JP2021183316A - Gas absorption film - Google Patents

Abstract

To provide a gas absorption film that can absorb amine, which is generally unfavorable odor component, while suppressing the adsorption of aroma component.SOLUTION: A gas absorbing film 100 of the present invention has a barrier substrate layer 110, a gas absorption layer 120, and an amine selective permeation layer 130, in which the gas absorption layer 120 contains a thermoplastic resin and a gas absorber dispersed in the thermoplastic resin, and the amine selective permeation layer 130 is made of a polyester-based resin.SELECTED DRAWING: Figure 1

Description

The present invention relates to a gas absorbing film.

When a content containing an aroma component, for example, a pharmaceutical product, is stored in a general package such as polyethylene, the aroma component may be adsorbed on the package and the aroma may not remain at the time of use. The aroma component may correspond to the medicinal component of the content, and a package that does not easily adsorb the aroma component has been proposed for the purpose of preventing the efficacy of the content from being reduced.

Patent Document 1 contains an ethylene-vinyl alcohol copolymer: 70% by weight or more and 90% by weight or less, and an ethylene-vinyl acetate copolymer: 10% by weight or more and 30% by weight or less, and is melt-kneaded. Disclosed is a resin composition, wherein the sealing strength when two films formed by forming the resin composition are heat-sealed is a given value or more.

In addition, such contents themselves may give off a foul odor inside the package, which may cause discomfort to the user when the package is opened. Therefore, a package that absorbs malodorous components has been proposed.

In Patent Document 2, a base material layer that becomes the outermost layer during molding as a PTP (press-through package) or a blister pack is laminated on the base material layer via an adhesive layer, and is laminated at the time of molding as a PTP or a blister pack. A laminate for PTP or blister packs comprising an absorbent layer facing the contents and absorbing at least one of a liquid and a gas, wherein the absorbent layer consists of an outer skin layer, an intermediate layer and an inner skin layer in this order. The outer skin layer is adhered to the base material layer via the adhesive layer, the outer skin layer is made of polyethylene resin, and the intermediate layer is made of a mixture of polyethylene resin and an absorbent. As the inner skin layer, a PTP or blister pack laminate made of a blended resin blended resin made of a given polyethylene resin is disclosed.

Japanese Unexamined Patent Publication No. 2011-80039 International Publication No. 2013/140821

There is a need to provide a gas absorbing film capable of absorbing amines, which are generally unfavorable odor components, while suppressing the adsorption of aroma components.

As a result of diligent 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:
<Aspect 1> It has a barrier base material layer, a gas absorption layer, and an amine selective permeation layer.
The gas absorbing layer contains a thermoplastic resin and a gas absorbent dispersed in the thermoplastic resin, and the amine selective permeation layer is made of a polyester resin.
Gas absorption film.
<Aspect 2> The gas absorbing film according to Aspect 1, wherein the amine selective permeation layer is made of a heat-sealing polyester resin.
<Aspect 3> The gas absorbing film according to Aspect 1 or 2, wherein the gas absorbent is a physical absorbent.
<Aspect 4> The gas absorption film according to Aspect 3, wherein the physical absorbent is at least one selected from the group consisting of hydrophobic zeolite, silica gel, mesoporous substances, activated carbon, and plant shell powder.
<Aspect 5> The gas absorption film according to any one of aspects 1 to 4, further comprising a skin layer laminated on one side or both sides of the gas absorption layer.
<Aspect 6> A part of the amine selective permeation layer of the gas absorbing film comprising one or more of the gas absorbing films according to any one of aspects 1 to 5. Is adhered to another part of the gas absorbing film or another film, and is formed into a bag shape so that the barrier base material layer of the gas absorbing film is located on the outside and the amine selective permeation layer is located on the inside. ,
Packaging bag.
<Aspect 7> The packaging bag according to Aspect 6, wherein the adhesion is performed by a heat seal.
<Aspect 8> The packaging bag according to the aspect 6 or 7, and a packaging bag containing the contents contained in the packaging bag.

