JP7087573B2 - Odor-adsorbing sealant film and packaging materials and packaging bags made from the odor-adsorbing sealant film. - Google Patents

Description

The present invention has excellent pinhole resistance, and the elution organic substance originally contained in the packaging material and the odorous component generated from the sealant film during sterilization / sterilization treatment are added to the liquid content in the packaging. A sealant film having excellent odor resistance and odor resistance that prevents the contents from being transferred and giving a strange odor to the contents, and packaging materials and packaging bodies made from the odor-absorbing sealant film, particularly BIB (Bag). In Box) liquid contents package.

As a packaging material, a packaging material containing an odor adsorbent that adsorbs an odor has been proposed (Patent Document 1). In such a packaging material, an odor adsorbent such as synthetic zeolite or activated carbon is kneaded into the resin material.
However, such a packaging material has a problem that it adsorbs not only odor but also moisture in the atmosphere and desorbs the odor once adsorbed, so that a sufficient odor adsorption effect can be obtained. Not.

A packaging material containing an odor adsorbent in which a chemical adsorbent is carried on an inorganic porous body is also known (Patent Document 2), but the main adsorbed object adsorbs an odor component having a specific functional group. However, in the situation where the resin material is not selected, the amount of organic substances having no functional group cannot be suppressed, and the odorous component cannot be sufficiently adsorbed.

Further, the BIB liquid content packaging bag-filled material filled with the liquid content tends to cause pinholes in the package due to rubbing during transportation and the contents are likely to leak, and is durable to prevent the occurrence of pinholes. A packaging material containing a base film or a thick base film has been used, but the packaging material tends to be hard and costly, and it is difficult to strike a balance with usability.

Japanese Patent No. 2538487 Japanese Unexamined Patent Publication No. 2014-233408

The present invention solves the above-mentioned problems, is excellent in manufacturing suitability, and sterilizes and sterilizes the elution organic substance originally contained in the sealant film by UV irradiation, hot pack, boil, γ-ray irradiation, EB irradiation, etc. During the treatment, it exerts a high adsorption effect on the odor generated by the decomposition of the resin constituting the sealant film and deodorizes it, and it is difficult to desorb the odor once adsorbed and efficiently adsorbs the odor. Because it is possible, the odor adsorption capacity does not decrease, it exhibits a high adsorption effect for a long period of time, it has excellent odor resistance changeability to liquid contents, and it also has pinhole resistance against rubbing during transportation. It is an object of the present invention to provide a packaging material having excellent leakage resistance of a liquid content and a liquid content package for BIB made of the packaging material.

As a result of various studies, the present inventors consisted of at least an outer layer film and an inner layer film, and the outer layer film and the inner layer film were only partially adhered to each other, and each of the outer layer film and the inner layer film had a sealant layer. The sealant film of the inner film contains an odor adsorbing layer, and the odor adsorbing layer is a sealant film containing low elution polyethylene and a specific hydrophobic zeolite as an odor adsorbent to achieve the above object. I found it.

The present invention is characterized by the following points.
1. 1. An odor-adsorbing sealant film consisting of at least an outer layer film and an inner layer film.
The outer layer film and the inner layer film are only partially adhered to each other.
Each of the outer layer film and the inner layer film contains a sealant layer containing low-eluting polyethylene.
The sealant layer of the inner film includes an odor adsorbing layer and contains an odor adsorbing layer.
The odor adsorbing layer contains low-eluting polyethylene and an odor adsorbent.
The odor adsorbent contains hydrophobic zeolite and
The hydrophobic zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 30/1 to 8000/1.
An odor-adsorbing sealant film in which the content of the hydrophobic zeolite in the sealant layer is 0.1% by mass or more and 13% by mass or less.
2. 2. The odor-adsorbing sealant film according to 1 above, wherein the sealant layer of the outer layer film includes the odor-adsorbing layer.
3. 3. The odor adsorbent further comprises a chemisorbent-supported inorganic porous body.
The odor-adsorbing sealant film according to 1 above, wherein the content of the chemisorbent-supported inorganic porous body in the sealant layer is 0.1% by mass or more and 10% by mass or less.
4. The odor-adsorbing sealant film according to any one of 1 to 3, wherein the density of the low-eluting polyethylene is 0.90 g / cm ³ or more and 0.94 g / cm ³ or less.
5. The odor-adsorbing sealant film according to any one of 1 to 4, wherein the low-eluting polyethylene is LLDPE.
6. The odor-adsorbing sealant film according to any one of 1 to 5, wherein the low-eluting polyethylene is one or more selected from the group of C4-LLDPE, C6-LLDPE, and C8-LLDPE.
7. In the low-eluting polyethylene, the number of pinholes generated after 5000 times of gelboflex at 23 ° C. in a 50 μm-thick film made only of the low-eluting polyethylene is 0, or 1 or more, 160. The odor-adsorbing sealant film according to any one of 1 to 6 above, wherein the number is less than one.
8. The odor according to any one of 1 to 7 above, wherein the low-eluting polyethylene has a concentration of elution TOC contained in a film made only of the low-eluting polyethylene of 1.5 ppm or more and 250 ppm or less. Adsorption sealant film.
9. The hydrophobic zeolite is previously melt-kneaded at a mass ratio of the thermoplastic resin to the hydrophobic zeolite / thermoplastic resin at a ratio of 0.5 / 99.5 to 40/60. The odor-adsorbing sealant film described in any of the above.
10. The chemical adsorbent-supported inorganic porous body is previously melt-kneaded with a thermoplastic resin at a ratio of 0.5 / 99.5 to 40/60 of the chemical adsorbent-supported inorganic porous body / thermoplastic resin. The odor-adsorbing sealant film according to any one of 2 to 9.
11. The odor-adsorbing sealant film according to 9 or 10 above, wherein the melt flow rate of the thermoplastic resin is 0.2 to 10.0 g / 10 minutes.
12. The chemical adsorbent constituting the chemical adsorbent-supporting inorganic porous body has a functional group reactive with one or more selected from the group of aldehydes, ketones, and carboxylic acids. The odor-adsorbing sealant film according to any one of 11 to 11.
13. The odor-adsorbing sealant film according to any one of 2 to 12, wherein the chemical adsorbent constituting the chemical adsorbent-supported inorganic porous body has an amino group.
14. The odor adsorption layer includes a non-odor adsorption layer on one side or both sides.
The non-odor adsorbing layer is a layer containing low-eluting polyethylene and not containing the odor adsorbent.
The odor-adsorbing sealant film according to any one of 1 to 13 above.
15. The odor-adsorbing sealant film according to any one of 1 to 14, wherein the outer layer film further includes a base material layer.
16. An odor-adsorbing packaging material comprising the odor-adsorbing sealant film according to any one of 1 to 15 above.
17. A liquid content packaging bag for BIB made from the odor-adsorbing packaging material according to 16 above.

