JP7187657B2 - Laminates, blister containers, and press-through packages - Google Patents

Description

The present invention relates to laminates, blister containers and press-through packages.

Film laminates with high barrier properties are used as packaging materials for foods, pharmaceuticals, and the like. In the pharmaceutical field, a press-through package (hereinafter sometimes referred to as "PTP") is used for individual packaging of tablets and capsules.
In order to suppress the deterioration of the contents, the resin film, which is the material for forming the PTP, is required to have barrier properties against water vapor. In addition, since PTP is generally manufactured by deep drawing, the resin film, which is the material for forming PTP, is required to have good moldability. For example, Patent Literatures 1 and 2 describe laminates in which fluororesin films are laminated in order to improve barrier properties against water vapor.

JP 2014-28508 A Japanese Unexamined Patent Application Publication No. 2012-135980

When producing a laminate having a high barrier property against water vapor using a fluororesin having a high barrier property, it is required to provide a laminate having a high barrier property and excellent moldability.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a laminate having excellent formability, a blister container using the laminate, and a press-through package.

That is, the present invention employs the following configurations.
[1] A laminate having a substrate layer, an intermediate layer, and a fluororesin layer in this order and having a total thickness of 400 μm or less, wherein the thickness of the fluororesin layer is 20 μm or more and 50 μm or less, A laminate having a water vapor transmission rate of 0.5 g/m ² /24 hours or less.
[2] The laminate according to [1], further comprising a second intermediate layer and a second substrate layer in this order on the surface of the fluororesin layer opposite to the intermediate layer.
[3] The laminate according to [1] or [2], wherein the fluororesin layer is made of polychlorotrifluoroethylene.
[4] The laminate according to any one of [1] to [3], wherein the laminate has an upper yield point stress of 1500 N/cm ² or more.
[5] The laminate according to any one of [1] to [4], wherein the intermediate layer comprises a polyethylene resin and a modified polyethylene resin.
[6] The laminate according to any one of [1] to [4], wherein the intermediate layer comprises an acid-modified polyolefin resin, an epoxy group-containing resin, and an elastomer resin.
[7] The laminate according to any one of [2] to [6], wherein the second intermediate layer comprises a polyethylene resin and a modified polyethylene resin.
[8] The laminate according to any one of [2] to [6], wherein the second intermediate layer comprises an acid-modified polyolefin resin, an epoxy group-containing resin, and an elastomer resin.
[9] A blister container comprising the laminate according to any one of [1] to [8].
[10] A press-through package including the laminate according to any one of [1] to [8].

ADVANTAGE OF THE INVENTION According to this invention, the laminated body excellent in moldability, the blister container using this laminated body, and a press through package can be provided.

It is a schematic sectional drawing of the laminated body of this invention. It is a schematic sectional drawing of the laminated body of this invention.

The present invention will be described below based on preferred embodiments.

<Laminate>
<<First embodiment>>
1st Embodiment of the laminated body of this invention is described with reference to FIG.
In the laminate 1 of the present embodiment shown in FIG. 1, a substrate layer 12, an intermediate layer 10, and a fluororesin layer 11 are laminated in this order. The intermediate layer 10 functions as an adhesive layer that bonds the fluororesin layer 11 and the substrate layer 12 , and the substrate layer 12 and the fluororesin layer 11 are laminated via the intermediate layer 10 . The thickness of the fluororesin layer 11 is 20 μm or more and 50 μm or less.
The laminate 1 of this embodiment has a three-layer structure of a substrate layer 12 , an intermediate layer 10 and a fluororesin layer 11 . A laminate having a three-layer structure is preferable because it can be manufactured without a complicated process and the uniformity of each film in the laminate is further improved.