According to the present invention, it is possible to provide a gas absorbing film capable of absorbing an amine, which is a generally unfavorable odor component, while suppressing adsorption of an aroma component.

FIG. 1 is a side sectional view showing a layer structure of the gas absorbing film of the present invention.

《Gas absorption film》
As shown in FIG. 1 (a), the gas absorbing film 100 of the present invention is
It has a barrier substrate layer 110, a gas absorption layer 120, and an amine selective permeation layer 130.
The gas absorbing layer 120 contains a thermoplastic resin and a gas absorbent dispersed in the thermoplastic resin, and the amine selective permeation layer 130 is made of a polyester resin.

Even if a non-adsorbent film and a gas-absorbing film are simply laminated or opposed to each other, it is easy to obtain a film that selectively absorbs amines while suppressing the adsorption of aroma components. is not it.

More specifically, when a film having non-adsorption property and a film having gas absorption are laminated, only the function of the layer in contact with the content can be exhibited. When the non-adsorbent film is used as the innermost layer, the non-adsorbent film tends to have a high gas barrier property, so that the permeation of amine is restricted and does not reach the gas absorption layer, so that it cannot be sufficiently absorbed. there were. On the other hand, when a film having gas absorbency is used as the innermost layer, this layer may adsorb aroma components because it is not non-adsorbent.

On the other hand, the present inventors have found that the above-mentioned configuration can selectively absorb amines while suppressing the adsorption of aroma components. I do not want to be bound by theory, but it is thought that this is because the polyester resin functions as a barrier layer for the aroma component and selectively permeates the amine.

Here, examples of the aroma component include alcohol-based aroma components such as l-menthol and phenethyl alcohol, olefin-based aroma components such as limonene, and ester-based aroma components such as ethyl acetate and ethyl cinnamate.

Examples of the amine include primary amines such as methylamine and ethylamine, secondary amines such as dimethylamine and diethylamine, and tertiary amines such as trimethylamine and triethylamine.

As shown in FIG. 1 (b), the gas absorbing film 100 of the present invention may further have a skin layer 140 laminated on one side or both sides of the gas absorbing layer 120.

Hereinafter, each component of the present invention will be described.

<Barrier base material layer>
The barrier base material layer is a base material having a barrier property. The barrier base material layer may be a single barrier layer, or may be a layer having a barrier layer and a base material resin layer. In this case, an adhesive layer may be present between the barrier layer and the base resin layer.

(Barrier layer)
As the barrier layer, a material that can suppress the permeation of moisture, organic gas and inorganic gas from the outside into the gas absorption layer can be used. Examples of the barrier layer include a single metal foil layer such as copper foil and aluminum foil, an alloy foil layer such as stainless steel foil, a silica vapor deposition film, an alumina vapor deposition film, an inorganic vapor deposition film such as a silica-alumina binary vapor deposition film, or an inorganic vapor deposition film. An organic coating film such as a polyvinylidene chloride coating film, a polychlorotrifluoroethylene coating film, or a polyvinylidene fluoride coating film can be used.

When an inorganic vapor-film-deposited film is used as the barrier layer, the thickness of the barrier layer is preferably 100 nm or more, 200 nm or more, 300 nm or more, 500 nm or more, 700 nm or more, or 1 μm or more from the viewpoint of ensuring strength and barrier properties. Further, it is preferably 5 μm or less, 4 μm or less, 3 μm or less, or 2 μm or less from the viewpoint of improving handleability when used as a packaging bag.

When a metal foil layer, a barrier resin layer or an organic coating film is used as the barrier layer, the thickness of the barrier layer is preferably 7 μm or more, 10 μm or more, or 15 μm or more, from the viewpoint of ensuring strength and barrier properties. Further, it is preferably 100 μm or less, 80 μm or less, 60 μm or less, 55 μm or less, 50 μm or less, 45 μm or less, 40 μm or less, or 35 μm or less from the viewpoint of improving handleability when used as a packaging bag.