Since the odor-adsorbing sealant film of the present invention has an odor-adsorbing layer having a specific composition and contains a specific low-eluting polyethylene, the elution organic substances and odors originally contained in the packaging material are contained. It is reduced and has the effect of efficiently adsorbing the odor generated by the decomposition of the resin constituting the sealant film during sterilization / sterilization treatment such as UV irradiation, γ-ray irradiation, EB irradiation, hot pack, boil, etc. for a long period of time. Have.

Due to these effects, when a liquid content package is produced using the odor-adsorbing sealant film of the present invention, the amount of organic matter eluted in the filled liquid content is reduced and the change in odor is suppressed. Can be done.
Therefore, the odor-adsorbing sealant film of the present invention is suitable as a packaging bag for liquid foods, pharmaceuticals, and medical products to be sterilized and sterilized.
Further, since the odor-adsorbing sealant film of the present invention is composed of an outer layer film and an inner layer film that are partially adhered to each other, the generation of pinholes due to rubbing during transportation or the like can be suppressed, and liquid leakage or the like can be suppressed. ..

It is a schematic bird's-eye view which shows an example of the odor adsorption sealant film of this invention. This is an example of a schematic cross-sectional view taken along the cross-sectional line A of the odor-adsorbing sealant film of FIG. It is sectional drawing which shows an example of the layer structure of the outer layer film or the inner layer film. It is sectional drawing which shows an example of another aspect of the layer structure of the outer layer film or the inner layer film. It is sectional drawing which shows an example of still another aspect of the layer structure of the outer layer film or the inner layer film. It is sectional drawing which shows an example of still another aspect of the layer structure of the outer layer film or the inner layer film. It is sectional drawing which shows an example of another aspect of the layer structure of an outer layer film. It is a figure which shows the adsorption mechanism to the odor substance of a chemical adsorbent-supported inorganic porous body. It is a schematic bird's-eye view which shows an example of the liquid contents packaging bag for BIB. 9 is an example of a schematic cross-sectional view taken along the cross-sectional line A of the liquid content packaging bag for BIB in FIG. 9.

The odor-adsorbing sealant film, the odor-adsorbing packaging material, and the odor-adsorbing package of the present invention will be described in more detail below. The present invention will be described with reference to specific examples, but the present invention is not limited thereto.

<Odor adsorption sealant film>
As shown in FIGS. 1 and 2, the odor-adsorbing sealant film of the present invention is composed of at least an outer layer film and an inner layer film, and the outer layer film and the inner layer film are only partially adhered to each other.
The partially bonded portion between the outer layer film and the inner layer film is preferably at least on the peripheral edge of the odor-adsorbing sealant film, and may be in the form of a grid with continuous lines or the shape with discontinuous lines. It may be point-shaped.

When the odor-adsorbing sealant film of the present invention is used as a packaging material, fatigue fracture progresses due to local repeated bending due to vibration during the packaging process or transportation, and contact with packaging parts such as a content extraction port. When used as a package for liquid contents for BIB, pinholes that leak the liquid contents may occur. Therefore, pinhole resistance is especially important for packaging materials for foods and medical supplies. be.
When used for aseptic filling, the package is sterilized with an electron beam, γ-ray, ethylene oxide gas or the like, and then supplied to the next step or the user.

<Layer composition of outer layer film and inner layer film>
Each of the outer layer film and the inner layer film is a film having a sealant layer containing at least a low-eluting polyethylene.
The sealant layer of the inner film includes an odor adsorbing layer. Further, if necessary, the sealant layer of the outer film can also include an odor adsorbing layer.

The sealant layer having the odor adsorption layer may be a layer consisting only of the odor adsorption layer as shown in FIG. 3, and as shown in FIGS. 4 and 5, in order to improve the sealing strength and the interlayer adhesion strength. In addition, a multilayer structure with a non-odor adsorbing layer containing low-eluting polyethylene but not containing an odor adsorbent may be used.

Further, as shown in FIG. 6, the odor adsorbing layer may have a multilayer structure in which the type of the main low-eluting polyethylene and the type and content of the odor adsorbent are the same or different.

In the packaging bag using the odor-adsorbing sealant film of the present invention, the innermost layer in contact with the liquid content may be an odor-adsorbing layer or a non-odor-adsorbing layer. When the non-odor adsorbing layer is the innermost layer, the sealing strength of the packaging bag can be improved, and when the odor adsorbing layer is the innermost layer, the interlayer adhesion strength in the packaging bag can be improved.

Further, as shown in FIG. 7, each of the outer layer film and the inner layer film has a base material layer, a functional layer such as a reinforcing layer, and an adhesive layer in order to improve the strength of the film and to impart various functions. Etc., and it is particularly preferable that the outer layer film contains a base material layer. As the base material layer, the functional layer, and the adhesive layer, known ones can be laminated and used by a known method.

<Sealant layer of outer film and inner film>
The sealant layer of the inner film includes an odor-adsorbing layer, and may further include a non-odor-adsorbing layer.
The sealant layer of the outer film may include a non-odor adsorbing layer and / or an odor adsorbing layer.

[Odor adsorption layer]
The odor adsorbing layer in the present invention contains a resin composition containing a low-eluting polyethylene and an odor adsorbent.
Furthermore, general-purpose polyethylene, polypropylene, methylpentene polymer, acid-modified polyolefin-based resin, and a mixture of these thermoplastic resins may be contained within a range that does not impair the low elution property and heat-sealing property of the sealant film. It is possible, but not limited to these resins.

In one aspect of the present invention, the odor adsorbing layer is a single layer structure formed by using a resin composition obtained by kneading an odor adsorbent and low-eluting polyethylene. Here, the odor adsorbent may be uniformly dispersed in the layer, or may be dispersed with a concentration gradient.
For example, it may be dispersed from the inner surface to the outer surface at the time of forming the package with an increasing concentration gradient, and this configuration improves the heat sealability. On the contrary, the particles may be dispersed from the inner surface to the outer surface at the time of forming the package with a decreasing concentration gradient, and this configuration improves the interlayer adhesion strength.
Further, the odor adsorbing layer may be dispersed from the central portion in the thickness direction toward both surfaces with a decreasing concentration gradient, and this configuration improves the heat sealability and the interlayer adhesion strength.

In still another embodiment, the odor adsorbing layer may have a multi-layered structure in which two or more layers are laminated, wherein each layer is composed of a main type of low-eluting polyethylene or an odor adsorbent. It may consist of resin compositions having different types and contents.
A film can be formed if the thickness of the entire odor adsorbing layer is 5 μm or more, but it is preferably 10 μm to 200 μm in order to obtain good film forming property, heat sealing property, interlayer adhesion strength and odor adsorbing property.
The odor adsorbent contains hydrophobic zeolite, and can further include a chemical adsorbent-supported inorganic porous body.

