JP2020157560A - Deodorant laminate - Google Patents

Abstract

To provide a package which is excellent in manufacturing suitability, exhibits suppression of occurrence of an odor component from contents and a deodorant effect by high odor adsorption effect and/or odor decomposition effect for a long period of time, and is excellent in resistance to change in odor of the contents for a long period of time.SOLUTION: A deodorant laminate has a structure such that at least a base material layer, a gas barrier layer and a sealant layer are layered in this order, in which the sealant layer is a layer formed by an extrusion coat method or a cast film-formation method, and has an odor adsorption layer. The odor adsorption layer contains a polyolefin-based resin and an odor absorbent, and the odor adsorbent is hydrophobic zeolite having a molar ratio of SiO2 to AL2O3 of 30/1 or more and 10,000/1 or less, and/or an inorganic chemical odor adsorbent.SELECTED DRAWING: Figure 1

Description

In the present invention, the elution organic substance originally contained in the packaging material and the odorous component generated from the packaging material during the sterilization / sterilization process are transferred to the content in the packaging and discolored into the content. A deodorant laminate having excellent long-term odor resistance changeability, which prevents giving an odor and has an odor improving effect on odor components generated from the contents themselves, and the deodorant laminate. Concerning packaging materials and deodorant packaging manufactured using.

As a packaging material, a packaging material containing an odor adsorbent that adsorbs odor has been proposed (Patent Document 1). In such packaging materials, odor adsorbents such as synthetic zeolite and activated carbon are 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 supported 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.

Japanese Patent No. 2538487 JP-A-2014-233408

The present invention solves the above-mentioned problems, is excellent in manufacturing suitability, and is based on the odorous organic substance originally contained in the laminate and the contents themselves when the packaging bag filler is produced using the laminate of the present invention. A laminate that exerts a deodorizing effect due to a high adsorption action on the generated odor component for a long period of time and has excellent long-term odor resistance changeability to the contents, and a packaging material using the laminate. , The purpose is to provide packaging.

As a result of various studies, the present inventors have obtained at least a base material layer, a gas barrier layer, and a sealant layer containing a specific deodorant and formed by an extraction coating method or a cast film forming method. It has been found that the laminate having the above-mentioned purpose is achieved.

That is, the present invention is characterized by the following points.
1. 1. It is a deodorant laminate having a structure in which at least a base material layer, a gas barrier layer, and a sealant layer are laminated in this order.
The sealant layer is a layer formed by an extraction coating method or a cast film forming method, and has an odor adsorption layer.
The odor adsorbing layer contains a polyolefin resin and an odor adsorbent.
The odor adsorbent is a hydrophobic zeolite having a SiO ₂ / AL ₂ O ₃ molar ratio of 30/1 or more and 10000/1 or less, and / or an inorganic chemical odor adsorbent. ..
2. 2. The polyolefin resin is characterized by being LDPE and / or LLDPE having a density of 0.90 g / cm ³ or more and 0.94 g / cm ³ or less.
The deodorant laminate according to 1 above.
3. 3. The deodorant laminate according to 1 or 2 above, wherein the content of the odor adsorbent in the odor adsorbing layer is 0.5% by mass or more and 15% by mass.
4. The sealant layer is a layer laminated at 250 ° C. or higher and 350 ° C. or lower by an extraction coating method or a cast film forming method.
The deodorant laminate according to any one of 1 to 3 above.
5. The sealant layer further comprises a heat seal layer.
The heat-sealing layer is a layer containing a polyolefin-based resin and not containing the odor adsorbent.
The deodorant laminate according to any one of 1 to 4 above.
6. A deodorant packaging material made from the deodorant laminate according to any one of 1 to 5 above.
7. A deodorant packaging body made from the deodorant packaging material according to 6 above.

According to the present invention, the odorous organic matter originally contained in the laminate, which is excellent in production suitability, and the odor component generated from the content itself when the packaging bag filling material is produced using the laminate of the present invention. On the other hand, we provide a laminate that exhibits a deodorizing effect due to its high adsorption action for a long period of time and has excellent long-term odor resistance changeability to the contents, and packaging materials and packages using the laminate. can do.

