JP2019010768A - Film for moisture absorption and gas adsorption, and laminate for packaging - Google Patents

Abstract

To provide a film for moisture absorption and gas adsorption capable of adsorbing a larger volume of out gas even with a small amount of a gas adsorbent while having a moisture absorbing function and having high versatility.SOLUTION: There is provided a film for moisture absorption and gas adsorption (100) which comprises: a hydrophilic physical adsorption layer (10) containing a first thermoplastic resin (12) and a hydrophilic physical adsorbent (14) dispersed in the first thermoplastic resin; and a hydrophobic physical adsorption layer (20) containing a second thermoplastic resin (22) and a hydrophobic physical adsorbent (24) dispersed in the second thermoplastic resin, where the hydrophilic physical adsorption layer (10) and the hydrophobic physical adsorption layer (20) are laminated each other and the equilibrium humidity of the hydrophobic physical adsorbent is 35%RH or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a film for moisture absorption and gas adsorption, and a laminate for packaging.

  Conventionally, in the fields of foods, pharmaceuticals, electronic parts, precision machines, recording materials, etc., a method of bundling a desiccant has been taken for the purpose of preventing quality deterioration caused by moisture. In addition, a desiccant is contained in the packaging material itself so that the packaging material itself has a moisture absorption function without putting a separate desiccant in the package.

  For example, Patent Document 1 discloses a desiccant film using a desiccant-containing resin including a molecular sieve and a resin having an MFR of 10 or more.

  Some contents emit volatile organic gas or inorganic gas called outgas. When this outgas has a smell, the smell spreads when opened, which may cause discomfort to the user. Therefore, in order to reduce outgas in the packaging, a gas adsorbent is included in the packaging material itself.

  For example, Patent Document 2 discloses a film for a PTP (press-through package) blister having an adsorption layer containing a hydrophobic zeolite as a deodorant.

JP-A-2005-280188 JP 2006-334819 A

  When there is a lot of moisture in the package, the outgas, which is an odor component, stays without being dispersed, and as a result, the odor may be strongly felt. In addition, the contents packaged by moisture may be hydrolyzed to generate outgas, which may make it easier to feel the smell. Therefore, in order to effectively remove the odor in the package, it is desirable not only to remove outgas but also to remove moisture in the package.

  Also, depending on the contents to be packaged, there are those that generate a large amount of outgas, so it may be necessary to increase the amount of outgas adsorption. In this case, if the content of the gas adsorbent is increased, the amount of outgas adsorbed can be increased. However, considering the moldability and cost of the packaging material, it is preferable to increase the content of the gas adsorbent. There may not be.

  Furthermore, it may be preferable from the viewpoint of versatility to control whether moisture or outgas is preferentially adsorbed without changing the amount of moisture and outgas that can be adsorbed.

  Accordingly, there is a need to provide a hygroscopic and gas adsorption film that has a hygroscopic function and can adsorb a larger amount of outgas even with a small amount of gas adsorbent and has high versatility.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means, and have completed the present invention. That is, the present invention is as follows:
<1> A hydrophilic physical adsorption layer containing a first thermoplastic resin and a hydrophilic physical adsorbent dispersed in the first thermoplastic resin, a second thermoplastic resin, and the above Comprising a hydrophobic physical adsorption layer containing a hydrophobic physical adsorbent dispersed in a second thermoplastic resin;
The hydrophilic physical adsorption layer and the hydrophobic physical adsorption layer are laminated with each other, and the equilibrium humidity of the hydrophobic physical adsorbent is 35% RH or more.
Film for moisture absorption and gas adsorption.
<2> The film for moisture absorption and gas adsorption according to the item <1>, wherein the hydrophilic physical adsorbent has an equilibrium humidity of less than 35% RH.
<3> The film for moisture absorption and gas adsorption according to <1> or <2>, wherein the hydrophilic physical adsorbent is a hydrophilic zeolite.
<4> The film for moisture absorption and gas adsorption according to <3>, wherein the hydrophilic zeolite has a pore diameter of 5 mm or less.
<5> Moisture absorption according to any one of <1> to <4> above, wherein the hydrophobic physical adsorbent is selected from the group consisting of hydrophobic zeolite, activated carbon, mesoporous material, and mixtures thereof. Gas adsorption film.
<6> The film for moisture absorption and gas adsorption according to any one of <1> to <5>, wherein the hydrophilic physical adsorption layer and the hydrophobic physical adsorption layer are fused to each other.
<7> The film for moisture absorption and gas adsorption according to any one of <1> to <6>, further including a skin layer on one or both surfaces of the film for moisture absorption and gas adsorption.
<8> A packaging laminate including the moisture absorption and gas adsorption film according to any one of <1> to <7> above, and a base material layer in this order.
<9> The laminate for packaging according to <8>, wherein the base material layer includes a barrier layer and a resin layer.
<10> The packaging according to <8> or <9>, wherein the moisture absorption and gas adsorption film has a skin layer on at least a surface opposite to a surface on which the base material layer is laminated. Laminated body.
<11> One or more of the packaging laminates according to any one of <8> to <10> above, and the moisture absorption of one or more of the packaging laminates And a part of the gas adsorbing film side is made into a bag by being heat-sealed with the other part of the laminate or another film,
Packaging bag.
<12> A content-containing packaging bag containing the content, and the packaging bag according to <11>, which contains the content.
<13> The laminate for packaging according to any one of <8> to <10> above, which is a laminate for blister packs.
<14> A blister pack comprising the laminate for packaging according to the item <13> having a pocket portion for storing contents, and a lid.
<15> A blister pack containing contents, and the blister pack containing the contents described above, the blister pack according to <14> above.