The laminate of the present embodiment has a water vapor transmission rate of 0.5 g/m ² /24 hours or less, preferably 0.4 g/m ² /24 hours or less, more preferably 0.3 g/m ² /24 hours or less. .
Since the laminate of the present embodiment has a water vapor transmission rate within the above specific range, for example, when a press-through package for pharmaceuticals is produced, it exhibits high barrier properties and can prevent deterioration of contents. In the present embodiment, the water vapor transmission rate can be controlled by adjusting the material and thickness of each of the substrate layer, the fluororesin layer, and the intermediate layer. In the present embodiment, it is preferable to control the water vapor transmission rate within the above-mentioned specific numerical range by adjusting the material and thickness of the fluororesin layer, especially by adjusting the thickness of the fluororesin layer. is more preferable.

The laminate of the present embodiment preferably has an upper yield point stress of 1500 N/cm ² or more, more preferably 2000 N/cm ² or more, and particularly preferably 2100 N/cm ² or more, measured under the following measurement conditions.
When the upper yield point stress of the laminate is equal to or higher than the above lower limit, the formability during deep drawing is good. That is, when deep drawing is performed, the deep drawn portion of the laminate becomes convex and a portion that is longer than the original laminate is formed. The force to return to the original shape is reduced, which improves the moldability of the laminate. This makes it possible to improve compatibility with, for example, an automatic packaging line.
The upper limit of the upper yield point stress is not particularly limited, and for example, it can be 5000 N/cm ² or less.
The upper yield point stress can be controlled by adjusting the material and thickness of each of the substrate layer, the fluororesin layer, and the intermediate layer. More preferably, it is controlled by adjusting the composition of the layer.

The upper yield point stress is measured under the following measurement conditions.
Measuring machine: Autograph 100A type manufactured by Shimadzu Corporation Measurement conditions: JIS K-6732 (tensile speed: 50 inches, test temperature: 25 ° C.)
Shape and dimensions of test piece: Dimensions based on JIS K-7127 test piece type 5.
Unit: N/cm ² , value measured according to JIS K 6732

Each layer constituting the present invention will be described below.

[Base material layer]
In this embodiment, the material forming the base material layer 12 is either polyolefin resin, polyester resin, or vinyl resin.
Polyolefin resins include polyethylene resins, polypropylene resins, polymethylpentene resins, and the like.
Polyester-based resins include polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, and polybutylene terephthalate.
Examples of vinyl-based resins include polyvinyl acetate-based resins and polyvinyl chloride-based resins.
In the present embodiment, polyester-based resins are preferred, and polyethylene terephthalate is more preferred.

In the present embodiment, by using any of the above resin materials for the base material layer 12, moldability is improved when the base material layer 12 is formed by, for example, drawing.

In the present embodiment, the thickness of the base material layer 12 is not particularly limited, and for example, the lower limit is 50 μm or more, 80 μm or more, or 100 μm or more. Moreover, the upper limit is 250 μm or less, 220 μm or less, or 200 μm or less.
The above upper limit and lower limit can be combined arbitrarily.

[Middle layer]
・Intermediate layer (1)
In the present embodiment, an intermediate layer containing a polyethylene resin and a modified polyethylene resin (hereinafter sometimes referred to as "intermediate layer (1)") is preferably used as the intermediate layer 10 . The polyethylene resin includes linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE), preferably linear low density polyethylene. .

A modified polyethylene resin is a polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof, and has an acid functional group such as a carboxy group or a carboxylic anhydride group in the polyethylene resin. In the present embodiment, one obtained by acid-modifying a polyethylene resin is preferred.
Examples of the acid modification method include graft modification in which a polyethylene resin and an acid functional group-containing monomer are melt-kneaded in the presence of a radical polymerization initiator such as an organic peroxide or an aliphatic azo compound.

The polyethylene resin material before modification is not limited as long as it contains ethylene as a raw material monomer, and a known polyethylene resin is appropriately used. Specifically, in addition to the above examples of polyethylene resins, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer Polymers, ethylene/α-olefin copolymers such as ethylene-1-octene copolymers; ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylic acid ester copolymers Examples thereof include ethylene-based copolymer resins such as polymers.