It is also possible to mix hydrophobic zeolite or chemical adsorbent-supported inorganic porous material directly with low-eluting polyethylene and knead it, or to mix hydrophobic zeolite or chemical adsorbent-supported inorganic porous material at a high concentration in a thermoplastic resin. It is also possible to prepare a master batch by melt-kneading after mixing with the above, and this is also possible by a so-called master batch method in which the master batch is mixed with low-eluting polyethylene at a ratio according to the target content and melt-kneaded.

In the present invention, if the amount of the hydrophobic zeolite added is 0.05% by mass or more in the sealant layer including the odor adsorbing layer, a sufficient odor adsorbing effect can be exhibited, but the packaged product. In order to obtain a good odor adsorption effect, it is preferably 0.1% by mass or more, and more preferably 0.25% by mass or more. On the other hand, the content of the hydrophobic zeolite is preferably 13% by mass or less, preferably 10% by mass, in order to obtain good film-forming property at the time of producing the laminate and to achieve good heat-sealing property. The following is more preferable.

As for the content of the chemically adsorbent-supported inorganic porous body, if it is contained in the sealant layer including the odor adsorbing layer in an amount of 0.05% by mass or more, a sufficient adsorption effect can be exhibited, but as a package. In order to obtain a good adsorption effect, it is preferably 0.1% by mass or more, and more preferably 0.25% by mass or more.

On the other hand, in order to obtain good film-forming property at the time of producing the laminate and to achieve good heat-sealing property, the content of the chemisorbent-supported inorganic porous body is set in the sealant layer including the odor adsorbing layer. In addition, it is preferably 10% by mass or less, and more preferably 9% by mass or less.

[Low-elution polyethylene]
In the present invention, the sealant layer of the outer layer film and the inner layer film contains low-elution polyethylene having a heat-sealing property and a small amount of organic matter eluted.
When the amount of the organic substance eluted is small, the concentration of the organic substance eluted in the liquid content filled in the package of the present invention can be reduced and the change in odor can be suppressed.
Here, the concentration of the organic substance in the liquid content is indicated by the concentration of total organic carbon (TOC) in the present invention.
TOC indicates the concentration of the total amount of organic substances (organic carbon bodies) that can be oxidized in water by the concentration of carbon content, and is used as one of the typical water quality indexes. It is standardized by organic carbon (TOC) automatic measuring instrument) and the like.

The concentration of elution TOC contained in the film made of low-elution polyethylene is 1.5.
It is ppm or more and 250 ppm or less.
Here, the reason why the concentration of the elution TOC related to the low-eluting polyethylene as a single raw material is measured not in the state of raw material pellets or the like but in the filmed state is that the low-eluting polyethylene is used for forming a sealant layer or the like. This is because when the film is formed, various thermal histories and the like may be given to increase the elution amount of TOC.

The increase concentration of TOC in the filled water after filling 1 kg of distilled water as filling water in a pouch packaging bag having a thickness of 15 cm × 44 cm × 50 μm made from low-eluting polyethylene in the present invention and eluting is , 0.01 ppm or more and 1.5 ppm or less, more preferably 0.02 ppm or more and 1.45 ppm or less, and further preferably 0.025 ppm or more and 1.4 ppm or less.
When the increased concentration of TOC in the filling water is larger than 1.5 ppm, it is difficult to suppress the change in the odor of the filled water, and the cost is high to obtain the one smaller than 0.01 ppm. The effect is limited. From the viewpoint of achieving both cost and performance, the above range is preferable.

As a specific method for determining the increased concentration of TOC, for example, 1000 g of distilled water at 40 ° C to 80 ° C is filled in the above pouch packaging bag, and the temperature is 25 ° C to 50 ° C for several days to 4 weeks. The TOC concentration of the filled water after storage can be measured with a total organic carbon meter or HS-GC, and the TOC concentration of the distilled water can be subtracted as a blank.

In the present invention, a pouch bag (15 cm × 44 cm) package is prepared using an outer layer film, an inner layer film, and an odor-adsorbing sealant film, and water at 65 ° C. (distilled water for high-speed liquid chromatography, genuine chemistry) 1000 g. The standard method is to prepare a packaged liquid filler by filling it with water, store it at 35 ° C for 2 weeks, and then measure the TOC concentration of the filled water with a TOC-L total organic carbon meter manufactured by Shimadzu Corporation. , Find the increased concentration of TOC.
Then, the elution TOC concentration contained in the sealant film is calculated from the obtained TOC increase concentration of the filled water and the mass part of the filled water and the mass part of the sealant film.

Specific examples of low-eluting polyethylene include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear (linear) low-density polyethylene (LLDPE), and ethylene-vinyl acetate. Low elution of polymers, polyethylene-ethyl acrylate copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-methylmethacrylic acid copolymers, ethylene-propylene copolymers, etc. These include, but are not limited to, those and mixtures of their resins.
In order to reduce the amount of organic matter eluted from the low-elution polyethylene film, the following methods can be mentioned, but the method is not limited thereto.

When producing polyethylene, it is effective to reduce the residual amount of unreacted raw materials, the amount of low molecular weight products and by-products, and to remove the polymerization catalyst. Specifically, it improves the purity of raw materials, precisely controls conditions such as reaction temperature and pressure, and removes unreacted raw materials, low molecular weight products, by-products, and polymerization catalysts by distillation and washing. Examples thereof include a method of preventing oxidation due to contact with oxygen in the air at a high temperature.

When pelletizing the produced polyethylene, there is a method of limiting the use of lubricants, antioxidants, and other additives that are likely to increase the elution amount of organic substances.
When forming polyethylene into a film, there is a method of limiting the use of lubricants, antioxidants, solvents, and other additives that are likely to increase the amount of organic matter elution to prevent oxidation due to high temperatures. Can be mentioned.

In the present invention, the sealant layer has a heat-sealing property and contains a low-eluting polyethylene, so that the packaging material made from the odor-adsorbing sealant film has an excellent heat-sealing property and the amount of organic matter eluted. It is possible to reduce the increase in the concentration of TOC in the liquid content in the package.

Further, polyethylene is suitable in that it is resistant to sterilization and sterilization treatments such as UV and has a property of being hard to be decomposed.
Among these low-eluting polyethylenes, LLDPE is preferable as the type, and further, LLDPE having side chains of C4, C6, and C8 tends to reduce the elution amount of organic substances, and therefore C4-LLDPE. , C6-LLDPE, C8-LLDPE and the like are more preferable.

Here, C4, C6, and C8 are partially copolymerized with LLDPE, indicating that the monomer having the number of carbon atoms described is present in the side chain. For example, C4 represents butene-1, C6 represents hexene-1, or 4-methylpentene-1, and C8 represents the side chain of the structure of octene-1.
Alternatively, low-eluting polyethylene having a density of 0.90 g / cm ³ or more and 0.94 g / cm ³ or less is preferable, and low-eluting polyethylene having a density of 0.905 g / cm ³ or more and 0.933 g / cm ³ or less is preferable. More preferred. Low-eluting polyethylene with a density in this range tends to reduce the amount of organic matter eluted.
Further, the low-eluting polyethylene can also contain a small amount of additives such as an antioxidant and an anti-blocking agent.
Furthermore, it is preferable that the low-eluting polyethylene in the present invention is excellent in pinhole resistance due to bending when it is formed into a film by itself.

