JP2020158142A - Deodorant laminate for liquid paper container - Google Patents

Abstract

To provide: a deodorant laminate for a liquid paper container which has excellent manufacturing suitability, which exhibits a deodorant effect for a long period of time by a high adsorption action with respect to an odorous organic material which the laminate contains and an odor component generating from the content itself, and which has excellent anti-odor variability to the content for a long period of time; a packaging material; and a package.SOLUTION: A deodorant laminate 1 for a liquid paper container includes a structure in which a base material layer 2, a gas barrier layer 3, an odor adsorption adhesive agent layer 4 and a sealant layer 5 are laminated in this order. The base material layer includes a paper material layer 2b, and a base material protective layer 2a for covering one side surface of the paper material layer. The odor adsorption adhesive agent layer is the layer formed by the extrusion-coating method and it includes polyolefin resin and an odor adsorbent. The odor adsorbent is an inorganic chemical odor adsorbent and/or hydrophobic zeolite. The base material protective layer is the layer formed by the extrusion-coating method and it includes polyolefin resin, and the sealant layer includes low elution property polyethylene.SELECTED DRAWING: Figure 1

Description

In the present invention, the eleasing 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 inside the packaging and discolored into the content. A deodorant laminate for liquid paper containers, which prevents giving off odors, has an odor improving effect on odor components generated from the contents themselves, and has excellent long-term odor resistance changeability, and The present invention relates to a packaging material and a deodorant package produced by using the deodorant laminate.

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 deodorant laminate for liquid paper containers, which exerts a deodorizing effect due to a high adsorption action on the generated odorous components for a long period of time and has excellent long-term odor resistance changeability to the contents, and An object of the present invention is to provide a packaging material and a packaging body for a liquid paper container using the deodorant laminate.

As a result of various studies, the present inventors have constructed a structure in which at least a specific base material layer, a gas barrier layer, an odor adsorption adhesive layer, and a specific low-eluting sealant layer are laminated in this order. It has been found that the odor adsorbing adhesive layer is a layer formed by the elution coating method, and a laminate containing a polyolefin resin and a specific odor adsorbent achieves the above object. It was.

That is, the present invention is characterized by the following points.
1. 1. At least, it is a deodorant laminate having a structure in which a base material layer, a gas barrier layer, an odor adsorbing adhesive layer, and a sealant layer are laminated in this order.
The base material layer has a paper material and a base material protective layer that covers one side surface of the paper material.
The odor-adsorbing adhesive layer is a layer formed by the extraction coating method, and contains a polyolefin resin and an odor-adsorbing agent.
The odor adsorbent is an inorganic chemical odor adsorbent and / or a hydrophobic zeolite having a SiO ₂ / AL ₂ O ₃ molar ratio of 30/1 or more and 10000/1 or less.
The base material protective layer is a layer formed by an extraction coating method and contains a polyolefin-based resin.
The sealant layer contains low elution polyethylene and contains
A deodorant laminate for a liquid paper container, characterized in that the content of the elution TOC of the low-eluting polyethylene is 1.5 ppm or more and 250 ppm or less.
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 content of the odor adsorbent in the odor adsorbing adhesive layer is 0.5% by mass or more and 15% by mass.
The deodorant laminate according to 1 or 2 above.
4. The odor-adsorbing adhesive layer is a layer laminated at 250 ° C. or higher and 350 ° C. or lower by an extraction coating method.
The deodorant laminate according to any one of 1 to 3 above.
5. The density of the low-eluting polyethylene is 0.90 g / cm ³ or more and 0.94 g / cm ³ or less.
The deodorant laminate according to any one of 1 to 4 above.
6. A deodorant packaging material for a liquid paper container, which is produced from the deodorant laminate according to any one of 1 to 5 above.
7. A deodorant liquid paper container 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.

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 for a liquid paper container having at least a base material layer, a gas barrier layer, an odor adsorption adhesive layer, and a sealant layer laminated in this order. ..

[Base material layer]
In the present invention, the deodorant laminate is for a liquid paper container, the base material layer contains a paper material, and a resin film may be further contained.
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.

As the paper material, those having shapeability, bending resistance, rigidity, waist, strength, etc. can be used. For example, strong size bleached or unbleached paper material, pure white roll paper, kraft paper, etc. can be used. Various types of paper materials such as paper, paperboard, processed paper, milk base paper, and others can be used. Further, a plurality of layers of these papers may be stacked.
Further, in the present invention, the basis weight of the paper material is preferably 10~600g / m ^2, more preferably 80~600g / m ^2, when the stiffness is required, 100 to 500 g / m ² is Preferably, 250-450 g / m ² is more preferred.

It is also possible to provide a base material protective layer made of resin on the surface of the paper material, and the base material protective layer can physically protect the base material layer made of paper material, and is a heat-sealable resin. When is used, heat sealability can be imparted to the surface of the base material layer made of paper material.
As the heat-sealing resin for the base material protective layer, a polyolefin-based resin is preferable, and specific examples thereof include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), and linear (wire). State) Low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methylmethacrylate copolymer , Low-elution products such as ethylene-propylene copolymer and mixtures of their resins.
Among the above, polyethylene-based resins are preferable, and among polyethylene-based resins, LDPE and / or LLDPE and ethylene-methylmethacrylate copolymers are more preferable.