The acid functional group-containing monomer is a compound having an ethylenic double bond and a carboxyl group or a carboxylic anhydride group in the same molecule, and includes various unsaturated monocarboxylic acids, dicarboxylic acids, or acids of dicarboxylic acids. Anhydrides are mentioned.
Acid functional group-containing monomers having a carboxy group (carboxy group-containing monomers) include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, tetrahydrophthalic acid, endo α,β-unsaturated carboxylic acid monomers such as -bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid (endic acid).
Acid functional group-containing monomers having a carboxylic anhydride group (carboxylic anhydride group-containing monomers) include unsaturated dicarboxylic acids such as maleic anhydride, nadic anhydride, itaconic anhydride, citraconic anhydride, and endic anhydride. Anhydride monomers are included.
These acid functional group-containing monomers may be used singly or in combination of two or more in the components constituting the intermediate layer.

Among them, the acid functional group-containing monomer is preferably an acid functional group-containing monomer having an acid anhydride group, more preferably a carboxylic anhydride group-containing monomer, and particularly preferably maleic anhydride.
When a part of the acid-functional group-containing monomer used for acid modification is unreacted, the unreacted acid-functional group-containing monomer is removed in advance in order to prevent a decrease in adhesive strength due to the unreacted acid-functional group-containing monomer. It is preferable to use a material.

In this embodiment, the modified polyethylene resin is preferably maleic anhydride-modified polyethylene.

In the present embodiment, when the total mass of the polyethylene resin and the modified polyethylene resin is 100%, the lower limit of the ratio of the polyethylene resin to the total amount of the polyethylene resin and the modified polyethylene resin is preferably 10% or more, and 20% or more. is more preferred. Moreover, the upper limit of the ratio of the polyethylene resin to the total amount of the polyethylene resin and the modified polyethylene resin is preferably 70% or less, more preferably 60% or less. For example, the mixing ratio of the polyethylene resin and the modified polyethylene resin can be [polyethylene resin]:[modified polyethylene resin]=20:80 to 60:40.
In this embodiment, by using the intermediate layer (1) using a mixed material of polyethylene resin and modified polyethylene resin, the adhesion between the fluororesin layer and the substrate layer is improved. Therefore, it is possible to provide a laminate in which delamination is less likely to occur.

・Intermediate layer (2)
In the present embodiment, an intermediate layer containing an acid-modified polyolefin resin, an epoxy group-containing resin, and an elastomer resin (hereinafter referred to as "intermediate layer (2)") is preferably used as the intermediate layer 10.
Each component contained in the intermediate layer (2) will be described.

.. Acid-modified polyolefin resin Acid-modified polyolefin resin (hereinafter referred to as "(A) component") is a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, wherein carboxy and an acid functional group such as a carboxylic acid anhydride group.
Component (A) can be obtained by modifying a polyolefin resin with an unsaturated carboxylic acid or a derivative thereof, or by copolymerizing an acid functional group-containing monomer with an olefin. Among them, the component (A) is preferably obtained by acid-modifying a polyolefin resin.
Examples of the acid modification method include graft modification in which a polyolefin resin and an acid functional group-containing monomer are melt-kneaded in the presence of a radical polymerization initiator such as an organic peroxide or an aliphatic azo compound.

Examples of the polyolefin resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymers of propylene and ethylene or α-olefin, block copolymers of propylene and ethylene or α-olefin, and the like. be done. Among them, homopolypropylene (propylene homopolymer; hereinafter sometimes referred to as "homo PP"), propylene-ethylene block copolymer (hereinafter sometimes referred to as "block PP"), propylene-ethylene Random copolymers (hereinafter sometimes referred to as "random PP") and other polypropylene resins are preferable, and random PP is particularly preferable.
Examples of the olefins to be copolymerized include olefinic monomers such as ethylene, propylene, 1-butene, isobutylene, 1-hexene and α-olefins.