The pinhole resistance of the low-eluting polyethylene in the present invention is, for example, that the number of pinholes generated in a 50 μm-thick film made of a low-eluting polyethylene alone after 5000 gelboflexes at 23 ° C. is 0. Alternatively, the number is preferably 1 or more and 160 or less.
When the number of pinholes generated in the sealant film is within the above range, it is possible to produce a packaging material that can withstand practical use in applications that require pinhole resistance.

[Odor adsorbent]
In the present invention, the odor adsorbent contains a specific hydrophobic zeolite, and can further include a chemical adsorbent-supported inorganic porous body.

(Hydrophobic zeolite)
Generally, the higher the molar ratio of SiO ₂ / Al ₂ O ₃ , the higher the hydrophobicity of the zeolite. In the present invention, the hydrophobic zeolite contained in the odor adsorption layer is the molar of SiO ₂ / Al ₂ O ₃ . The ratio is preferably 30/1 to 8000/1.
The hydrophobic zeolite does not lose its odor adsorbing ability even when the package or the packaging material is exposed to 230 ° C. or higher, and can exert a deodorizing effect by adsorbing an odor component.
The hydrophobic zeolite may have an arbitrary outer shape such as a spherical shape, a rod shape, or an elliptical shape, and may have any shape such as a powder shape, a lump shape, or a granular shape. In the form of powder, it is preferable from the viewpoint of uniform dispersion and kneading characteristics.

In the present invention, the average particle size of the hydrophobic zeolite can be appropriately selected depending on the intended use, but the average particle size is preferably 0.01 μm to 10 μm. Here, the average particle size is a value measured by a dynamic light scattering method.

When the average particle size is smaller than 0.01 μm, the hydrophobic zeolite tends to aggregate and the dispersibility in the low-eluting polyethylene tends to decrease. Further, when the average particle size is larger than 10 μm, the film-forming property of the odor adsorbing layer tends to be inferior, so that it tends to be difficult to add a large amount of hydrophobic zeolite, and the surface area is also reduced, so that it is sufficiently consumed. There is a possibility that the odor effect cannot be obtained.

Since hydrophobic zeolite is hydrophobic, it is difficult to adsorb highly polar water molecules, and conversely, it has low polarity and affinity with odorous molecules, hydrophobic gases, and lipophilic gases (including solvent-based gases). Is high and it is easy to adsorb these. Further, the zeolite surface is basic due to the effects of alkali metals such as Ca, Na and K and alkaline earth metals existing on the zeolite surface, and acid gas is easily adsorbed by the neutralization reaction.

(Chemisorbent-supported inorganic porous material)
In the present invention, the chemical adsorbent-supported inorganic porous body is an inorganic porous body on which a chemical adsorbent is supported, and is an elution organic substance, UV irradiation, γ-ray irradiation, EB irradiation, hot pack, boil. It has a function of adsorbing odorous substances generated from the package during sterilization and sterilization.

As a supporting method, a known or conventional supporting method can be applied. For example, the inorganic porous body may be impregnated with a solution containing a chemical adsorbent described below and dried to support the inorganic porous material. can.

In the present invention, by containing the odor adsorbent in which the chemical adsorbent is carried on the inorganic porous body in the odor adsorbent layer, the adsorption capacity per unit mass of the chemical adsorbent can be significantly enhanced, and the odor adsorbent can be contained in the odor adsorbent layer. The content of the chemical adsorbent-supported inorganic porous body can be reduced. In addition, physical adsorption characteristics for the pores of the inorganic porous body can be expected.

By reducing the content, high sealing strength can be obtained, and the excellent heat-sealing property and film-forming property required for a sealant film can be maintained.
Further, the chemisorbent-supported inorganic porous body may have an arbitrary outer shape such as a spherical shape, a rod shape, or an elliptical shape, and may have any shape such as a powder shape, a lump shape, or a granular shape. From the viewpoint of film properties, uniform dispersion in thermoplastic resin, kneading characteristics, etc., powdery form is preferable.

As the chemisorbent-supported inorganic porous body, an arbitrary average particle size can be appropriately selected depending on the intended use, but in the present invention, an average particle size of 0.01 μm to 10 μm is particularly preferable, and 0. .1 μm to 8 μm is more preferable, and 1 μm to 7 μm is further preferable. Here, the average particle size is a value measured by a dynamic light scattering method.
When the average particle size is smaller than 0.01 μm, aggregation of the chemisorbent-supported inorganic porous material tends to occur, and the dispersibility of the chemisorbent-supported inorganic porous material in the low-eluting polyethylene tends to decrease.
Further, when the average particle size is larger than 10 μm, the film-forming property of the odor adsorption layer is inferior, so that it tends to be difficult to contain a large amount of the chemisorbent-supported inorganic porous material, and a sufficient adsorption effect cannot be obtained. Sex arises.

(Inorganic porous body)
In the present invention, any inorganic compound having a large number of pores on its surface can be used as the inorganic porous body, and for example, inorganic phosphoric acid such as zeolite, silicon dioxide, silicate, activated carbon, titania, and calcium phosphate. Examples include salts, alumina, aluminum hydroxide, magnesium hydroxide, and mixtures thereof.

In particular, it is preferable to apply aluminum hydroxide, zeolite, or silicate from the viewpoint of having a porous state with a pore size effective for the molecular size and cluster size of the substance to be adsorbed and from the viewpoint of safety.
Further, these may have any external shape such as a spherical shape, a rod shape, an elliptical shape, etc., and may have any shape such as a powder shape, a lump shape, a granular shape, etc. After that, the powdery state is preferable from the viewpoints of film forming property of the odor adsorbing layer, uniform dispersion in the thermoplastic resin, kneading property and the like.

As the inorganic porous body, one having an arbitrary average particle size can be appropriately selected depending on the intended use, but in the present invention, in particular, in order to obtain a chemical adsorbent-supported inorganic porous body having the above average particle size. The average particle size is preferably 0.01 μm to 10 μm, more preferably 0.1 μm to 8 μm, and even more preferably 1 μm to 7 μm.

(Chemisorbent)
In the present invention, the chemical adsorbent has a reactive functional group that chemically reacts with an elution organic substance or an odorous substance generated by decomposition of a resin during sterilization / sterilization treatment to bond with the above-mentioned chemical adsorbent. A compound that can be carried on an inorganic porous body.
More specifically, a functional group having reactivity to bind to various aldehydes, ketones, carboxylic acids and the like generated during UV irradiation, γ-ray irradiation, EB irradiation, sterilization / sterilization treatment such as hot pack and boil. It is a compound that has.