(Base resin layer)
As the base resin layer, a thermoplastic resin having excellent impact resistance, abrasion resistance, etc., for example, a thermoplastic resin such as a polyolefin resin, a vinyl polymer, polyester, or a polyamide is used alone or in combination of two or more. It can be used in multiple layers. The base resin layer may be a stretched film or a non-stretched film. Further, the base resin layer may be present on one side or both sides of the barrier layer. The barrier layer can be protected by this base resin layer.

Examples of the polyolefin-based resin include polyethylene-based resin and polypropylene-based resin.

In the present specification, the polyethylene-based resin is a resin containing a repeating unit of an ethylene group in the main chain of a polymer in an amount of more than 50 mol%, 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, ionomer , And derivatives thereof, and mixtures thereof.

As used herein, the polypropylene-based resin is a resin containing a repeating unit of a propylene group in the main chain of a polymer in an amount of more than 50 mol%, 60 mol% or more, 70 mol% or more, or 80 mol% or more, and is, for example, polypropylene (PP). Examples include homopolymers, random polypropylene (random PP), block polypropylene (block PP), chlorinated polypropylene, acid-modified polypropylene, derivatives thereof, and mixtures thereof.

Examples of the vinyl polymer include polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polychlorotrifluoroethylene, polytetrafluoroethylene, polyacrylonitrile (PAN) and the like.

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

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

The thickness of the base resin layer is preferably 7 μm or more, 10 μm or more, or 15 μm or more from the viewpoint of good protection of the barrier layer, and 55 μm or less, 50 μm or less, or 45 μm or less is used for packaging. It is preferable from the viewpoint of improving the handleability when used as a bag.

<Gas absorption layer>
The gas absorbing layer contains a thermoplastic resin and a gas absorbent dispersed in the thermoplastic resin.

For the gas absorption layer, the resin composition constituting the gas absorption layer is kneaded using a batch type kneader such as a kneader, a Banbury mixer, a mixing roll conical mixer, or a continuous kneader such as a twin-screw kneader. Then, the kneaded resin can be produced by molding into a film by an extrusion molding method such as an inflation method or a T-die method. When the skin layer is present on one side or both sides of the gas absorption layer, it may be laminated with the skin layer together with the film formation by a coextrusion method such as a multi-layer inflation method or a multi-layer T-die method.

The thickness of the gas absorption layer is preferably 5 μm or more, 7 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, or 25 μm or more, and is preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm. Hereinafter, it is preferably 40 μm or less, 35 μm or less, or 30 μm or less from the viewpoint of film forming property.

(Thermoplastic resin)
As the thermoplastic resin, for example, the thermoplastic resin mentioned for the base resin layer can be used. As the thermoplastic resin, it is particularly preferable to use a polyolefin-based resin from the viewpoint of achieving both moldability and gas absorption.

(Gas absorber)
As the gas absorbent, a physical absorbent and a chemical absorbent can be used. Above all, it is preferable to use a physical absorbent from the viewpoint of preferentially adsorbing the amine and, as a result, increasing the absorption efficiency.

As the physical absorbent, for example, hydrophobic zeolite, silica gel, hydrophobically treated silica gel, mesoporous substances, activated carbon, plant shell powder and the like can be used. These may be used alone or as a mixture.

As the hydrophobic zeolite, for example, beta-type, ZSM-5-type, ferrienite-type, mordenite-type, L-type, or Y-type zeolite can be used. Further, ZSM-11, silicalite, silicalite-2, and pentasyl-type metallosilicate, which are analogs of ZSM-5 type zeolite, can also be used. These may be used alone or as a mixture.

The mesoporous substance is a substance having a pore diameter intermediate between micropores (2 nm or less) and macropores (50 nm or more), and examples thereof include mesoporous silica. As the plant shell powder, a porous peanut shell finely crushed can be used. These physical adsorbents may be used alone or as a mixture.