The acid functional group-containing monomer is a compound having an ethylenic double bond and a carboxyl group or a carboxylic anhydride group in the same molecule, and includes various unsaturated monocarboxylic acids, dicarboxylic acids, or acids of dicarboxylic acids. Anhydrides are mentioned.
Acid functional group-containing monomers having a carboxy group (carboxy group-containing monomers) include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, tetrahydrophthalic acid, endo α,β-unsaturated carboxylic acid monomers such as -bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid (endic acid).
Acid functional group-containing monomers having a carboxylic anhydride group (carboxylic anhydride group-containing monomers) include unsaturated dicarboxylic acids such as maleic anhydride, nadic anhydride, itaconic anhydride, citraconic anhydride, and endic anhydride. Anhydride monomers are included.
These acid functional group-containing monomers may be used singly or in combination of two or more in the component (A).

Among them, the acid functional group-containing monomer is preferably an acid functional group-containing monomer having an acid anhydride group, more preferably a carboxylic acid anhydride group-containing monomer, because of its high reactivity with the component (B) described later. Maleic acid is particularly preferred.
When a part of the acid-functional group-containing monomer used for acid modification is unreacted, the unreacted acid-functional group-containing monomer is removed in advance in order to prevent a decrease in adhesive strength due to the unreacted acid-functional group-containing monomer. is preferably used as the (A) component. Here, "unreacted" means not used for acid modification.

Among them, maleic anhydride-modified polypropylene is preferable as component (A) from the viewpoint of exhibiting high adhesiveness to the fluororesin layer.

..Resin containing an epoxy group In the present embodiment, the resin containing an epoxy group is preferably a component having an epoxy group and a vinyl group. The epoxy group-containing resin preferably has a 1,2-vinyl structure, and more preferably epoxidized polybutadiene obtained by partially epoxidizing butadiene. Partially epoxidized 1,2-polybutadiene is particularly preferred.
Examples of the epoxy group-containing resin that can be used in the present embodiment include liquid polybutadiene JP-100 and JP-200 available from Nippon Soda Co., Ltd., and ADEKA CIZER BF-1000 available from Adeka Corporation.
The resin containing epoxy groups preferably has a number average molecular weight of 500 or more and 4,000 or less.
When the number average molecular weight of the epoxy group-containing resin is equal to or less than the above upper limit, it is possible to suppress a decrease in adhesiveness due to solidification at room temperature, and to prevent a decrease in adhesiveness.
In the present invention, the number average molecular weight is a polystyrene-equivalent value measured by GPC (gel permeation chromatography).
It is particularly preferable to use epoxidized polybutadiene as the resin containing epoxy groups.

Elastomer resin Elastomer resin (hereinafter referred to as "(C) component") may be any component as long as it has properties as an elastomer, such as styrene elastomer, acrylic elastomer, urethane elastomer, olefin elastomer, ester system elastomers and the like.
Among them, olefinic elastomers are preferred, and examples thereof include block copolymers having hard segments made of polystyrene or the like and soft segments made of polyethylene, polybutadiene, polyisoprene or the like. Examples of the olefinic polymer that can be used for the olefinic elastomer include aromatic olefin-aliphatic olefin copolymers such as styrene-butadiene copolymers, styrene-isoprene copolymers, and styrene-ethylene copolymers. .

In this embodiment, component (C) is preferably contained in an amount of 1 part by mass or more and 50 parts by mass or less with respect to 50 parts by mass or more and 99 parts by mass or less of component (A). Above all, it is more preferable that 15 to 25 parts by mass of component (B) is contained in 65 to 85 parts by mass of component (C).

In the present embodiment, the thickness of the intermediate layer 10 is 5 μm or more and 50 μm or less, preferably 10 μm or more and 30 μm or less.
In the present embodiment, when the thickness of the intermediate layer 10 is equal to or greater than the above lower limit, adhesion can be improved and delamination can be prevented. Further, when the thickness of the intermediate layer is equal to or less than the above upper limit, it is possible to prevent deterioration of formability due to thickening of the intermediate layer.

[Fluorine resin layer]
Examples of fluorine-based resin materials used for the fluorine-based resin layer 11 include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP). ), tetrafluoroethylene/hexafluoropropylene/perfluoroalkyl vinyl ether (EPA), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene Ethylene copolymers (ECTFE), mixtures of one or more of these can be used, and polychlorotrifluoroethylene (PCTFE) is preferred.