It is a schematic external view which shows an example of the deodorant laminated body of this invention. It is the schematic sectional drawing which shows an example about the layer structure of the deodorant laminate of this invention. It is the schematic sectional drawing which shows an example of the other aspect about the layer structure of the deodorant laminate of this invention.

In each figure, the size and ratio of the members may be changed or exaggerated for the sake of clarity. In addition, for the sake of readability, unnecessary parts for explanation and repeated codes may be omitted.

The deodorant laminate 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.

<Layer structure of deodorant laminate>
The deodorant laminate of the present invention is a deodorant laminate having at least a structure in which a base material layer, a gas barrier layer, and a sealant layer are laminated in this order.
Then, an adhesive layer formed by an extraction coating method or a cast film forming method may be provided between the base material layer and the gas barrier layer, if necessary.

[Base material layer]
As the base material layer, a known and publicly available resin film, paper material, or the like can be used, and the base material layer may be composed of one layer or may have a multi-layer structure including two or more layers having the same or different composition.
Further, in order to improve the adhesiveness, an adhesive layer is provided between each layer constituting the base material layer 1 or another layer, or a desired surface is previously provided on the surface of each layer, if necessary. A treatment layer can be provided.
For example, pretreatment such as corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. is arbitrarily performed to perform corona treatment layer, ozone treatment, etc. A layer, a plasma-treated layer, an oxidation-treated layer and the like can be formed and provided.
Alternatively, various coating agent layers such as a primer coating agent layer, an undercoating agent layer, an anchor coating agent layer, an adhesive layer, and a vapor deposition anchor coating agent layer can be arbitrarily formed on the surface to form a surface treatment layer. ..

The above-mentioned various coating agent layers include, for example, polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, polyolefin such as polyethylene or polypropylene. A resin composition containing a based resin or a copolymer or modified resin thereof, a cellulose based resin, or the like as the main component of the vehicle can be used.

The thickness of the base material layer depends on the material, but in the case of a resin film, it is preferably 5 to 30 μm, more preferably 10 to 30 μm.
As the resin film used for the base material layer, a film of a thermoplastic resin can be used, which has excellent chemical or physical strength, withstands the conditions for forming a vapor-deposited film of metal oxide, and metal oxidation thereof. It is preferably a thermoplastic resin that can be held well without impairing the characteristics of the vapor-deposited film of the material.

Examples of such resins include polyolefin resins such as polyethylene resins or polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), and acrylonitrile-butadiene-styrene copolymers. (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyester resin such as polyethylene naphthalate, polyamide resin such as various nylons, polyurethane resin, acetal resin, cellulose resin, etc. Various resins can be mentioned.
In the present invention, as the resin, polyester-based resin, polyamide-based resin, and polyolefin-based resin are preferable, and polyethylene terephthalate (PET), nylon, and polypropylene (PP) are particularly preferable.

In the present invention, the thermoplastic resin used for the base material layer can be formed into a film by various known and publicly used film forming methods.
For example, a method of forming a film using one kind of resin and a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, and an inflation method, using two or more kinds of resins. Examples thereof include a method of forming a multi-layer co-extrusion film, a method of mixing two or more kinds of resins before forming a film, and forming a film by the above-mentioned film forming method. Further, a film stretched in the uniaxial or biaxial direction can be obtained by using a tenter method, a tubular method, or the like.

Alternatively, one type or two or more types of resin may be applied, dried and coated on another resin film, or a resin melted by a T-die method or the like may be laminated.
In the present invention, as the resin film, a biaxially stretched PET film, a biaxially stretched nylon film, a biaxially stretched PP film or a sheet is preferably used.