  According to the present invention, it is possible to provide a film for moisture absorption and gas adsorption that has a moisture absorption function and can adsorb a larger amount of outgas even with a small amount of gas adsorbent and has high versatility.

FIG. 1 is a diagram showing a layer structure of one embodiment of the film for moisture absorption and gas adsorption of the present invention. FIG. 2 is a diagram showing a layer configuration of one embodiment of the film for moisture absorption and gas adsorption of the present invention. FIG. 3 is a diagram showing a layer configuration of one aspect of the packaging laminate of the present invention. FIG. 4 is a diagram showing evaluation results of equilibrium humidity for specific hydrophilic physical adsorbents and hydrophobic physical adsorbents. FIG. 5 is a diagram illustrating the moisture absorption behavior of the film of Example 1 and the packaging laminates of Examples 1A and 1B. FIG. 6 is a diagram showing the moisture absorption behavior of the film of Example 2 and the packaging laminates of Examples 2A and 2B. FIG. 7 is a diagram showing the moisture absorption behavior of the film of Example 3 and the packaging laminates of Examples 3A and 3B. FIG. 7 (a) shows the moisture absorption behavior of the film of Example 3, FIG. 7 (b) shows the moisture absorption behavior of the packaging laminate of Example 3A, and FIG. The hygroscopic behavior of the packaging laminate of Example 3B is shown, and FIG. 7 (d) shows the hygroscopic behavior of all these packaging laminates.

《Hygroscopic and gas adsorption film》
As shown in FIG. 1, the film for moisture absorption and gas adsorption (100) of the present invention comprises a first thermoplastic resin (12) and a hydrophilic physical adsorbent (14) dispersed in the first thermoplastic resin. ) Containing a hydrophilic physical adsorption layer (10), a second thermoplastic resin (22), and a hydrophobic physical adsorbent (24) dispersed in the second thermoplastic resin. The hydrophobic physical adsorption layer (20), the hydrophilic physical adsorption layer (10) and the hydrophobic physical adsorption layer (20) are laminated to each other, and the equilibrium humidity of the hydrophobic physical adsorbent Is 35% RH or more.

  Here, the “equilibrium humidity” of the hydrophilic physical adsorbent or the hydrophobic physical adsorbent means that the film containing the hydrophilic physical adsorbent or the hydrophobic physical adsorbent is hydrophilic with respect to moisture in the sealed container. The physical adsorbent or the hydrophobic physical adsorbent is excessive, that is, in a simple quantity, the hydrophilic physical adsorbent or the hydrophobic physical adsorbent reduces the humidity in the sealed container to 0% RH (relative humidity). It is the relative humidity in the sealed space in an equilibrium state when left in a sealed space in an environment of 23 ° C. and 55% RH so that it can be as much as possible.

  The equilibrium humidity is determined by, for example, adding 20% by mass of a low-density polyethylene or a hydrophilic physical adsorbent to a 100 μm-thick film, and then cutting the film into a size of 5 cm × 5 cm, and The measurement can be performed by leaving one or two cut films in a 140 mL sealed space in an environment of 23 ° C. and 55% RH for 24 hours.

  Specific equilibrium humidity of the hydrophilic physical adsorbent and the hydrophobic physical adsorbent are shown with reference to FIG. In FIG. 4, 20 mass% of hydrophilic physical adsorbent or hydrophobic physical adsorbent and 80 mass% of low density polyethylene were kneaded with a kneader, and the resulting resin composition was heated to form a film with a hot press. A film having a thickness of 100 μm was cut into a 5 × 5 cm square, and this and a temperature / humidity logger (Higlocron, KN Laboratories Co., Ltd.) were placed in a 140 mL glass bottle together with air at 23 ° C. and 55% RH, and sealed at 23 ° C. The figure shows that the humidity in the bottle was measured over time after being stored for one day in an environment of 55% RH.

  Referring to FIG. 4, the equilibrium humidity of the hydrophilic zeolite 3A, which is a hydrophilic physical adsorbent referred to in the present invention, is lower than 35% RH, whereas the hydrophobic physical adsorbent referred to in the present invention is hydrophobic. It can be seen that the equilibrium humidity of the zeolitic zeolite, mesoporous silica, and activated carbon exceeds 35% RH.

  The inventors of the present invention have found that a large amount of outgas can be adsorbed while having a moisture absorption function by the moisture absorption and gas adsorption film having the above-described configuration.

  Although not wishing to be bound by theory, this is because rapid degassing by the hydrophobic physical adsorbent described above prevents rapid deactivation of the hydrophilic physical adsorbent, thereby The gas adsorption capacity can be maximized, and / or the water adsorbed by the hydrophobic physical adsorbent is adsorbed and removed by the hydrophilic physical adsorbent, and / or the hydrophilic physical adsorbent preferentially removes the water. It is considered that the ability to adsorb does not inhibit rapid outgas adsorption by the hydrophobic physical adsorbent.

  In addition, the hydrophilic physical adsorbent and the hydrophobic physical adsorbent have different adsorption behaviors, that is, the relationship between the pressure in the enclosed space and the adsorption rate, thereby producing a mutually complementary adsorption behavior. It is considered that outgas can be adsorbed efficiently.

  Furthermore, when the hydrophilic physical adsorption layer and the hydrophobic physical adsorption layer are laminated to each other, when a base material layer is laminated on one side and a laminate for packaging is produced, either moisture or outgas Therefore, the film for moisture absorption and gas adsorption of the present invention has versatility according to the handling and use during processing.