Examples of such a compound include a compound having a basic functional group such as an amino group and a hydroxyl group, a metal carbonate, a metal hydrogen carbonate, an amide group-containing compound and the like, and specific compounds thereof include the following. However, it is not limited to these.

Examples of the compound containing an amino group include alkylamine, ethylenediamine, tetramethylenediamine, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, piperazine, metaphenylenediamine, polyamine and the like.
Examples of the compound having a hydroxyl group include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and iron hydroxide.
Examples of the metal carbonate include sodium carbonate, calcium carbonate and the like.
Examples of the hydrogen carbonate include sodium hydrogen carbonate.
Examples of the amide group-containing compound include 2-acrylamide-2-methylpropanesulfonic acid.

In the present invention, a compound having an amino group is preferable as the chemisorbent that exhibits a particularly excellent adsorption effect.
The adsorption mechanism of the chemical adsorbent on the substance to be adsorbed such as the eluted organic substance and the odorous substance will be described in more detail with reference to the specific examples of FIGS. 8A to 8B, but the present invention is not limited thereto.

For example, when the substance to be adsorbed (odorous substance) is an acid-based odorous substance, as shown in FIG. 8A, for example, a compound having a hydroxyl group is selected as a chemical adsorbent and placed on the inorganic porous body. It can be supported and used as a chemically adsorbent-supported inorganic porous body. As a result, the carboxyl group and the hydroxyl group cause a chemical reaction to bond with each other, and the substance to be adsorbed is adsorbed.
When the substance to be adsorbed is an aldehyde, as shown in FIG. 8B, for example, a compound having an amino group is selected as the chemical adsorbent and supported on the inorganic porous body to be a chemical adsorbent. It can be used as a supported inorganic porous body. As a result, the aldehyde group and the amino group cause a chemical reaction to bond with each other, and the substance to be adsorbed is adsorbed.

At this time, due to the chemical adsorption, the substance to be adsorbed (odorous substance) once adsorbed does not desorb, and the odor can be efficiently adsorbed.
Further, unlike the physical adsorbent in which the substance to be adsorbed (odorous substance) and water vapor are adsorbed to the same adsorption site, the chemical adsorbent in the present invention binds the substance to be adsorbed to a specific functional group of the chemical adsorbent. Therefore, it is not easily affected by various substances that reduce the odor adsorption ability, such as water vapor.

<Non-odor adsorption layer>
The non-odor adsorbing layer in the present invention is a layer containing low-eluting polyethylene and not containing an odor adsorbent.
Further, it contains highly elution polyethylene, polypropylene, methylpentene polymer, acid-modified polyolefin resin, and a mixture of these thermoplastic resins within a range that does not impair the low elution property and heat sealability of the sealant film. It is possible, but not limited to these resins.

<Method of producing outer layer film or inner layer film>
(Dispersion method of odor adsorbent)
As a method for kneading the odor adsorbent and the low-eluting polyethylene, a known or conventional kneading method can be applied.
It is also possible to directly mix the odor adsorbent with low-eluting polyethylene and knead it, or to mix the odor adsorbent with a thermoplastic resin at a high concentration and then melt-knead it to prepare a masterbatch. It is also possible to use a so-called masterbatch method in which the polyethylene is mixed with low-eluting polyethylene at a ratio according to the target content and melt-kneaded.

The content of the hydrophobic zeolite in the masterbatch is preferably 0.5% by mass or more and 40% by mass or less, and more preferably 1% by mass or more and 20% by mass or less.
The content of the chemisorbent-supported inorganic porous body in the masterbatch is preferably 0.5% by mass or more and 40% by mass or less, and more preferably 1% by mass or more and 20% by mass or less.

In the case of the masterbatch method, the odor adsorbent can be uniformly dispersed in the low-eluting polyethylene even if the combination of the odor adsorbent and the low-eluting polyethylene, which easily cause aggregation, is used.
At this time, the thermoplastic resin in the masterbatch may or may not be the same as the low-eluting polyethylene in the odor adsorption layer. It is possible to combine the same types of low-elution polyethylene and other thermoplastic resins according to the purpose.

For example, if an odor adsorbent and low-eluting polyethylene are melt-mixed in advance, when they are mixed or melt-kneaded again with low-eluting polyethylene, they are homogeneous and have good film-forming property, heat-sealing property, and interlayer adhesion strength. And it is possible to obtain odor adsorption.

Examples of the thermoplastic resin other than the low-eluting polyethylene in the odor adsorption layer include general-purpose non-low-eluting polyethylene, polypropylene, methylpentene polymer, polyolefin resins such as acid-modified polyolefin resins, and mixtures of these resins. However, the present invention is not limited to these resins.

The thermoplastic resin preferably has a low elution property equivalent to that of the low elution polyethylene in the present invention, but a general-purpose resin is used as long as it does not significantly adversely affect the amount of organic substances eluted from the entire sealant layer. Can be used.

(Film formation / lamination method)
In the present invention, the film forming and laminating methods for each layer of the outer layer film or the inner layer film are not particularly limited, and known or conventional film forming methods and laminating methods can be applied.
An odor-adsorbing layer or a non-odor-adsorbing layer may be laminated by extrusion-coating on another layer, optionally via an adhesive layer, or, for example, a plurality of odor-adsorbing layers and non-odor-adsorbing layers may be laminated. It can also be formed by coextrusion by the inflation method or the casting method.

When laminating by extrusion coating, first, the resin composition forming the odor adsorption layer and the resin composition forming the non-odor adsorption layer are heated and melted, and then expanded and expanded in the required width direction with a T-die. The molten resin is extruded into a curtain shape, and the molten resin is allowed to flow down onto the surface to be laminated and sandwiched between a rubber roll and a cooled metal roll to form an odor-adsorbing layer or a non-odor-adsorbing layer and adhere to the surface to be laminated. And laminating at the same time.

The melt flow rate (MFR) of the low-eluting polyethylene contained in the odor-adsorbing layer and the thermoplastic resin contained in the non-odor-adsorbing layer when laminated by the extrusion coating shall be 0.2 to 50 g / 10 minutes. Is preferable, and more preferably 0.5 to 30 g / 10 minutes. In this specification, MFR is a value measured by a method based on JIS K7210.
If the MFR is less than 0.2 g / min or 50 g / min or more, it is difficult to be effective in terms of processing suitability.
When the inflation method is used, the melt flow rate (MFR) of the low-eluting polyethylene contained in the odor adsorption layer and the thermoplastic resin contained in the non-odor adsorption layer is 0.2 to 10.0 g / 10 minutes. It is preferably 0.2 to 9.5 g / 10 minutes.
If the MFR is less than 0.2 g / 10 minutes or 10.0 g / 10 minutes or more, it tends to be inferior in terms of processing suitability.