In addition, when the resin film is formed into a film, for example, the film's workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant property, slipperiness, releasability, flame retardancy, and resistance Various plastic compounding agents and additives can be added for the purpose of improving and modifying moldiness, electrical properties, strength, etc., and the amount of the addition can be from a very small amount to several tens of percent. It can be arbitrarily added depending on the purpose.
In the above, as general additives, for example, lubricants, cross-linking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, modifying resins and the like are used. be able to.

[Gas barrier layer]
The gas barrier layer prevents water vapor, oxygen, etc. from permeating from the outside to the inside of the deodorant package and further to the contents in the deodorant package produced by using the deodorant laminate of the present invention. It is a layer that suppresses the formation of odorous substances due to hydrolysis and oxidation of the contents, and can suppress deterioration due to moisture.
As the gas barrier layer, one or more selected from the group consisting of a gas barrier resin film, a metal foil, a resin film with a metal vapor deposition layer, a resin film with a metal oxide vapor deposition layer, and a gas barrier resin coating film may be used. it can.

As the gas barrier resin film, a known and publicly available resin film having a gas barrier property can be used. For example, as the gas barrier film, specifically, a resin film made of a resin such as PET, polybutylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyvinyl alcohol, or ethylene / vinyl alcohol copolymer, the above-mentioned group. A vapor-deposited film in which a vapor-deposited film such as a silica vapor-deposited film or an alumina vapor-deposited film is provided on at least one surface of the material film, or a metal foil such as an aluminum foil can be used, but the present invention is not limited thereto.
The metal foil is preferably an aluminum foil, the resin film with a metal vapor deposition layer is preferably a resin film with an aluminum vapor deposition film, the resin film with a metal oxide vapor deposition layer is preferably a resin film with an aluminum oxide vapor deposition film, and a gas barrier resin coating is used. As the film, a coating film containing a solgel method hydrolyzed polycondensate formed from a metal alkoxide and a water-soluble polymer is preferable.

As a commercially available resin film with an aluminum oxide vapor deposition film, for example, an alumina vapor deposition IB-PET-PIR (thickness) manufactured by Dainippon Printing Co., Ltd., which is a PET film in which alumina is vapor-deposited on one side by the PVD method. 12 μm), silica-deposited IB-ON-UB (thickness 15 μm) can be mentioned.

The metal foil for the gas barrier layer, the resin film with the metal vapor deposition layer, or the resin film with the metal oxide vapor deposition layer can be adhered to other layers by using a dry laminate adhesive.
Alternatively, the resin film for the base material layer can be used for the resin film of the resin film with the metal vapor deposition layer or the resin film with the metal oxide vapor deposition layer, and the lamination to the base material layer can be omitted.

[Sealant layer]
The sealant layer in the present invention is a layer formed by an extraction coating method or a cast film forming method, and is a layer having an odor adsorption layer. The sealant layer may further have a heat seal layer, if necessary.
The outer surface layer of the sealant layer may be a deodorant layer or a heat seal layer. Further, the layer on the outermost base layer side of the sealant layer may be a heat seal layer.
Since the heat-sealing layer has excellent heat-sealing properties, when the outer surface layer of the sealant layer is a heat-sealing layer, the heat-sealing properties of the deodorant laminate can be improved.
Further, by forming the layer on the outermost base layer side of the sealant layer as a heat seal layer, the adhesive strength at the interface of the sealant layer inside the deodorant laminate can be increased.
The sealant layer can also contain lubricants, antioxidants, antiblocks and other additives.

(Method of forming and laminating the sealant layer)
In the present invention, the sealant layer or each layer constituting the sealant layer is preferably formed by an extraction coating method at 250 ° C. or higher and 350 ° C. or lower, or a cast film forming method.
The sealant layer, deodorant layer, or heat seal layer is laminated on another layer by extrusion or co-extrusion by the extrusion coating method, but at that time, it is laminated via an adhesive layer if necessary. You may.