  The hydrophilic physical adsorption layer and the hydrophobic physical adsorption layer are preferably fused with each other from the viewpoint of maximizing the adsorptivity of the hydrophilic physical adsorption layer and the hydrophobic physical adsorption layer. The fusion may be performed independently of the production of the hydrophilic physical adsorption layer and the hydrophobic physical adsorption layer by heat sealing using a heat roll, or by coextrusion inflation method and coextrusion T die method, etc. You may carry out together with preparation of a hydrophilic physical adsorption layer and a hydrophobic physical adsorption layer.

  In another aspect of the present invention, the moisture absorption and gas adsorption film may further have a skin layer on one or both surfaces of the moisture absorption and gas adsorption film. More specifically, the film for moisture absorption and gas adsorption may have a skin layer (30) on the hydrophilic physical adsorption layer (10) side as shown in FIG. As shown in b), it may have a skin layer (30) on the hydrophobic physical adsorption layer (20) side, or have a skin layer (30) on both sides as shown in FIG. You may do it.

  Below, each component of this invention is demonstrated.

<Hydrophilic physical adsorption layer>
The hydrophilic physical adsorption layer is a layer containing a first thermoplastic resin and a hydrophilic physical adsorbent dispersed in the first thermoplastic resin.

  The content of the hydrophilic physical adsorbent in the hydrophilic physical adsorption layer is more than 0 mass%, 5 mass% or more, 10 mass% or more, or 15 mass% or more based on the mass of the entire hydrophilic physical adsorption layer. It can be 70% by weight or less, 50% by weight or less, or 40% by weight or less.

  The thickness of the hydrophilic physical adsorption layer can be 5 μm or more, 10 μm or more, 20 μm or more, or 30 μm or more, and is 200 μm or less, 180 μm or less, 160 μm or less, 140 μm or less, 120 μm or less, or 100 μm or less. Can do.

{First thermoplastic resin}
As the first thermoplastic resin, a thermoplastic resin having high moisture and outgas permeability and excellent kneadability can be used. As such a thermoplastic resin, for example, at least one selected from polyolefins, vinyl polymers, polyesters, ionomers, polycarbonates, polyamides, thermoplastic elastomers, etc., or a combination thereof can be used.

  Examples of the polyolefin include polyethylene resins and polypropylene resins.

  In the present specification, the polyethylene-based resin includes a repeating unit of an ethylene group in a polymer main chain of 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 80 mol% or more. For example, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), ethylene-acrylic acid copolymer (EAA), ethylene- Methacrylic acid copolymer (EMAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene vinyl acetate copolymer (EVA), carboxylic acid-modified polyethylene, carboxylic acid-modified ethylene Vinyl acetate copolymer and Derivatives of al, and is selected from the group consisting of mixtures.

  In this specification, the polypropylene resin is a resin containing propylene group repeating units in a polymer main chain of 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 80 mol% or more. Yes, for example, polypropylene (PP) homopolymer, random polypropylene (random PP), block polypropylene (block PP), chlorinated polypropylene, carboxylic acid-modified polypropylene, and derivatives thereof, and mixtures thereof.

  Examples of the vinyl polymer include PVC (polyvinyl chloride) and polystyrene.

  Examples of the polyester include PET (polyethylene terephthalate) and polybutylene terephthalate.

  Examples of the ionomer include a resin obtained by crosslinking a copolymer of ethylene and methacrylic acid with a metal such as zinc.

  Examples of the polycarbonate include a resin obtained by condensation polymerization of bisphenol A and carbonyl chloride.

  Examples of the polyamide include nylon such as nylon (registered trademark) 6 and nylon MXD6.

  Examples of the thermoplastic elastomer include styrene-butadiene rubber and ethylene-propylene rubber.

{Hydrophilic physical adsorbent}
The hydrophilic physical adsorbent is a hydrophilic physical adsorbent dispersed in the first thermoplastic resin.

  In particular, the equilibrium humidity of the hydrophilic physical adsorbent can be less than 35% RH, less than 33% RH, or less than 30% RH, and more than 5% RH, more than 13% RH, or more than 15% RH. Can be. When the equilibrium humidity of the hydrophilic physical adsorbent is within the above range, the hydrophilic physical adsorbent can have a role as a hygroscopic agent that can preferentially adsorb moisture.

  As the hydrophilic physical adsorbent, for example, hydrophilic zeolite can be used.

  A hydrophilic zeolite is a zeolite having a Si / Al molar ratio of less than 1.5. This Si / Al molar ratio can be less than 1.5 or 1.0 or less.

  Here, a small Si / Al molar ratio means that the zeolite has hydrophilic properties. Therefore, hydrophilic zeolite is a physical adsorbent mainly intended for adsorption of moisture.

  As the hydrophilic zeolite, for example, A-type, X-type, or LSX-type zeolite can be used. These may be used alone or as a mixture.

  The pore diameter of the hydrophilic zeolite can be, for example, 1 mm or more, 2 mm or more, or 3 mm, and can be 20 mm or less, 18 mm or less, or 16 mm or less. This pore diameter can be selected according to the effective diameter of the outgas to be adsorbed.

  The average particle size of the hydrophilic physical adsorbent (particle size at an integrated value of 50% in the particle size distribution determined by the laser diffraction / scattering method) can be 1 μm or more, 3 μm or more, or 5 μm or more, and 50 μm or less. , 40 μm or less, or 30 μm or less.

<Hydrophobic physical adsorption layer>
The hydrophobic physical adsorption layer contains a second thermoplastic resin and a hydrophobic physical adsorbent dispersed in the second thermoplastic resin.