Alternatively, the odor-adsorbing layer and the non-odor-adsorbing layer formed in advance may be laminated via the adhesive layer by dry lamination, non-solvent lamination, sand lamination or the like.

<Adhesive layer>
In the present invention, it is also possible to provide and laminate an adhesive layer between each layer in the sealant layer, each layer such as the sealant layer-base material layer, and the like.
The adhesive layer may consist of an adhesive or any anchor coating agent.
The adhesive may be a heat-curable type, an ultraviolet-curable type, an electron beam-curable type, or the like, and may be in any form such as an aqueous type, a solution type, an emulsion type, a dispersed type, and the properties thereof are film / sheet. It may be in any form such as a form, a powder form, a solid form, and the like, and the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a thermal pressure type.

The adhesive layer may be an EC (extrusion coat) layer, a dry laminating adhesive, a non-solvent laminating adhesive, or the like.

The components forming such an adhesive layer include polyvinyl acetate adhesives such as polyvinyl acetate and vinyl acetate-ethylene copolymers, and copolymers of polyacrylic acid with polystyrene, polyester, polyvinyl acetate and the like. Polyacrylic acid adhesive, cyanoacrylate adhesive, ethylene copolymer adhesive consisting of a copolymer of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, and methacrylic acid, cellulose adhesive, Polyurethane adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive, polyolefin adhesive such as LDPE, amino resin adhesive composed of urea resin or melamine resin, phenol resin adhesive, epoxy adhesive Adhesives, reactive (meth) acrylic adhesives, chloroprene rubbers, nitrile rubbers, elastomeric adhesives made of styrene-butadiene rubbers, silicone adhesives, alkali metal silicates, inorganic adhesives made of low melting point glass, etc. And so on.

As the anchor coating agent, for example, an organic titanium-based, isocyanate-based, polyethyleneimine-based, acid-modified polyethylene-based, polybutadiene-based anchor coating agent can be used.
When the adhesive layer is laminated by the extrusion coating, the adhesive can be formed by the extrusion coating on the layer to be adhered, without particular limitation.

In the extrusion coating, first, the adhesive is heated and melted, expanded and stretched in the required width direction with a T-die, extruded into a curtain shape, and the melt is allowed to flow down onto the layer to be bonded to be cooled with a rubber roll. By sandwiching it with the metal roll, the adhesive layer is formed, and the adhesive layer is adhered to and laminated at the same time.

When an adhesive for dry laminating is used as the adhesive layer, an adhesive dispersed or dissolved in a solvent is applied onto one layer, dried, and the other layer to be adhered is laminated and then laminated at 30 to 120 ° C. By aging for several hours to several days, the adhesive is cured and laminated.
When using a non-solvent laminating adhesive, the adhesive itself is applied onto the layer without being dispersed or dissolved in a solvent, dried, and the other layer to be adhered is laminated and then laminated at 30 to 120 ° C. By aging for several hours to several days, the adhesive is cured and laminated.

The adhesive layer is formed by applying the above adhesive with, for example, a roll coat, a gravure roll coat, a kiss coat, or the like, and the coating amount thereof is preferably about 0.1 to 10 g / m ² (dry state). Good adhesiveness can be obtained by setting the coating amount of the adhesive within the above range.

When laminating by sand lamination, the adhesive layer can be melted by heating and any resin applicable to the extruder can be used. Specifically, the thermoplastic resin used for the above-mentioned non-odor adsorbing layer can be preferably used.

<Packaging material>
The packaging material can be produced by using the odor-adsorbing sealant film of the present invention as it is or by laminating a base material layer or a functional layer as needed. In particular, it is also suitable as a packaging material for liquid contents for BIB.

<Packaging body, liquid content packaging bag for BIB>
The package of the present invention is used, for example, as a liquid content packaging bag for BIB, and is used for filling the contents in a state where the content extraction port is capped and sealed. That is, when used for normal purposes, the sealed liquid content package for BIB is put in a cardboard box and supplied to the user, but when used for aseptic filling, the sealed liquid content package for BIB is packaged. The body is sterilized with electron beam, γ ray, ethylene oxide gas or the like, and then supplied to the user.

As shown in FIG. 9, for example, the liquid content packaging bag for BIB of the present invention comprises, at least, a double bag portion using a packaging material made from the odor-adsorbing sealant film of the present invention, and a resin molded product. It consists of a product extraction port.
The double bag portion is composed of an upper film and a lower film as shown in FIGS. 9 and 10, and the content extraction port is attached to the upper film.

<Liquid contents>
In the present invention, the liquid content refers to all seasoning liquids such as drinking water, juices, infusions for drip, soy sauce, sauces, and liquids such as soup, honey, sauce, and dressing.
[How to make a package]
In the package of the present invention, for example, as shown in FIG. 10, the packaging material is bent or 2 so that the sealant layer of the upper film to which the content extraction port is attached faces the sealant layer of the lower film. The sheets are stacked, and the peripheral ends thereof are, for example, side seal type, two-way seal type, three-way seal type, four-way seal type, envelope sticker seal type, gassho sticker sticker type (pillow seal type), fold seal type, flat bottom. It can be manufactured by heat-sealing in a heat-sealing form such as a seal type, a square bottom seal type, or a gusset type.
As a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal can be applied.

As a method of attaching the content extraction port to the upper film, a hole is made at the attachment position of the content extraction port of the upper film, and the content extraction port is inserted into the hole from the inside of the upper film to form the content extraction port. The inner surface of the upper film is heat-sealed on the outer side of the flange to fix it, and the content extraction port is covered with a cap to make it sealed.

<Content extraction port>
The content extraction port is an inlet / outlet for filling and / or taking out the contents, and one content extraction port may be used for filling and taking out the contents. The contents may be filled and taken out at separate content extraction ports.

The mounting position of the content extraction port is not particularly limited, but it is preferably mounted near the four sides of the package.
The content extraction port contains a polyolefin-based resin.

Specific examples of the polyolefin-based resin include polyethylene-based resins (LDPE, MDPE, HDPE, LLDPE, etc.), various ethylene copolymers, polypropylene-based resins, cyclic polyolefin-based resins, methylpentene polymers, acid-modified polyolefin-based resins, and the like. However, it is not limited to these.

The melt flow rate of the polyolefin resin is preferably 5 g / min or more and 100 g / min or less from the viewpoint of moldability.

In addition, the content extraction port has workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, flame retardancy, antifungal properties, electrical properties, strength, etc. Various plastic compounding agents, additives and the like can be contained for the purpose of improving and modifying the above.
Further, the content extraction port may contain low-eluting polyethylene or an odor adsorbent, if necessary.
The content extraction port can be obtained by mixing and kneading the above-mentioned various raw materials by a known method to prepare a resin composition, and molding the resin composition by a known method.