When laminating by the extrusion coating method, first, the resin composition forming the sealant layer, the deodorant layer, the hydrolysis suppression layer, the heat seal layer, etc. is heated and melted, and then the width direction required by the T-die is used. A sealant layer, a deodorant layer, and a hydrolysis suppressing layer are formed by expanding and stretching the resin to form a curtain (co), allowing the molten resin to flow down onto the surface to be laminated, and sandwiching the molten resin between a rubber roll and a cooled metal roll. , The heat seal layer and the like can be formed, laminated and bonded to the surface to be laminated, laminated and bonded between the layers, and the like at the same time.
The melt flow rate (MFR) of the resin component contained in the sealant layer when laminated by the extrusion coating method is preferably 0.2 to 50 g / 10 minutes, 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 / 10 minutes or larger than 50 g / 10 minutes, the processing suitability tends to be inferior.

(Heat seal layer)
The heat-sealing layer is a layer containing a polyolefin-based resin and not containing an odor adsorbent, and is a layer having excellent heat-sealing properties.

(Odor adsorption layer)
The odor adsorbing layer is a layer containing a polyolefin resin and an odor adsorbent, is a layer that exerts an odor adsorbing action, may have a one-layer structure, or may have two or more layers having the same or different composition. Good.
The content of the odor adsorbent in the odor adsorbing layer is preferably 0.5% by mass or more and 15% by mass or less, and more preferably 0.8% by mass or more and 15% by mass or less. If it is less than the above range, the deodorizing effect is difficult to be exhibited, and if it is more than the above range, the film forming property tends to deteriorate.

(Odor adsorbent)
The odor adsorbent is a compound having an action of adsorbing an odorous substance. The origin of the odorous substance may be any of the contents, the laminate, and the outside.
Since the sealant layer containing the odor adsorbent is laminated at 250 ° C. or higher and 350 ° C. or lower by the extraction coating method or the cast film forming method, the odor adsorbent can withstand this high temperature. Those containing an organic compound are preferable because their odor adsorption performance is not easily deteriorated, and those containing only an inorganic compound are preferable because of their low heat resistance.
Specifically, hydrophobic zeolites having a SiO ₂ / AL ₂ O ₃ molar ratio of 30/1 or more and 10000/1 or less, and / or an inorganic chemical odor adsorbent are preferable.

The shape of the odor adsorbent may be any outer shape such as spherical, rod-shaped, or elliptical, and may be any shape such as powder, lump, or granular, but when dispersed in the resin, From the viewpoint of uniform dispersibility, kneading characteristics, film forming property, etc., the powder form is preferable.
In the present invention, the average particle size of the odor adsorbent 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 odor adsorbent tends to aggregate and the dispersibility tends to decrease. Further, when the average particle size is larger than 10 μm, the film-forming property of the layer containing the odor adsorbent tends to be inferior, so that it tends to be difficult to add a large amount of the odor adsorbent and the surface area is further reduced. In addition, there is a possibility that a sufficient deodorizing effect cannot be obtained.

(Hydrophobic zeolite)
The SiO ₂ / Al ₂ O ₃ molar ratio of the hydrophobic zeolite is preferably 30/1 to 10000/1, more preferably 35/1 to 9000/1, and even more preferably 40/1 to 8500/1.
Generally, the higher the SiO ₂ / Al ₂ O ₃ molar ratio, the higher the hydrophobicity of zeolite. As the hydrophobicity increases, it becomes difficult to adsorb highly polar water molecules, and conversely, the affinity with low-polarity odorous substances, hydrophobic gases, and lipophilic gases (including solvent-based gases) is high. Therefore, it becomes 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.
In the present invention, hydrophobic zeolite having a molar ratio in the above range is preferably used from the viewpoint of the balance between the adsorption performance of odorous substances and the availability.
In addition, hydrophobic zeolite has high heat resistance and can maintain the adsorption effect of odorous substances even when exposed to a high temperature of 230 ° C. or higher.