As the chemical absorber, an iron-based oxygen absorber, a metal halide, a metal oxide, a sulfate, a sulfite, a hydrogen sulfite, a nitionate and the like can be used. These may be used alone or as a mixture.

As the iron-based oxygen absorber, iron powder (for example, reduced iron powder, sprayed iron powder, activated iron powder, etc.), ferrous oxide, ferrous salt, and the like can be used. These may be used alone or as a mixture.

As the metal halide, for example, calcium chloride, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, calcium chloride, magnesium chloride, barium chloride and the like can be used. These may be used alone or as a mixture.

As the metal oxide, for example, calcium oxide, aluminum oxide, cerium oxide having an oxygen deficiency, titanium oxide having an oxygen deficiency, or the like can be used. These may be used alone or as a mixture.

The content of the gas absorbent may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, and 50% by mass or less, 45% by mass or less, 40, based on the entire mass of the gas absorbing layer. It may be 0% by mass or less, 35% by mass or less, 30% by mass or less, or 25% by mass or less.

<Amine selective permeation layer>
The amine selective permeation layer is a layer made of a polyester resin. This makes it possible to suppress the permeation of the aroma component while selectively permeating the amine.

As the polyester-based resin, the above-mentioned polyester-based resin can be used, and it is particularly preferable to use a heat-sealable polyester-based resin from the viewpoint that a separate adhesive layer is not required.

Here, in the present invention, the "heat-sealing polyester resin" is, for example, a polyester resin having a heat-sealing strength of 5N / 15 mm or more according to JIS K 6854-3 when bonded to each other. You can do it. This heat seal strength can be 7N / 15mm or more, 10N / 15mm or more, 12N / 15mm or more, 14N / 15mm or more, or 15N / 15mm or more, and 100N / 15mm or less, 80N / 15mm or less, 60N. It can be / 15 mm or less, 50 N / 15 mm or less, 40 N / 15 mm or less, 30 N / 15 mm or less, or 25 N / 15 mm or less.

As the heat-sealing polyester-based resin, a commercially available polyester-based resin that can be heat-sealed or a film made of this resin can be used. Further, as the heat-sealing polyester-based resin, for example, a polyester-based resin having an amorphous component, for example, a polyester commercially available as "amorphous polyester" or "copolymerized polyester" can be used.

As the amorphous polyester, for example, amorphous polyethylene terephthalate (PET) can be used. As the amorphous PET, for example, Hytron PG available from Tamapoli Co., Ltd. can be used.

As the copolymerized polyester, for example, an oryester (registered trademark) available from Toyobo Co., Ltd. can be used.

The thickness of the amine selective transmission layer is preferably 5 μm or more, 7 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, or 25 μm or more, and is preferably 100 μm or less, 80 μm or less, 60 μm or less from the viewpoint of handling during production. , 50 μm or less, 40 μm or less, 35 μm or less, or 30 μm or less is preferable from the viewpoint of amine permeability.

<Skin layer>
The skin layer is a layer that contains a resin for a skin layer and can be laminated on one side or both sides of the gas absorption layer. Further, the skin layer may be fused to the gas absorption layer.

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 there are a plurality of skin layers, the thickness of each skin layer may be the same or different.

(Skin layer: Resin for skin layer)
As the resin for the skin layer, the thermoplastic resins mentioned for the gas absorption layer can be used alone or in combination, and among them, it is preferable to use a polyolefin resin, particularly a polyethylene resin, from the viewpoint of processability and the like. .. When skin layers are present on both sides of the gas absorption layer, the skin layer resins constituting the skin layers may be the same or different.

<Other layers>
The gas absorbing film of the present invention may have other optional layers. As the other layer, for example, an adhesive layer can be used. As the adhesive layer, for example, a dry laminate adhesive, a hot melt adhesive, or the like can be used.

《Packaging bag》
The packaging bag of the present invention is
One or more of the above gas absorbing films are provided, and a part of the amine selective transmission layer of one or more gas absorbing films is adhered to another part of this gas absorbing film or another film. The barrier base material layer of the gas absorbing film is located on the outside, and the amine selective permeation layer is located on the inside.