  The content of the hydrophobic physical adsorbent in the hydrophobic physical adsorption layer is more than 0 mass%, 5 mass% or more, 10 mass% or more, or 15 mass% or more based on the mass of the entire hydrophobic physical adsorption layer. It can be 70% by weight or less, 50% by weight or less, or 40% by weight or less.

  The thickness of the hydrophobic physical adsorption layer can be 5 μm or more, 10 μm or more, 20 μm or more, or 30 μm or more, and 200 μm or less, 180 μm or less, 160 μm or less, 140 μm or less, 120 μm or less, or 100 μm or less. Can do.

{Second thermoplastic resin}
As the second thermoplastic resin, the thermoplastic resins mentioned as the first thermoplastic resin can be used. The second thermoplastic resin may be the same as or different from the first thermoplastic resin.

{Hydrophobic physical adsorbent}
The hydrophobic physical adsorbent is a physical adsorbent dispersed in a thermoplastic resin and having an equilibrium humidity of 35% RH or higher.

  This equilibrium humidity can be 35% RH or more, 38% RH or more, or 40% RH or more, and can be 50% RH or less, 48% RH or less, or 45% RH or less. When the equilibrium humidity of the hydrophobic physical adsorbent is within the above range, the hydrophobic physical adsorbent can have a role as a gas adsorbent that can preferentially adsorb outgas.

  Here, the outgas is volatile organic gas or inorganic gas (excluding water vapor) released from the contents stored in the package. Specifically, examples of the outgas include aromatic compounds such as benzene and toluene, esters such as ethyl acetate, aliphatic hydrocarbons such as methane and ethane, alcohols such as ethanol, aldehydes such as acetaldehyde, and isobutylamine. An amine etc. are mentioned. Such outgas may not only be unfavorable with respect to odor, but may also adversely affect the contents.

  Examples of the hydrophobic physical adsorbent include hydrophobic zeolite, silica gel, silica gel subjected to hydrophobic treatment, mesoporous material, activated carbon, plant shell powder and the like. The mesoporous material is a material having a pore diameter intermediate between micropores (2 nm or less) and macropores (50 nm or more), such as mesoporous silica. As plant shell powder, finely ground porous peanut shell can be used. These hydrophobic physical adsorbents may be used alone or as a mixture.

  In the present specification, the hydrophobic zeolite is a zeolite having a Si / Al molar ratio larger than 1.5. The Si / Al molar ratio can be greater than 1.5, 2.0 or greater, 5.0 or greater, 10.0 or greater, 30.0 or greater, 50.0 or greater, or 100.0 or greater. Zeolite having a Si / Al molar ratio within the above range can have an equilibrium humidity of 35% RH or more, thereby having a role as a gas adsorbent capable of preferentially adsorbing outgas.

  As such a hydrophobic zeolite, for example, a beta type, ZSM-5 type, ferrierite type, mordenite type, L type, or Y type zeolite can be used. Further, ZSM-11, silicalite, silicalite-2, and pentasil-type metallosilicate, which are analogs of ZSM-5 type zeolite, can also be used. These may be used alone or in combination.

  The average particle size of the hydrophobic physical adsorbent (particle size at an integrated value of 50% in the particle size distribution determined by the laser diffraction / scattering method) can be 1 μm or more, 3 μm or more, or 5 μm or more, and 50 μm or less. , 40 μm or less, or 30 μm or less.

<Skin layer>
The skin layer prevents the hydrophilic physical adsorbent contained in the hydrophilic physical adsorbing layer and / or the hydrophobic physical adsorbent contained in the hydrophobic physical adsorbing layer from falling off and has strength as a packaging container, for example, tensile strength. It is an optional layer that is laminated on one or both surfaces of the hygroscopic and gas adsorbing films in order to give them fracture strength and heat seal strength with other films and laminates.

  The skin layer can be composed of a thermoplastic resin to improve the film-forming stability and / or prevent the hydrophilic physical adsorbent and / or hydrophobic physical adsorbent from falling off and direct contact with the outside. And / or the surface smoothness laminated | stacked with a base material layer can be provided.

  As the thermoplastic resin constituting the skin layer, the thermoplastic resins mentioned as the first thermoplastic resin can be used. When skin layers are laminated on both sides of the moisture absorption and gas adsorption film, the thermoplastic resins constituting each skin layer may be the same or different.

  The thickness of the skin layer can be 1 μm or more, 3 μm or more, 5 μm or more, or 7 μm or more, and can be 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 15 μm or less. When skin layers are laminated on both sides of the moisture absorption and gas adsorption film, the thicknesses of these skin layers may be the same or different.

《Packaging for packaging》
The packaging laminate of the present invention comprises the above-described film for moisture absorption and gas adsorption, and a base material layer.

  In one embodiment, the film for moisture absorption and gas adsorption in the packaging laminate of the present invention has a hydrophilic layer on at least a surface opposite to the surface on which the base material layer is laminated. The adsorbent and the hydrophobic physical adsorbent are preferable from the viewpoint of preventing them from being exposed to the atmosphere and preventing them from falling off.

  More specifically, as shown in FIG. 3 (a), the packaging laminate (200) of this embodiment includes a skin layer (30), a hydrophilic physical adsorption layer (10), and a hydrophobic physical adsorption layer (20). ) And the base material layer (150). Moreover, as shown in FIG.3 (b), the laminated body (200) has the skin layer (30) and the base material layer (150) in the position opposite to the aspect of Fig.3 (a). May be. Further, as shown in FIGS. 3C and 3D, the laminated body for packaging (200) includes a hydrophilic physical adsorption layer (10) or a hydrophobic physical adsorption layer (20) and a base material layer (150). Further, a skin layer (30) may be further provided.