(Inorganic chemical odor adsorbent)
The inorganic chemical odor adsorbent is an adsorbent composed of an inorganic compound other than zeolite.
Specifically, oxides and / or salts of one or more elements selected from the group consisting of copper, zinc, silver, platinum, gold, iron and cobalt are preferred. Examples of the metal oxide include CuO, Cu ₂ O, ZnO, Ag ₂ O, PtO ₂ , Au ₂ O ₃ , FeO, Fe ₃ O ₄ , Fe ₂ O ₃ , CoO, Co ₂ O ₃ , and Co ₃ O. ₄ mag, and aluminosilicate containing various metals oxide can be mentioned. Among these, copper oxide / zinc oxide composite aluminosilicate is preferably used.

(Polyolefin resin)
The polyolefin resin contained in the sealant layer is preferably one having excellent dispersibility and heat sealability of the odor adsorbent.
Specific examples of the polyolefin resin include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene (PP), linear (linear) low density polyethylene (LLDPE), and ethylene. Low of -vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methylmethacrylic acid copolymer, ethylene-propylene copolymer, etc. Examples include those eluted and mixtures of their resins.
Among the above, polypropylene-based resin or polyethylene-based resin is preferable, and among polyethylene-based resins, LDPE and / or LLDPE are more preferable, and the density is 0.90 g / cm ³ or more and 0.94 g / cm ³ or less. , LDPE and / or LLDPE are more preferred.

<Deodorant packaging material>
The deodorant packaging material of the present invention is a packaging material produced from the deodorant laminate of the present invention.
The deodorant packaging material can also include various functional layers in addition to the deodorant laminate, if necessary.

<Deodorant packaging>
The deodorant packaging body of the present invention is a packaging body made from the deodorant packaging material of the present invention.

<Raw materials>
Details of the raw materials used in the examples are as follows.
[polyethylene]
-LDPE1: LDPE manufactured by Japan Polyethylene Corporation, Novatec LC600A. Density 0.918 g / cm ³ .
-LDPE2: LDPE manufactured by Japan Polyethylene Corporation, Novatec LC520. Density 0.923 g / cm ³

[Resin film]
-PET film 1: Espet T4102, film thickness: 12 μm, Toray Film Processing Co., Ltd.
[Hydrophobic zeolite]
-Mizuka Sieves EX-122: Made by Mizusawa Industrial Chemicals, Inc. SiO ₂ / AL ₂ O ₃ molar ratio = 32/1, average particle size = 2.5 to 5.5 μm.
-Silton MT400: Made by Mizusawa Industrial Chemicals, Inc. SiO ₂ / AL ₂ O ₃ molar ratio = 400/1, average particle size = 5-7 μm.
-Silton MT2000: Made by Mizusawa Industrial Chemicals, Inc. SiO ₂ / AL ₂ O ₃ molar ratio = 2000/1, average particle size = 2-4 μm.
-Silton MT-8000: Made by Mizusawa Industrial Chemicals, Inc. SiO ₂ / AL ₂ O ₃ molar ratio = 8000/1, average particle size = 0.8 μm.
[Inorganic chemical odor adsorbent]
・ Dashlight CZU = Made by Shinanen Zeomic Co., Ltd. Copper oxide / zinc oxide composite aluminosilicate, average particle size = 3-5 μm.

[Other]
-AC agent 1: Mitsui Chemicals Polyurethane Co., Ltd., anchor coating agent A3210 / A3075, diluting solvent is ethyl acetate.
-Aluminum foil 1: 7 μm thick-Mizuka Sieves 5AP: Hydrophilic zeolite manufactured by Mizusawa Industrial Chemicals, Inc.
-Kesmon NS-241: Toagosei Co., Ltd., organic chemical odor adsorbent-supported inorganic porous body, containing amino groups. Average particle size 3.5 μm.

<Preparation of masterbatch>
[Preparation of Masterbatch 1]
LDPE1 and Mizuka Sieves EX-122, which is a hydrophobic zeolite, were melt-blended at the following ratios to obtain Masterbatch 1 (MB1).
LDPE1 90 parts by mass Mizuka Sieves EX-122 10 parts by mass

[Preparation of master batches 2-11]
According to the formulations shown in Tables 1 and 2, masterbatch 2-11 (MB2-11) was obtained by melt blending in the same manner as in masterbatch 1.