Adhesion may be via an adhesive layer or by heat sealing. In particular, when the amine selective permeation layer is used as a heat seal layer, the adhesion is performed by heat seal.

The other film may be another gas absorbing film, or may be another film other than the above gas absorbing film.

The packaging bag of the present invention can be a packaging bag containing the above-mentioned packaging bag and the contents contained in the packaging bag.

<Contents>
The contents are the contents stored in the packaging bag. The contents are not limited as long as they can be deteriorated by contact with the outside air, and include foods, cosmetics, medical instruments, medical devices, electronic members, precision machines, recording materials, etc. in addition to drugs. Can be done. Further, the drug includes a cleaning agent, a pesticide and the like in addition to a pharmaceutical preparation.

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

<< Production of gas absorption film >>
<Example 1>
In a multilayer film forming machine, the skin layer, the gas absorption layer, and the skin layer were arranged in this order, and a two-kind three-layer film was produced by coextrusion molding by an air-cooled multilayer inflation method. Linear low-density polyethylene (LLDPE, Evolu SP2520, Prime Polymer Co., Ltd.) is used as the skin layer, and 80 parts by mass of low-density polyethylene (LDPE, Petrosen 202, Tosoh Co., Ltd.) and a gas absorber are used as the gas absorption layer. A resin composition prepared by melt-kneading 20 parts by mass of hydrophobic zeolite (Polycular Sieve ABSCENTS3000, Union Showa Co., Ltd.) was used. The thickness of each layer was 10 μm for the skin layer, 30 μm for the gas absorption layer, and 10 μm for the skin layer.

The AL side of the PET (12 μm) // AL (9 μm) substrate (“//” indicates a dry laminate adhesive) was dry-laminated on one skin layer side of the produced film. The dry laminating was carried out by mixing 9 parts by weight of Mitsui Chemicals' Takelac A-525S as an adhesive main agent and 1 part by weight of Takenate A-50 as a curing agent, and diluting this with ethyl acetate.

Copolymerized polyester (Olyester (registered trademark) SS DE046, Toyobo Co., Ltd., 30 μm) as an amine selective permeation layer was dry-laminated on the other skin layer side of the produced film by the same method as described above. The gas absorption film of Example 1 was prepared.

<Examples 2 to 3 and Comparative Examples 1 to 4>
The gas absorbing films of Examples 2 to 3 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1 except that the gas absorbing layer and the amine selective permeation layer were changed as shown in Table 1. Here, as the various gas absorbing layers and amine selective permeation layers referred to in Table 1, the following are used:
PE: LDPE that does not contain a gas absorber (Petrosen 202, Tosoh)
Crystalline polyester: E5100, Toyobo, 12 μm
Amorphous polyester: Hytron PG, Tamapoli, 30 μm
Cyclic olefin: COC COXEC TCS-1, Kurabo Industries, Ltd., 25 μm
EVOH: Non-catch (registered trademark), Kyodo Printing Co., Ltd., 50 μm

"evaluation"
<Heat sealability>
Each of the prepared gas absorbing films was cut into a width of 15 mm, the amine selective transmission layers were opposed to each other, and heat-sealed under the conditions of 150 ° C., time 0.5 seconds, and pressure 0.2 MPa. According to JIS K 6854-3, this was T-shaped peeled off under the condition of a tensile speed of 300 mm / min using a tensile tester, and the seal strength (heat seal strength) was measured.

<Aroma component retention>
After exposing the amine-selective permeation layer side of each gas absorbing film cut to a size of 10 cm × 10 cm to saturated l-menthol steam for one week in an environment of 40 ° C., the adsorbed l-menthol was extracted with methyl ethyl ketone and contained in the extract. The amount of l-menthol was quantified by gas chromatography, and the amount of l-menthol adsorbed per unit area was calculated.

A similar test was performed by replacing l-menthol with limonene.