<Base material layer>
The base material layer may be, for example, a resin layer, a barrier layer, or a laminate thereof.

  The base material layer may be laminated on the film for moisture absorption and gas adsorption. More specifically, the base material layer may be laminated on the film for moisture absorption and gas adsorption directly or via another layer.

{Resin layer}
As the resin layer, a thermoplastic resin excellent in impact resistance, wear resistance, etc., for example, polyolefin, vinyl polymer, polyester, polyamide, etc. can be used alone or in combination of two or more kinds in multiple layers. . This resin layer may be a stretched film or an unstretched film.

  As the polyolefin, a copolymer of ethylene and an oxygen-containing ethylenically unsaturated monomer or the like can be used in addition to the polyethylene resin and the polypropylene resin mentioned for the hydrophilic physical adsorption layer. Examples of the copolymer of ethylene and an oxygen-containing ethylenically unsaturated monomer include EVOH (ethylene-vinyl alcohol copolymer).

  As the vinyl polymer, PVDC (polyvinylidene chloride), polychlorotrifluoroethylene, PAN (polyacrylonitrile) and the like can be used in addition to the vinyl polymers mentioned for the hydrophilic physical adsorption layer.

  As polyester and polyamide, the polyester and polyamide mentioned regarding the hydrophilic physical adsorption layer can be used.

  The thickness of the resin layer can be 3 μm or more, 5 μm or more, 7 μm or more, 10 μm or more, or 12 μm or more, and is 120 μm or less, 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, Or it can be 20 micrometers or less.

{Barrier layer}
As the barrier layer, a material that can prevent moisture from the outside from permeating into the hydrophilic physical adsorption layer or the hydrophobic physical adsorption layer can be used. When the resin layer has sufficient water vapor barrier properties and gas barrier properties, a barrier layer is not necessary, but when the resin layer does not have sufficient barrier properties, it is preferable to provide a barrier layer. For example, but not limited to, metal foil such as aluminum foil or aluminum alloy, aluminum vapor deposition film, silica vapor deposition film, alumina vapor deposition film, inorganic vapor deposition film such as silica / alumina binary vapor deposition film, or polyvinylidene chloride An organic coating film such as a coating film or a polyvinylidene fluoride coating film can be used.

  The thickness of the barrier layer can be 1 μm or more, 3 μm or more, 5 μm or more, or 7 μm or more, and is 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less. Can do.

<Other layers>
The packaging laminate of the present invention may have another layer, for example, an adhesive layer, between each layer. As the adhesive layer, for example, a dry laminate adhesive, a hot melt adhesive, a water-soluble adhesive, an emulsion adhesive, and a thermoplastic resin for extrusion lamination can be used.

<Laminated body for blister pack>
The laminated body for blister packs can comprise the above moisture absorption and gas adsorption film, a reinforcing layer, and a base material layer.

<Reinforcing layer>
As the reinforcing layer, at least one selected from high-density polyethylene, PVC (polyvinyl chloride), polypropylene, PET (polyethylene terephthalate), and polyamide, or a combination thereof can be used.

  Examples of the polyamide include the polyamides mentioned for the hydrophilic physical adsorption layer.

  The thickness of the reinforcing layer for use in the laminated body for blister packs is preferably 12 μm or more, 15 μm or more, or 20 μm or more from the viewpoint of imparting an appropriate stiffness to the laminated body, and maintains an appropriate moldability. It is preferable that it is 60 micrometers or less, 55 micrometers or less, or 50 micrometers or less from the viewpoint to do.

<Base material layer>
The base material layer may be, for example, a resin layer, a barrier layer, or a laminate thereof.

(Resin layer)
As the resin layer, the resins listed above can be used, but an unstretched film is preferable from the viewpoint of imparting pocket moldability.

  Although the thickness of the resin layer can be the above-mentioned thickness, it is preferably 12 μm or more, 13 μm or more, or 15 μm or more from the viewpoint of imparting an appropriate stiffness to the blister pack laminate. Moreover, it is preferable that it is 25 micrometers or less, 22 micrometers or less, or 20 micrometers or less from a viewpoint of hold | maintaining moderate moldability.

(Barrier layer)
As the barrier layer, the barrier layers mentioned above can be used, but it is preferable to use a metal foil such as an aluminum foil or an aluminum alloy. Similarly to the above, when the resin layer has sufficient water vapor barrier property and gas barrier property, the barrier layer is not necessary, but when the resin layer does not have sufficient barrier property, it is preferable to provide the barrier layer. .

  The thickness of the barrier layer can be the above-mentioned thickness, but from the viewpoint of imparting appropriate stiffness to the blister pack laminate, it is preferably 7 μm or more, 10 μm or more, or 15 μm or more, Moreover, it is preferable that it is 45 micrometers or less, 40 micrometers or less, or 35 micrometers or less from a viewpoint of hold | maintaining moderate moldability.

<Other layers>
The laminated body for blister packs of the present invention may have another layer, for example, an adhesive layer, between each layer. As the adhesive layer, the adhesive layers mentioned for the laminate for packaging can be used.

《Packaging bag》
The packaging bag of the present invention comprises one or a plurality of the above-mentioned packaging laminates, and a part of the one or a plurality of packaging laminates on the moisture absorption and gas adsorption film side is this laminate. It is made into a bag shape by being heat-sealed with other parts or other films. Here, the other film may be another packaging laminate, or may be another film other than the packaging laminate.

  The packaging bag of the present invention can be a packaging bag containing contents containing the contents.

<Contents>
The contents are not limited as long as they can be deteriorated by contact with the outside air, and include drugs, foods, cosmetics, medical instruments, medical equipment, electronic parts, precision machines, recording materials, etc. Can do. Moreover, as a chemical | medical agent, a cleaning agent, an agricultural chemical, etc. are included besides a pharmaceutical formulation.