In this embodiment, the thickness of the fluororesin layer 11 is 20 μm or more and 150 μm or less, preferably 25 μm or more and 100 μm or less, and more preferably 50 μm or less.
In the present embodiment, when the thickness of the fluororesin layer 11 is at least the above lower limit, the moisture vapor transmission rate of the laminate can be reduced, and for example, when used in a press-through package for pharmaceuticals, high moisture resistance can be obtained. It can prevent deterioration of the contents due to water vapor.
In this embodiment, if the thickness of the fluororesin layer 11 is equal to or less than the above upper limit, production costs can be reduced.

<<Second embodiment>>
2nd Embodiment of the laminated body of this invention is described with reference to FIG.
In the laminate 2 of this embodiment shown in FIG. 2, a substrate layer 12, an intermediate layer 10, a fluororesin layer 11, a second intermediate layer 13, and a second substrate layer 14 are laminated in this order. .
The laminate 2 having a five-layer structure is preferable because the strength of the laminate increases. Moreover, the laminate 2 having a five-layer structure is preferable because curling is less likely to occur.
Materials constituting the substrate layer, the intermediate layer, and the fluororesin layer in this embodiment are the same as those described in the first embodiment.
The material constituting the second base material layer 14 is the same as that of the base material layer 12 . The materials of the second base material layer 14 and the base material layer 12 may be the same or different, but are preferably the same material.
The material constituting the second intermediate layer 13 is the same as that of the intermediate layer 10 described above. The second intermediate layer 13 and the intermediate layer 10 may be made of the same material or different materials, but are preferably made of the same material.

In addition, the vapor transmission rate of the laminate 2 of the present embodiment is 0.5 g/m ² /24 hours or less, preferably 0.4 g/m ² /24 hours or less, and 0.3 g/m ² /24 hours or less. is more preferred.
Since the laminate of the present embodiment has a water vapor transmission rate within the above specific range, for example, when a press-through package for pharmaceuticals is produced, it exhibits high barrier properties and can prevent deterioration of contents.
In the present embodiment, as in the first embodiment, the water vapor transmission rate of the laminate 2 is the base layer 12, the intermediate layer 10, the fluororesin layer 11, the second intermediate layer 13, It can be controlled by adjusting the material and thickness of each layer of the material layer 14 . In the present embodiment, it is preferable to control the water vapor transmission rate within the above specific numerical range by adjusting the material and thickness of the fluororesin layer 11 . Control is more preferable.

The laminate of the present embodiment preferably has an upper yield point stress of 1500 N/cm ² or more, more preferably 2000 N/cm ² or more, and particularly preferably 2200 N/cm ² or more, measured under the above measurement conditions.
When the upper yield point stress of the laminate is equal to or higher than the above lower limit, the laminate has good deep drawability. For this reason, it is possible to improve compatibility with, for example, an automatic packaging line.
The upper yield point stress can be controlled by adjusting the material and thickness of each layer of the base material layer, the fluororesin layer, and the intermediate layer. It is more preferable to control by adjusting the composition of the intermediate layer 10 and the second intermediate layer 13 .

In the present embodiment, the material forming the base layer and the material forming the second base layer may be the same or different, but are preferably made of the same resin material.
The thickness of the second base layer with respect to the base layer is preferably 0.5 times to 1.1 times, more preferably 0.9 times to 1.1 times, and 0.95 times to 1.05 times is particularly preferred.

In the present embodiment, the material forming the intermediate layer and the material forming the second intermediate layer may be the same or different, but are preferably made of the same resin material.
More preferably, the thickness of the second base material layer is 0.9 to 1.1 times, particularly preferably 0.95 to 1.05 times, the thickness of the base material layer.

In the laminate of the present invention, the upper limit of the total film thickness is 400 µm or less, preferably 300 µm or less. Also, the lower limit of the total film thickness is preferably 80 μm or more, more preferably 200 μm or more. This film thickness facilitates protection of the contents and facilitates storage and use after molding.

