A substrate layer (I) whose main component resin is a thermoplastic resin, a polyvinylidene chloride-based resin layer (II) whose main component resin is a polyvinylidene chloride-based resin, and a polyolefin-based resin layer whose main component resin is a polyolefin-based resin (III) is laminated in this order, and the thickness of the base layer (I) is greater than the thickness of the polyolefin resin layer (III). 2. The pharmaceutical packaging sheet according to claim 1, wherein the polyolefin resin layer (III) has a melting point measured by DSC of 130[deg.] C. or higher. The pharmaceutical packaging sheet according to claim 1 or 2, further comprising an anchor coat layer (A) between the polyvinylidene chloride resin layer (II) and the polyolefin resin layer (III). 4. The pharmaceutical packaging sheet according to claim 3, wherein the main component resin of the anchor coat layer (A) is a polyester-based resin, a polyurethane-based resin, or both. Claims 1 to 4, wherein the polyolefin resin that is the main component resin of the polyolefin resin layer (III) contains a propylene unit and an ethylene unit as monomer components, and the composition ratio of the propylene unit is 60% by mass or more. The pharmaceutical packaging sheet according to any one of items 1 and 2. The pharmaceutical packaging sheet according to any one of claims 1 to 5, wherein the polyolefin resin layer (III) is a layer formed by coating. The pharmaceutical packaging sheet according to any one of claims 1 to 5, wherein the polyolefin resin layer (III) is a layer formed by laminating a film. The pharmaceutical packaging sheet according to any one of claims 1 to 7, comprising an anchor coat layer (B) between the substrate layer (I) and the polyvinylidene chloride resin layer (II). The pharmaceutical packaging sheet according to claim 8, wherein the main component resin of the anchor coat layer (B) is a resin obtained by reacting a compound containing a hydroxyl group and a compound containing an isocyanate group. A bottom material for a press-through package, using the pharmaceutical packaging sheet according to any one of claims 1 to 9. 11. The bottom material for a press-through package according to claim 10, wherein said polyolefin resin layer (III) is arranged so as to form an inner side surface of a recess forming a pocket. A press-through package comprising the press-through package bottom material according to claim 10 or 11 and a lid material.