《Method for manufacturing packaging bag》
The manufacturing method of the packaging bag of the present invention includes the following steps:
A step of melt-kneading the first thermoplastic resin and the hydrophilic physical adsorbent to produce a first master batch,
Forming a first master batch to produce a hydrophilic physical adsorption layer;
Melt-kneading the second thermoplastic resin and the hydrophobic physical adsorbent to produce a second masterbatch,
Forming a second master batch to produce a hydrophobic physical adsorption layer;
A step of laminating a hydrophilic physical adsorption layer and a hydrophobic physical adsorption layer to produce a film for moisture absorption and gas adsorption;
Laminating a substrate layer on a film for moisture absorption and gas adsorption to produce a laminate for packaging, and a part on the moisture absorption and gas adsorption film side of the packaging laminate for other part of this laminate or others The process of heat-sealing the film and making it into a bag.

<Process for producing first and second master batches>
The first master batch can be produced by melt-kneading the first thermoplastic resin and the hydrophilic physical adsorbent. As the first thermoplastic resin, the resins listed for the hydrophilic physical adsorption layer can be used. The melt-kneading can be performed using, for example, a batch kneader such as a kneader, a Henschel mixer, a mixing roll, or a continuous kneader such as a twin-screw kneader. The second masterbatch can be produced in the same manner as the first masterbatch using the second thermoplastic resin and the hydrophobic physical adsorbent.

<Process for producing hydrophilic physical adsorption layer and hydrophobic physical adsorption layer>
Preparation of a hydrophilic physical adsorption layer and a hydrophobic physical adsorption layer can be performed by forming the above master batch. Examples of the film forming method include, but are not limited to, an inflation method, a T-die method, a calendar method, a casting method, press molding, extrusion molding, and injection molding.

<Process for producing film for moisture absorption and gas adsorption>
The film for moisture absorption and gas adsorption can be produced by laminating the hydrophilic physical adsorption layer and the hydrophobic physical adsorption layer. Lamination may be performed independently of the production of the hydrophilic physical adsorption layer and the hydrophobic physical adsorption layer by heat sealing using a heat roll or the like, or by the coextrusion inflation method and the coextrusion T-die method. May be performed together with the preparation of the hydrophobic physical adsorption layer and the hydrophobic physical adsorption layer.

  In addition, when the film for moisture absorption and gas adsorption has a skin layer, a master batch for skin layer is prepared separately. For example, using a coextrusion inflation method and a coextrusion T-die method, a hydrophilic physical adsorption layer and a hydrophobic layer are prepared. The skin layer can be formed and laminated together with the physical adsorption layer.

<Process for producing packaging laminate>
The laminate for packaging can be produced by laminating a base material layer on a film for moisture absorption and gas adsorption. Examples of the lamination method include, but are not limited to, an extrusion lamination method and a dry lamination method. Preferably, an extrusion lamination method is used.

<Process to form bag>
The step of forming a bag can be performed by heat-sealing a part of the packaging laminate in the moisture absorption and gas adsorption film side with another portion of the laminate or another film. Here, the other film may be another packaging laminate, or may be another film other than the packaging laminate.

  Examples of the packaging bag include a three-side seal bag, a four-side seal bag, a gusset bag, a bottom gusset bag, a stand bag, a bottom seal bag, and a tetrahedral bag.

《Blister Pack》
The blister pack of the present invention comprises the above-mentioned packaging laminate, particularly a packaging laminate for blister packs, and a lid. This laminated body for packaging has a pocket part for storing the contents.

  In using this blister pack, the contents can be taken out by pushing through the pocket from the blister pack side to break through the lid. In addition, when the same resin as the moisture absorption and gas adsorption film of the blister pack laminate is used as the resin layer included in the lid, the contents are taken out by peeling the lid by cohesive failure. You can also. Furthermore, when an easy peel resin or an easy peel film is used as the resin layer included in the lid, the contents can be taken out by peeling the lid at the adhesive interface between the blister pack and the lid.

<Cover material>
The lid material includes, for example, a lid resin layer and a metal layer.

  The lid member may be bonded to the packaging laminate. More specifically, the lid member may be bonded to the packaging laminate directly or via another layer.

(Cover resin layer)
The lid resin layer is disposed on the inner side of the blister pack of the metal layer, and is a layer capable of sealing the blister pack by adhering to the moisture absorbing and gas adsorbing film of the packaging laminate in which the pocket portion is formed. It is. As the resin layer, a thermoplastic resin can be used. Examples of the thermoplastic resin include the thermoplastic resins mentioned with respect to the adsorption layer, and the resin layer of the lid and the film for moisture absorption and gas adsorption of the packaging laminate described above are the same resin from the viewpoint of improving adhesiveness. Can be included.

  In addition, as the resin layer, an easy peel resin such as a polyolefin polymer alloy or an easy peel film can be used.

(Metal layer)
The metal layer is a layer that imparts barrier properties to the lid member and can prevent moisture, organic gas, inorganic gas, and the like from entering the pocket portion of the blister pack from the outside. As the metal layer, for example, an aluminum foil such as a pure aluminum foil or an aluminum alloy foil can be used.

<Pocket>
The pocket portion can have an arbitrary shape, for example, a dome shape, according to the contents stored in the blister pack.

<Contents>
An example of the contents of the blister pack is a pharmaceutical product.