<Blister container, press-through package>
The blister container and press-through package of this embodiment are manufactured by deep drawing the laminate of the first or second embodiment of the present invention.
When the laminate 1 of the first embodiment of the present invention is used, the fluororesin layer 11 can be on the inside or the outside, but it is preferable to mold it so as to be on the outside. The press-through package of this embodiment is used for individual packaging of tablets and capsules, for example. Useful for press-through packages and blister containers.
Since the laminate of the present invention has a low water vapor transmission rate, deterioration of contents such as tablets and capsules can be prevented.

The laminate of the present invention is produced by simultaneously melt extruding the resin that is the raw material of the substrate layer, the resin that is the raw material of the intermediate layer, and the resin that is the raw material of the fluororesin layer. is preferred.
Further, the laminate of the second embodiment includes a resin that is a raw material of the base material layer, a resin that is a raw material of the intermediate layer, a resin that is a raw material of the fluororesin layer, and the second intermediate layer. It is preferable to simultaneously melt-extrude the resin that is the raw material of the second base material layer and the resin that is the raw material of the second base material layer.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

<Laminate with three-layer structure>
<<Examples 1 to 5, Comparative Examples 1 to 2>>
A laminate having a three-layer structure was produced, which had a substrate layer, an intermediate layer, and a fluororesin layer in this order. The resins used as raw materials for each layer shown in Table 1 were separately heated and melted, and an extruder capable of simultaneous multi-layer extrusion molding was used to perform simultaneous multi-layer film formation to form a film. A laminate having a three-layer structure having fluorine-based resin layers in this order was obtained. The upper yield point stress of each laminate was measured by the following method. In Comparative Example 2, the upper yield point stress could not be measured because delamination occurred after the laminate was produced.

[Measurement of water vapor transmission rate]
For the laminate obtained according to the above <Laminate with three-layer structure>, according to JIS K7129: 2008 (A method), using a water vapor permeation meter (manufactured by LYSSY, product name "L80-5000", It was measured under the conditions of a cell temperature of 40° C. and a relative humidity difference of 90% RH.The water vapor transmission rate is expressed in grams of water vapor per square meter of area [g/(m ² 24 h)] permeated for 24 hours. .

In Table 1, each symbol means the following materials. The numbers in [ ] are the thickness of each layer.
- PET; polyethylene terephthalate resin. NOVAPEXI4 manufactured by Mitsubishi Chemical Corporation is used.
PCTFE; Polychlorotrifluoroethylene resin. DF0050-C1 manufactured by Daikin Industries, Ltd. is used.
- ECTFE; chlorotrifluoroethylene-ethylene copolymer.
Intermediate layers 1 to 3: Intermediate layers 1 to 3 shown in Table 2 below. In Table 2, the ratio of each material is mass ratio (%).

-Evaluation Each laminate of Examples 1 to 5 and Comparative Examples 1 and 2 was subjected to the following tests.

[Upper yield point stress]
The upper yield point stress was measured under the following measurement conditions.
Measuring machine: Shimadzu Corporation Autograph 100A Measurement conditions: JIS K-6732 (tensile speed: 50 mm / min, test temperature: 25 ° C.) Test piece shape and dimensions: JIS K-7127 test piece type 5 Dimensions based.
Unit: N/cm ² , value measured according to JIS K 6732

[Moldability]
The moldability of the laminate was evaluated by visually observing the presence or absence of molding defects when the press-through package was molded, and evaluated according to the following criteria.
⊚: Thickness unevenness at the deep drawing portion and shape retention after deep drawing were very good.
◯: Thickness unevenness at the deep drawing portion and shape retention after deep drawing were generally good.
Δ: The thickness of the deep-drawn portion was slightly uneven, or the shape could not be maintained after deep-drawing.
×: The thickness of the deep-drawn portion was uneven, or the shape of the deep-drawn portion could not be maintained after deep-drawing.