The details of the raw materials used in the examples are as follows.
[Low-elution polyethylene and general-purpose polyethylene for inner layer film and outer layer film]
The polyethylene shown in Table 1 and the following polyethylene were used.
-UMERIT0520F: LLDPE manufactured by Ube Kosan Co., Ltd.
-Novatec LC520: LDPE resin manufactured by Japan Polyethylene Corporation.

[Resin and molding for content extraction port]
The contents extraction ports A to E were obtained by injection molding at 200 ° C. using the low-eluting polyethylene for the resin molded product shown in the table.

[Odor adsorbent]
(Chemisorbent-supported inorganic porous material)
-Kesmon NS-241: An amino group-containing compound-supporting inorganic porous body manufactured by Toagosei Co., Ltd. Average particle size 3.5 μm.
(Hydrophobic zeolite)
・ Mizuka Sieves EX-122: Made by Mizusawa Industrial Chemicals Co., Ltd. SiO ₂ / AL _{2O 3} molar ratio = 32/1, average particle size 2.5 to 5.5 μm.
-Silton MT400: Made by Mizusawa Industrial Chemicals Co., Ltd. SiO ₂ / AL ₂ O ₃ molar ratio = 400/1, average particle size 5-7 μm.
-Silton MT2000: Made by Mizusawa Industrial Chemicals Co., Ltd. SiO ₂ / AL _{2O 3} molar ratio = 2000/1, average particle size 2-4 μm.
-Silton MT-8000: Made by Mizusawa Industrial Chemicals Co., Ltd. SiO ₂ / AL _{2O 3} molar ratio = 8000/1, average particle size 0.8 μm.
(Hydrophilic zeolite)
・ Mizuka Sieves Y-420: Made by Mizusawa Industrial Chemicals Co., Ltd. SiO ₂ / AL ₂ O ₃ molar ratio = 5/1, average particle size 5 μm.

[Base film]
Bonnil RX: Biaxially stretched nylon film manufactured by Kohjin Film & Chemicals Co., Ltd. 15 μm thick.
IB-ONY: Gas barrier biaxially stretched nylon film manufactured by Dai Nippon Printing Co., Ltd. 15 μm thick.

[others]
-EMB-21: Anti-blocking agent manufactured by Sumitomo Chemical Co., Ltd.
-PEX ABT-16: Japan Polyethylene Corporation, anti-blocking agent.
-EMB-10: Sumitomo Chemical Co., Ltd., slip agent.

[Adjustment of masterbatch]
The MB (masterbatch) of the outer layer film and the inner layer film was prepared by adjusting as follows.
(Adjustment of MB1)
Ultozex 1520L, which is a low-eluting polyethylene LLDPE, and Mizuka Sieves EX-122, which is a hydrophobic zeolite, were melt-blended at the following ratios to obtain Masterbatch 1 (MB1).
Ultozex 1520L 90 parts by mass Mizuka Sieves EX-122 10 parts by mass (adjustment of MB2 to 13)
According to the formulations shown in Tables 3 and 4, the raw materials were melt-blended in the same manner as in MB1 to obtain master batches 2 to 13 (MB2 to 13).

[Preparation of outer layer film]
The outer layer films A to I shown in Table 4 were prepared.
(Preparation of outer layer film A)
Inflation film formation of Ultozex 1520L at 160 ° C. was performed to prepare an 80 μm sealant film, which was used as an outer layer film A. The layer structure and evaluation results are shown in Table 4.
(Preparation of outer layer film B)
First, Ultozex 1520L was laminated by inflation film formation at 160 ° C. to prepare a 40 μm sealant film, which was used as an outer layer film A. The layer structure and evaluation results are shown in Table 4.
Next, using Novatec LC520 as an adhesive layer by an extraction coating method at 320 ° C., Bonil RX, a biaxially stretched nylon film, and the sealant film obtained above were laminated to obtain an outer layer film B. The layer structure and evaluation results are shown in Table 4.

(Preparation of outer layer film C)
First, a mixture of Ultozex 1520L, UMERIT0520F / MB2 = mass ratio 50/50, and a mixture of Ultozex 1520L / EMB-21 = mass ratio 97/3 are laminated by an inflation membrane at 160 ° C. to form a sealant. A film was made.
Next, using Novatec LC520 as an adhesive layer by an extraction coating method at 320 ° C., the Bonil RX biaxially stretched nylon film and the Ultozex 1520L surface of the sealant film obtained above are laminated to form an outer layer film. I got A.
The layer structure and evaluation results are shown in Table 4.

(Preparation of outer layer films D, F, H)
With the configuration shown in Table 4, the outer layer films D, F, and H were obtained by operating in the same manner as the outer layer film C. The layer structure and evaluation results are shown in Table 4.
(Preparation of outer layer films E, G, I)
With the configuration shown in Table 4, the outer layer films E, G, and I were obtained by operating in the same manner as the outer layer film A. The layer structure and evaluation results are shown in Table 4.

<Example 1>
[Preparation of inner layer film]
First, the following mixture 1 was prepared for the odor adsorption layer and the mixture 2 was prepared for the non-odor adsorption layer.

Mixture 1:
UMERIT0520F 50 parts by mass MB2 50 parts by mass Mixture 2:
Ultozex 1520L 97 parts by mass EMB-21 3 parts by mass Then, Ultozex 1520L, the above mixture 1 and the above mixture 2 are laminated by inflation film formation at 160 ° C. to prepare an inner layer film A having a three-layer structure. did. Details are shown in Table 5.

[Manufacturing and evaluation of packaging]
Using the outer layer film A, the inner layer film A, and the content extraction port A obtained above, the package shown in FIG. 1 (the size of the double bag portion is 450 mm × 450 mm, and the diameter of the content extraction port A is 31 m).
m) was prepared, and the heat sealability, bag breaking characteristics, pinhole resistance (inner layer film), and TOC increase concentration of filled water were evaluated.
Table 5 shows the detailed configuration and evaluation results of the laminated body.

<Examples 2 to 19, Comparative Examples 1 to 5>
A mixture for an odor-adsorbing layer and / or a non-odor-adsorbing layer was obtained in the same manner as in Example 1 according to the formulations shown in Tables 5 to 8, and an inner film was prepared.
Then, according to the description of Tables 5 to 8, a package was prepared by combining the outer layer film and the content extraction port, and evaluated in the same manner. Tables 5 to 8 show the detailed configuration and evaluation results of the package.

<Evaluation>
[Film formation]
The appearance of the was observed and sensually evaluated. The evaluation criteria are as follows.
◯: Film formation is possible without wrinkles or bumps on the film.
X: Many wrinkles and bumps occur on the film, making it difficult to form a film.