<Production method of blister pack>
The method for producing a blister pack of the present invention includes the following steps:
A step of melt-kneading the first thermoplastic resin and the hydrophilic physical adsorbent to produce a first master batch,
Forming a first master batch to produce a hydrophilic physical adsorption layer;
Melt-kneading the second thermoplastic resin and the hydrophobic physical adsorbent to produce a second masterbatch,
Forming a second master batch to produce a hydrophobic physical adsorption layer;
A step of laminating a hydrophilic physical adsorption layer and a hydrophobic physical adsorption layer to produce a film for moisture absorption and gas adsorption;
A step of laminating an optional reinforcing layer and a base material layer on a hygroscopic and gas adsorbing film to produce a packaging laminate,
A step of pressing the packaging laminate to form a pocket portion in the packaging laminate, and a step of laminating a lid on the packaging laminate having the pocket portion.

<Preparation of film for moisture absorption and gas adsorption>
The film for moisture absorption and gas adsorption can be produced by the methods mentioned for the method for producing a packaging bag.

<Process for producing packaging laminate>
The laminate for packaging can be produced by laminating a reinforcing layer and a base material layer on a hygroscopic and gas adsorbing film, and optionally aging. As a lamination method, it can carry out by the method mentioned regarding the manufacturing method of a packaging bag.

<Process for forming pocket part>
The step of forming the pocket portion can be performed by pressing the laminate for packaging by, for example, a flat plate type air forming method, a plug assist pressure forming method, a drum type vacuum forming method, a plug forming method, or the like.

<Process of laminating the lid material>
Lamination of the lid material may be performed by heat sealing, or may be performed via an adhesive layer.

  The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these.

<Production of sample>
<Production of single layer film>
{Comparative Example 1}
Hydrophilic zeolite (Molecular Sieve 3A, Union Showa Co., Ltd., Si / Al molar ratio 1.0) 20% by mass as a hydrophilic physical adsorbent and thermoplastic resin pellets (low density polyethylene, Petrocene 202, Tosoh Corporation) After dry blending with 80% by mass and kneading at 150 ° C. with a kneader, the obtained resin composition is pulverized and heated to 150 ° C. with a hot press to form a hydrophilic film having a thickness of 100 μm. A film of Comparative Example 1 having a physical adsorption layer was obtained.

{Comparative Examples 2-4}
A film of Comparative Examples 2 to 4 having a hydrophobic physical adsorption layer with a thickness of 100 μm was obtained in the same manner as Comparative Example 1 except that a hydrophobic physical adsorbent was used instead of the hydrophilic zeolite. As the hydrophobic physical adsorbent, hydrophobic zeolite (ABSENTS3000, Union Showa Co., Ltd.), mesoporous silica (Sigma Aldrich Japan LLC), activated carbon (FP-3, Osaka Gas Chemical Co., Ltd.) were used.

{Comparative Example 5}
A film of Comparative Example 5 which is a polyethylene film having a thickness of 100 μm was obtained in the same manner as Comparative Example 1 except that calcium oxide was not contained.

<Preparation of moisture absorption and gas adsorption film>
{Example 1}
The films of Comparative Examples 1 and 2 were stacked and heat-welded at 150 ° C. with a heat roll (Test Laminator MRK-350Y, MC Corporation) to obtain a laminated film having a thickness of 200 μm.

{Examples 2 and 3}
Films of Examples 2 and 3 were obtained in the same manner as Example 1 except that the films of Comparative Examples 3 and 4 were used instead of the film of Comparative Example 2.

<Preparation of packaging laminate>
{Example 1A}
As a base material layer, a laminate of polyethylene terephthalate (E5100, Toyobo Co., Ltd., 12 μm) // aluminum foil (UACJ, 9 μm) // LDPE (FCD-NP, Mitsui Chemicals, Inc., 40 μm) was prepared (“// "Indicates a dry laminate adhesive). The LDPE side of this base material layer and the hydrophobic physical adsorption layer side of the film of Example 1 were made to face each other, and heat-welded at 150 ° C. with a heat roll (Test Laminator MRK-350Y, MC Corporation). Thus, a packaging laminate of Example 1A was obtained.

{Example 1B}
The packaging laminate of Example 1B in the same manner as Example 1A, except that the LDPE side of the base material layer and the hydrophilic physical adsorption layer side of the film of Example 1 were opposed to each other and heat-welded. Got.

{Examples 2A and 2B}
A laminated body for packaging of Examples 2A and 2B was obtained in the same manner as in Examples 1A and 1B, except that the film of Example 2 was used instead of the film of Example 1.

{Examples 3A and 3B}
A laminated body for packaging of Examples 3A and 3B was obtained in the same manner as in Examples 1A and 1B, except that the film of Example 3 was used instead of the film of Example 1.

<Evaluation>
<Evaluation of gas adsorption amount>
The produced film was cut into a 5 × 5 cm square, and the mass of the film was measured. Next, the cut out film and a glass bottle filled with 2 mL of isobutylamine were put in a 140 mL glass bottle and stored hermetically for 7 days, and the mass of the film after storage was measured. The amount of gas adsorption was calculated from the change in mass before and after storage.

<Evaluation of moisture absorption>
The produced film and the laminate for packaging were cut into 5 × 5 cm squares, and the mass of the film was measured. Next, these films were stored in a constant temperature and humidity chamber at 40 ° C. and 90% RH for 7 days, and the mass of the film after storage was measured. The amount of moisture absorption was calculated from the change in mass before and after storage.

<Evaluation of moisture absorption behavior>
The produced film and packaging laminate were cut into 5 × 5 cm squares, and one piece of the cut film or packaging laminate and a temperature / humidity logger (High Glolon, KN Laboratories) were used at 23 ° C. and 55% RH. Was placed in a 140 mL glass bottle together with the air and stored in an environment of 23 ° C. and 55% RH for 150 hours, and the humidity in the bottle was measured over time.