[Protection of contents]
A press-through package was produced using each of the laminates of Examples 1 to 5 and Comparative Examples 1 and 2, and the content (test drug. Deliquescent) was put into the package, and the deterioration of the content was evaluated as follows. was visually evaluated according to the criteria of At this time, the press-through package was manufactured so that the fluororesin layer of the laminate was on the outside.
A: Deterioration of the contents was not observed.
◯: Almost no deterioration of the contents was observed.
Δ: Slight deterioration of contents was observed.
×: It was confirmed that the contents were remarkably deteriorated.

[judgement]
Each evaluation item was judged comprehensively and judged, and a three-grade evaluation (⊚, ○, x) was performed.

As shown in the above results, Examples 1 to 5 in which the present invention is applied, the fluororesin layer has a specific thickness, and the water vapor permeability of the laminate is in a specific range, the upper yield point stress is high. , the moldability and the protection of the contents were good. On the other hand, in Comparative Example 1, in which the thickness of the fluororesin layer is outside the scope of the present invention, the moldability is not good, and in Comparative Example 2, in which the water vapor permeability value is outside the range of the present invention, the contents are protected. was not of good quality.

<Laminate with 5-layer structure>
<<Examples 6 to 10, Comparative Examples 3 to 4>>
A laminate having a five-layer structure was produced, which had a substrate layer, an intermediate layer, a fluororesin layer, a second intermediate layer, and a second substrate layer in this order. The resins used as raw materials for the respective layers shown in Table 4 were separately heated and melted, and an extruder capable of simultaneous multilayer extrusion molding was used to perform simultaneous multilayer film formation to form a film. A five-layer laminate having a fluororesin layer, a second intermediate layer, and a second substrate layer in this order was obtained.

In Table 4, each symbol means the following materials. The numbers in [ ] are the thickness of each layer.
- PET; polyethylene terephthalate resin. NOVAPEXI4 manufactured by Mitsubishi Chemical Corporation is used.
PCTFE; Polychlorotrifluoroethylene resin. DF0050-C1 manufactured by Daikin Industries, Ltd. is used.
Intermediate layers 1 to 3: Intermediate layers 1 to 3 shown in Table 2 above.

[Water vapor transmission rate]
Measured in the same manner as above.

-Evaluation The laminates of Examples 6 to 10 and Comparative Examples 3 to 4 were evaluated for [higher yield point stress], [protection of contents], and [moldability] by the same method as described above. The results are listed in Table 5.

As shown in the above results, Examples 6 to 10, in which the fluororesin layer has a specific thickness and the water vapor permeability of the laminate is in a specific range, have a high upper yield point stress, moldability and content good protection against In contrast, Comparative Example 3, in which the thickness of the fluororesin layer was outside the range of the present invention and the water vapor transmission rate was also outside the range of the present invention, had poor moldability. In Comparative Example 4, the thickness of the fluororesin layer was thin, and the content protection property was poor.

1, 2: Laminate, 11: Fluorinated Resin Layer, 10: Intermediate Layer, 12: Base Layer, 13: Second Intermediate Layer, 14: Second Base Layer

Claims (6)

A laminate having a substrate layer, an intermediate layer, and a fluororesin layer in this order and having a total thickness of 400 μm or less,
the intermediate layer comprises an acid-modified polyolefin resin, an epoxidized polybutadiene, and an elastomer resin;
A laminate, wherein the thickness of the fluororesin layer is 20 μm or more and 150 μm or less, and the vapor permeability of the laminate is 0.5 g/m ² /24 hours or less. further having a second intermediate layer and a second substrate layer in this order on the surface of the fluororesin layer opposite to the intermediate layer;
2. The laminate of Claim 1, wherein said second intermediate layer comprises an acid-modified polyolefin resin, an epoxidized polybutadiene, and an elastomer resin. 3. The laminate according to claim 1, wherein the fluororesin layer is made of polychlorotrifluoroethylene. The laminate according to any one of claims 1 to 3, wherein the laminate has an upper yield point stress of 1500 N/cm ² or more. A blister container comprising the laminate according to any one of claims 1-4. A press-through package comprising the laminate according to any one of claims 1-4.

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