[Example 1]
(Preparation of laminate precursor)
The AC agent 1 was applied to the laminated surface of the PET film 1 and dried so that the applied amount after drying was 0.3 g / m ² to form an AC layer.
LDPE1 is extruded on the side surface of the AC layer of the PET film 1 by the EC (extrusion coating, extrusion temperature: 280 ° C.) method, aluminum foil 1 is laminated and pressed with a roll to be laminated to obtain a laminate precursor. It was.

(Preparation of resin composition for sealant layer)
The MB1 and LDPE2 obtained above were dry-blended at the following ratios to obtain an odor-adsorbing layer resin composition for the sealant layer.
Masterbatch 1 30 parts by mass LDPE2 70 parts by mass

(Preparation of deodorant laminate)
The AC agent 1 was applied and dried on the aluminum foil surface of the laminate precursor obtained above so that the applied amount after drying was 0.3 g / m ² , and an AC layer was formed. The odor adsorption layer resin composition was extruded by EC (extrusion coating, extrusion temperature: 280 ° C.) and pressed with a roll to form an odor adsorption layer to obtain a deodorant laminate having the following layer structure.
Base material layer (12 μm) / AC layer (0.3 g / m ² ) / Adhesive layer (15 μm) / Aluminum foil (7 μm) / AC layer (0.3 g / m ² ) / Sealant layer [Odor adsorption layer (30 μm) )]]
Next, various evaluations were performed on the obtained deodorant laminate.

[Examples 2 to 11 and 14, Comparative Examples 3 to 5]
The same operation as in Example 1 was carried out to obtain a deodorant laminate precursor.
Then, an odor-adsorbing layer resin composition for the sealant layer was prepared by operating in the same manner as in Example 1 according to the blending ratio of the masterbatch species and LDPE2 shown in Tables 3 to 6.
Next, using the obtained odor adsorption layer resin composition and the deodorant laminate precursor, the same operation as in Example 1 was carried out to obtain a deodorant laminate or laminate, which was evaluated in the same manner.

[Example 12]
The same operation as in Example 1 except that the sealant layer was formed by coextrusion of the odor adsorption layer resin composition and LDPE2 for the non-odor adsorption layer by EC (extrusion coating, extrusion temperature: 280 ° C.). Then, a deodorant laminate having the following layer structure was obtained.
Base material layer (12 μm) / AC layer (0.3 g / m ² ) / Adhesive layer (15 μm) / Aluminum foil (7 μm) / AC layer (0.3 g / m ² ) / Sealant layer [Odor adsorption layer (30 μm) ) / Non-odor adsorption layer (10 μm)]
Next, the obtained deodorant laminate was evaluated in the same manner as in Example 1.

[Example 13]
The same procedure as in Example 13 was carried out to obtain a deodorant laminate precursor, an odor adsorption layer resin composition was prepared according to the description in Table 5, and a sealant layer was formed together with LDPE2 for a non-odor adsorption layer. A deodorant laminate was prepared. However, the deodorant laminate having the following layer structure was obtained by co-extruding so that the odor adsorption layer became the surface layer of the deodorant laminate.
Base material layer (12 μm) / AC layer (0.3 g / m ² ) / Adhesive layer (15 μm) / Aluminum foil (7 μm) / AC layer (0.3 g / m ² ) / Sealant layer [Non-odor adsorption layer (non-odor adsorption layer (3 g / m ² )) 10 μm) / Odor adsorption layer (30 μm)]

[Comparative Examples 1 and 2]
The laminate was formed by extruding the sealant layer with only LDPE2 for the non-odor adsorbing layer by EC (extrusion coating, extrusion temperature: 280 ° C.) in the same manner as in Example 1 to form the laminate. Obtained and evaluated in the same manner.

[Result Summary]
The deodorant laminate of the embodiment of the present invention and the packaging bag prepared from the same showed good film-forming property, bag-forming property, heat-sealing property, and deodorizing effect.
On the other hand, in the comparative example, the laminate not corresponding to the present invention and the packaging bag produced from the laminate showed insufficient film-forming property, bag-forming property, heat-sealing property, or insufficient deodorizing effect.