[Bag resistance]
The operation of filling the inside of the packages prepared in Examples and Comparative Examples with 10 L of water and dropping the package after filling with water from a height of 1 m was repeated a total of 3 times, and the presence or absence of bag breakage was evaluated.
Pass / Fail Judgment ◎: No bag breakage after 3 drop evaluations. Passed ○: One bag broke after three drop evaluations. Passed ×: All bags were broken after 3 drop evaluations. failure

[Pinhole resistance of the inner film alone]
The produced inner layer film was cut into A4 size (30 cm x 21 cm), bent with a gelboflex tester (BE-1005 manufactured by Tester Sangyo Co., Ltd.), and then generated in the plane of 30 cm x 21 cm of each sample. The number of pinholes was counted. 160 or less were accepted.
Temperature: 23 ° C
Gerbo bending frequency: 5000 times

[Pinhole resistance of the package]
The prepared package was transported by an actual transportation route in a state of being packaged for transportation as a liquid content package for BIB, and the number of pinholes generated in the inner layer film of the bag portion was counted. 160 or less were accepted.

[Filled water TOC increase concentration]
Before producing the packaging in Examples and Comparative Examples, the inner film side of the packaging material constituting the packaging was subjected to UV irradiation sterilization treatment in advance.
The packages obtained in Examples and Comparative Examples were hot-packed with 1000 g of water at 65 ° C. (distilled water for high performance liquid chromatography, genuine chemistry) to prepare a packaged liquid filling, and the temperature was 35 ° C. for 2 weeks. After storage, the TOC concentration of the filled water was measured by a TOC-L total organic carbon meter manufactured by Shimadzu Corporation.

Next, the TOC concentration of the water before filling was measured in the same manner.
The TOC increase concentration in each package was calculated from the following formula.
TOC increase concentration = TOC concentration of filled water after storage-TOC concentration of water before filling TOC concentration of water before filling: 0.02 ppm
UV irradiation sterilization treatment conditions UV wavelength: 253.7 nm
Irradiation time: 10 seconds
Temperature: 25 ° C

<Summary of results>
The packages of all the examples showed good film forming property, bag breaking resistance, heat sealing property, and pinhole resistance, and the TOC increase concentration was also small.
Comparative Example 1 in which the outer layer film does not contain an odor adsorbent and the inner layer film contains neither low-eluting polyethylene nor an odor adsorbent, and the inner layer film does not contain low-eluting polyethylene and uses hydrophilic zeolite instead of hydrophobic zeolite. Comparative Example 2 including included tended to have a high TOC increase concentration. Further, in Comparative Examples 3, 4 and 5 in which the outer layer film or the inner layer film contains too much hydrophobic zeolite, the TOC concentration is greatly reduced, but the film forming property of the outer layer film or the inner layer film is inferior, and the heat sealability and the fracture resistance are reduced. The result was that the bag characteristics were inferior.

1. 1. Odor adsorption sealant film 2. Adhesive part between outer layer film and inner layer film 3. Outer layer film 4. Inner layer film 5. Sealant layer 6. Odor adsorption layer 6a. Odor adsorption layer 6b. Odor adsorption layer 7. Non-odor adsorption layer 8. Base material layer 9. Adhesive layer 11. Package, liquid content package for BIB
12. Double bag
13. Contents extraction port
14. Heat seal part of double bag part
15. Upper film
16. Lower film 20. Chemical adsorbent-supported inorganic porous material
A, B. Section line

Claims (16)

An odor-adsorbing sealant film consisting of at least an outer layer film and an inner layer film.
The outer layer film and the inner layer film are only partially adhered to each other.
Each of the outer layer film and the inner layer film contains a sealant layer containing low-eluting polyethylene.
The low-eluting polyethylene has a concentration of elution TOC contained in a film made only of the low-eluting polyethylene of 1.5 ppm or more and 250 ppm or less.
The sealant layer of the inner film includes an odor adsorbing layer and contains an odor adsorbing layer.
The odor adsorbing layer contains low-eluting polyethylene and an odor adsorbent.
The odor adsorbent contains hydrophobic zeolite and
The hydrophobic zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 30/1 to 8000/1.
An odor-adsorbing sealant film in which the content of the hydrophobic zeolite in the sealant layer is 0.1% by mass or more and 13% by mass or less. The odor-adsorbing sealant film according to claim 1, wherein the sealant layer of the outer layer film includes the odor-adsorbing layer. The odor adsorbent further comprises a chemisorbent-supported inorganic porous body.
The odor-adsorbing sealant film according to claim 1, wherein the content of the chemisorbent-supported inorganic porous body in the sealant layer is 0.1% by mass or more and 10% by mass or less. The odor-adsorbing sealant film according to any one of claims 1 to 3, wherein the density of the low-eluting polyethylene is 0.90 g / cm ³ or more and 0.94 g / cm ³ or less. The odor-adsorbing sealant film according to any one of claims 1 to 4, wherein the low-eluting polyethylene is LLDPE. The low-eluting polyethylene is C4-LLDPE, C6-LLDPE, C8-LLDP.
The odor-adsorbing sealant film according to any one of claims 1 to 5, which is one or more selected from the group E. In the low-eluting polyethylene, the number of pinholes generated after 5000 times of gelboflex at 23 ° C. in a 50 μm-thick film made only of the low-eluting polyethylene is 0, or 1 or more, 160. The odor-adsorbing sealant film according to any one of claims 1 to 6, wherein the number is less than one. The hydrophobic zeolite is previously melt - kneaded at a mass ratio of the thermoplastic resin to the hydrophobic zeolite / thermoplastic resin at a ratio of 0.5 / 99.5 to 40/60. The odor-adsorbing sealant film according to any one of the above items. The chemical adsorbent-supported inorganic porous body is previously melt-kneaded with a thermoplastic resin at a ratio of 0.5 / 99.5 to 40/60 of the chemical adsorbent-supported inorganic porous body / thermoplastic resin. Item 2. The odor-adsorbing sealant film according to any one of Items 2 to 8 . The odor-adsorbing sealant film according to claim 8 or 9 , wherein the melt flow rate of the thermoplastic resin is 0.2 to 10.0 g / 10 minutes. Claimed that the chemical adsorbent constituting the chemical adsorbent-supporting inorganic porous body has a functional group reactive with one or more selected from the group of aldehydes, ketones, and carboxylic acids. The odor-adsorbing sealant film according to any one of 2 to 10 . The odor-adsorbing sealant film according to any one of claims 2 to 11 , wherein the chemical adsorbent constituting the chemical adsorbent-supported inorganic porous body has an amino group. The odor adsorption layer includes a non-odor adsorption layer on one side or both sides.
The non-odor adsorbing layer is a layer containing low-eluting polyethylene and not containing the odor adsorbent.
The odor-adsorbing sealant film according to any one of claims 1 to 12 . The odor-adsorbing sealant film according to any one of claims 1 to 13 , wherein the outer layer film further includes a base material layer. An odor-adsorbing packaging material comprising the odor-adsorbing sealant film according to any one of claims 1 to 14 . A liquid content packaging bag for BIB made from the odor-adsorbing packaging material according to claim 15 .

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