  The results are shown in Table 1 and FIGS.

In Table 1, the calculated values in the examples are the sum of the measured values of the hydrophilic physical adsorption layer and the hydrophobic physical adsorption layer included in the examples. For example, the calculated value of the gas adsorption amount of the film of Example 1 is the gas adsorption amount of the hydrophilic physical adsorption layer (Comparative Example 1) and the hydrophobic physical adsorption layer (Comparative Example 2) constituting the film of Example 1. It is calculated as follows by adding up the measured values.
5.1 (Comparative Example 1) +6.9 (Comparative Example 2) = 12.0 (calculated value)

  From Table 1, the film for moisture absorption and gas adsorption of Examples 1 to 3 in which the hydrophilic physical adsorption layer and the hydrophobic physical adsorption layer are laminated with each other is the hydrophilic physical adsorption layer or the hydrophobic physical adsorption layer alone. It will be understood that it has an improved gas adsorption capacity compared to the comparative film it has.

  From Table 1, the film for moisture absorption and gas adsorption of Examples 1 to 3 in which the hydrophilic physical adsorption layer and the hydrophobic physical adsorption layer are laminated with each other is the hydrophilic physical adsorption layer or the hydrophobic physical adsorption layer alone. It will be understood that the film has substantially the same hygroscopic capacity as compared with the comparative film.

  Further, when the moisture absorption and gas adsorption film of Example 1 and the packaging laminates of Examples 1A and 1B were compared, there was no significant difference in the moisture absorption capacity depending on the presence and position of the substrate. Let's check from 1. On the other hand, as seen in FIG. 5, the base material layer is arranged on the hydrophilic physical adsorption layer side as compared with Example 1A in which the base material layer is arranged on the hydrophobic physical adsorption layer side. It can be understood that Example 1B can control whether moisture or outgas is preferentially adsorbed depending on the position of the substrate because the decrease in humidity is significantly slower. In addition, although the measurement of the gas adsorption amount of the packaging laminates of Examples 1A and 1B is not performed, the gas adsorption amount of the packaging laminates of Examples 1A and 1B is also considered, considering the measurement results of the moisture absorption amount. Naturally, it can be expected to be equivalent to the film of Example 1.

  Similar trends were found between the moisture absorption and gas adsorption film of Example 2 and the packaging laminates of Examples 2A and 2B, and the moisture absorption and gas adsorption film of Example 3 and Examples 3A and 3B. It can be understood from Table 1 and FIGS. 6 and 7 that it can be confirmed between the laminated body for packaging.

DESCRIPTION OF SYMBOLS 10 Hydrophilic physical adsorption layer 12 1st thermoplastic resin 14 Hydrophilic physical adsorption agent 20 Hydrophobic physical adsorption layer 22 Second thermoplastic resin 24 Hydrophobic physical adsorption agent 30 Skin layer 100 Hygroscopic and gas adsorption film 150 group Material layer 200 Laminate for packaging

Claims (15)

A first thermoplastic resin, a hydrophilic physical adsorption layer containing a hydrophilic physical adsorbent dispersed in the first thermoplastic resin, a second thermoplastic resin, and the second heat Comprising a hydrophobic physical adsorption layer containing a hydrophobic physical adsorbent dispersed in a plastic resin,
The hydrophilic physical adsorption layer and the hydrophobic physical adsorption layer are laminated with each other, and the equilibrium humidity of the hydrophobic physical adsorption agent is 35% RH or more.
Film for moisture absorption and gas adsorption.   The film for moisture absorption and gas adsorption according to claim 1, wherein an equilibrium humidity of the hydrophilic physical adsorption layer is less than 35% RH.   The film for moisture absorption and gas adsorption according to claim 1 or 2, wherein the hydrophilic physical adsorbent is a hydrophilic zeolite.   The film for moisture absorption and gas adsorption according to claim 3, wherein the hydrophilic zeolite has a pore diameter of 5 mm or less.   The film for moisture absorption and gas adsorption according to any one of claims 1 to 4, wherein the hydrophobic physical adsorbent is selected from the group consisting of a hydrophobic zeolite, activated carbon, a mesoporous material, and a mixture thereof.   The film for moisture absorption and gas adsorption according to any one of claims 1 to 5, wherein the hydrophilic physical adsorption layer and the hydrophobic physical adsorption layer are fused to each other.   The film for moisture absorption and gas adsorption according to any one of claims 1 to 6, further comprising a skin layer on one or both surfaces of the film for moisture absorption and gas adsorption. The laminated body for packaging which comprises the film for moisture absorption and gas adsorption as described in any one of Claims 1-7, and the base material layer in this order.   The packaging laminate according to claim 8, wherein the base material layer comprises a barrier layer and a resin layer.   The packaging laminate according to claim 8 or 9, wherein the moisture absorption and gas adsorption film has a skin layer on at least a surface opposite to a surface on which the base material layer is laminated. One or a plurality of the laminates for packaging according to any one of claims 8 to 10 are provided, and the moisture absorption and gas adsorption film side of the one or a plurality of the laminates for packaging is provided. A part is made into a bag by being heat-sealed with another part of this laminate or another film,
Packaging bag. A packaging bag containing contents, and the packaging bag according to claim 11, which contains the contents.   The laminated body for packaging according to any one of claims 8 to 10, which is a laminated body for blister packs. A blister pack comprising the laminate for packaging according to claim 12, which has a pocket for storing contents, and a lid. A blister pack containing contents, comprising the blister pack according to claim 14, which contains the contents and the contents.

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