In addition, ethyl acetate was used instead of l-menthol, and the aroma-retaining property of the aroma component was evaluated by the following procedure. Cut each gas absorption film into a size of 10 cm x 10 cm to make a three-way seal bag, enclose a filter paper with 10 μL of ethyl acetate dropped, and seal the remaining side so that the internal volume becomes a tetrahedron of about 86 mL. Sealed. This was stored in a constant temperature bath at 40 ° C. for 7 days, opened, and sensory evaluated by three people whether or not the scent remained inside the three-way seal bag. In the sensory evaluation, a score of 5 was given for those having a sufficient scent, and a score of 1 was given for those having a sufficient scent, and the total score was evaluated. The total score is a maximum of 15 points, and it is preferable that the score is high.

<Amine removing property>
Cut each gas absorption film into a size of 10 cm x 10 cm to make a three-way seal bag, enclose a filter paper with 10 μL of trimethylamine dropped, and seal the remaining side so that the internal volume becomes a tetrahedron of about 86 mL and seal it. bottom. This was stored in a constant temperature bath at 40 ° C. for 7 days and opened, and the odor reduction effect was sensory evaluated by 3 people. In the sensory evaluation, the one with a strong odor was evaluated as 5 points, and the one with a weak odor was evaluated as 1 point on a 5-point scale, and the total score was evaluated. The total score is a maximum of 15 points, and it is preferable that the score is low.

Table 1 shows the configurations and evaluation results of Examples and Comparative Examples.

From Table 1, the gas absorbing films of Examples 1 to 3 having a barrier base material layer, a gas absorbing layer, and an amine selective permeable layer and the amine selective permeable layer being made of a polyester resin are fragrant. It can be understood that both the fragrance-retaining property and the amine-removing property of the components were good.

Above all, it can be understood that Examples 1 and 3 in which the amine selective permeation layer is composed of the copolymerized polyester and the amorphous polyester, respectively, have good heat sealability.

On the other hand, it can be understood that in Comparative Example 2 in which the gas absorption layer was provided as the innermost layer, although the amine removing property was good as compared with the Example, the fragrance retaining property of the aroma component was extremely inferior. NS.

Further, it can be understood that Comparative Example 3 in which the cyclic olefin was used instead of the polyester resin could not suppress the adsorption of l-menthol and was inferior in amine removability as compared with Examples. ..

Further, it can be understood that Comparative Example 4, in which EVOH was used instead of the polyester resin, had the same aroma-retaining property as the example, but was extremely inferior in amine-removing property. ..

100 Gas absorption film 110 Barrier base material layer 120 Gas absorption layer 130 Amine selective permeation layer 140 Skin layer

Claims (8)

It has a barrier substrate layer, a gas absorption layer, and an amine selective permeation layer.
The gas absorbing layer contains a thermoplastic resin and a gas absorbent dispersed in the thermoplastic resin, and the amine selective permeation layer is made of a polyester resin.
Gas absorption film. The gas absorbing film according to claim 1, wherein the amine selective permeation layer is made of a heat-sealing polyester resin. The gas absorbing film according to claim 1 or 2, wherein the gas absorbent is a physical absorbent. The gas absorbing film according to claim 3, wherein the physical absorbent is at least one selected from the group consisting of hydrophobic zeolite, silica gel, mesoporous substances, activated carbon, and plant shell powder. The gas absorbing film according to any one of claims 1 to 4, further comprising a skin layer laminated on one side or both sides of the gas absorbing layer. The gas absorbing film according to any one of claims 1 to 5 is provided, and a part of the amine selective permeation layer of the gas absorbing film of one or a plurality of sheets is this gas. It is adhered to another part of the absorbent film or another film, and is formed into a bag shape so that the barrier base material layer of the gas absorbent film is located on the outside and the amine selective permeation layer is located on the inside.
Packaging bag. The packaging bag according to claim 6, wherein the adhesion is made by a heat seal. The packaging bag according to claim 6 or 7, and a packaging bag containing the contents contained in the packaging bag.

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