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

[Bag making]
◯: The packaging bag could be easily produced.
X: The packaging bag could not be easily manufactured, and many unfused parts and wrinkles were generated.

[Heat sealability]
The laminate is cut into 10 cm x 10 cm, the sealant layer surfaces are overlapped, and a 1 cm x 10 cm area is heat-sealed using a heat seal tester (manufactured by Tester Sangyo Co., Ltd .: TP-701-A), and the ends are heat-sealed. A sample was prepared in which it was not adhered without being bonded and was divided into two parts.
This sample was cut into strips with a width of 15 mm, each bifurcated end was mounted on a tensile tester, and the tensile strength (N / 15 mm) was measured to determine pass / fail.
(Heat seal condition)
Temperature: 160 ° C
Pressure: 1 kgf / cm ²
Time: 1 second (tensile strength test conditions)
Test speed: 300 mm / min Load range: 50 N
(Pass / fail criteria)
◯: 20N / 15mm or more, passed.
X: Less than 20N / 15mm and failed.

[Odor sensory evaluation]
The laminate was cut into 20 x 20 cm, 1000 ml of each odorous gas was placed in a gas sampling bag (IB-PET-PIR 12 μm / adhesive layer / ONy 15 μm / adhesive layer / LLDPE film 60 μm), and the odor change after being left for 2 days was sensory evaluated. Measured by. The odor component was adjusted so that acetaldehyde was 200 ppm and acetic acid was 30 ppm.
The evaluation criteria for odor sensory evaluation are as follows: ・ 1 = odor unchanged from the initial stage ・ 2 = odor was slightly alleviated from the initial stage ・ 3 = odor was significantly alleviated compared to the initial stage ・ 4 = totally Does not smell

[Filled water TOC increase concentration]
A pouch bag (15 cm × 44 cm) package was prepared using a resin film or the laminate prepared in Examples and Comparative Examples. The inner surface of the pouch bag was previously subjected to UV irradiation sterilization treatment.
Then, the obtained package was filled with 1000 g of water at 65 ° C. (distilled water for high performance liquid chromatography, Junsei Chemical Co., Ltd.) to prepare a packaged liquid filler, and after storage at 35 ° C. for 2 weeks, Co., Ltd. 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

1 Deodorant laminate, Deodorant packaging material 2 Base material layer 3 Gas barrier layer 4 Sealant layer 4a Odor adsorption layer 4b Heat seal layer

Claims (7)

It is a deodorant laminate having a structure in which at least a base material layer, a gas barrier layer, and a sealant layer are laminated in this order.
The sealant layer is a layer formed by an extraction coating method or a cast film forming method, and has an odor adsorption layer.
The odor adsorbing layer contains a polyolefin resin and an odor adsorbent.
The odor adsorbent is a hydrophobic zeolite having a SiO ₂ / AL ₂ O ₃ molar ratio of 30/1 or more and 10000/1 or less, and / or an inorganic chemical odor adsorbent. .. The polyolefin resin is characterized by being LDPE and / or LLDPE having a density of 0.90 g / cm ³ or more and 0.94 g / cm ³ or less.
The deodorant laminate according to claim 1. The deodorant laminate according to claim 1 or 2, wherein the content of the odor adsorbent in the odor adsorbing layer is 0.5% by mass or more and 15% by mass. The sealant layer is a layer laminated at 250 ° C. or higher and 350 ° C. or lower by an extraction coating method or a cast film forming method.
The deodorant laminate according to any one of claims 1 to 3. The sealant layer further comprises a heat seal layer.
The heat-sealing layer is a layer containing a polyolefin-based resin and not containing the odor adsorbent.
The deodorant laminate according to any one of claims 1 to 4. A deodorant packaging material made from the deodorant laminate according to any one of claims 1 to 5. A deodorant packaging body made from the deodorant packaging material according to claim 6.

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