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 the other layer, or the resin melted by the 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.

Although it depends on the material, the thickness of the resin film is preferably 5 to 30 μm, more preferably 10 to 30 μm.

[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, ethylene / vinyl alcohol copolymer, and the above-mentioned base film. 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 of the surfaces of the above, and 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.

[Odor adsorption adhesive layer]
The odor adsorbing adhesive layer is a layer formed by the extraction coating method, and is a layer containing a polyolefin resin and an odor adsorbent.
The odor-adsorbing adhesive layer is an adhesive layer that exerts an odor-adsorbing action, and may have a one-layer structure, or may have two or more layers having the same or different compositions.
The content of the odor adsorbent in the odor adsorbing adhesive 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.

(Laying method of odor adsorption adhesive layer)
In the present invention, the method of laminating the odor-adsorbing adhesive layer is preferably a method of laminating on another layer by an extraction coating method of 250 ° C. or higher and 350 ° C. or lower. High adhesiveness can be obtained by forming by the above-mentioned extraction coating method.

In the case of laminating by the extrusion coating method, first, the resin composition forming the odor-adsorbing adhesive layer is heated and melted, and then expanded and stretched in the required width direction with a T-die to form a curtain (co). By extruding, flowing the molten resin onto the surface to be laminated, and sandwiching it between a rubber roll and a cooled metal roll, the formation of an odor-adsorbing adhesive layer and the lamination and adhesion to the surface to be laminated are performed at the same time. Can be done.
The melt flow rate (MFR) of the resin component contained in the odor-adsorbing adhesive 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. preferable. 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.

(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 odor adsorbing adhesive layer containing the odor adsorbent is laminated at 250 ° C. or higher and 350 ° C. or lower by the extraction coating method, the odor adsorbent can withstand this high temperature and has odor adsorbing performance. Those containing an organic compound are preferable because of their low heat resistance, and those containing only an inorganic compound are preferable.
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-based resin contained in the odor-adsorbing adhesive layer is preferably one having excellent dispersibility and adhesiveness of the odor-adsorbing agent.
Specific examples of the polyolefin resin include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), and ethylene-vinyl acetate common weight. Low-elution products such as coalesced, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methylmethacrylic acid copolymer, ethylene-propylene copolymer, etc. And a mixture of their resins.
Among the above, polyethylene-based resins are preferable, and among polyethylene-based resins, LDPE and / or LLDPE are more preferable, and LDPE and / or LLDPE having a density of 0.90 g / cm ³ or more and 0.94 g / cm ³ or less are preferable. LLDPE is more preferred.

[Sealant layer]
The sealant layer in the present invention is a layer having a heat-sealing property and contains a heat-sealing resin. The sealant layer is preferably a layer formed by the extraction coating method.
In addition, the sealant layer can further contain a lubricant, an antioxidant, an antiblocking agent, and other additives, if necessary.

As the heat-sealing resin, a polyolefin-based resin is preferable.
Specific examples of the polyolefin resin include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), and ethylene-vinyl acetate common weight. Low-elution products such as coalesced, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methylmethacrylic acid copolymer, ethylene-propylene copolymer, etc. And a mixture of their resins.

Among the above, polyethylene-based resins are preferable, and among polyethylene-based resins, LDPE and / or LLDPE are more preferable, and LDPE and / or LLDPE having a density of 0.90 g / cm ³ or more and 0.94 g / cm ³ or less are preferable. LLDPE is more preferred.
Further, in order to suppress the change in the odor of the contents, the content of the elution TOC of the deodorant laminate is preferably 1.5 ppm or more and 250 ppm or less.
For that purpose, the polyolefin-based resin contained in the sealant layer in contact with the contents preferably has a low content of elution TOC.
Specifically, the sealant layer preferably contains low-eluting polyethylene as the polyolefin resin. The density of the low-eluting polyethylene is preferably 0.90 g / cm ³ or more and 0.94 g / cm ³ or less.

(Method of forming and laminating the sealant layer)
In the present invention, the sealant layer or the film forming and laminating method of each layer constituting the sealant layer is not particularly limited, and a known or conventional film forming method or laminating method can be applied.
The sealant layer may be laminated on another layer by an extrusion coating method by extrusion or co-extrusion, or may be laminated via an adhesive layer after film formation by an inflation method or a casting method. Even in the case of the extrusion coating method, the layers may be laminated via an adhesive layer if necessary.
Alternatively, a pre-formed sealant layer film may be laminated and bonded via an adhesive layer laminated by an extrusion coating method, a dry laminating method, a non-solvent laminating method, or the like.

<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.

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

<Raw materials>
Details of the raw materials used in the examples are as follows.
[Low-elution polyethylene and general-purpose polyethylene]

[Paperboard]
-Paperboard 1: Paper base material with a basis weight of 380 g / m ² .

[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.
-EMAA Adhesive 1: Mitsui-Dupont Polychemical Co., Ltd. EC Adhesive, N0908C.
-Aluminum-deposited film 1: Aluminum-deposited PET film, IB-PET-PIR manufactured by Dai Nippon Printing Co., Ltd. 12 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]
Novatec LC600A, which is an LDPE, and Mizuka Sieves EX-122, which is a hydrophobic zeolite, were melt-blended at the following ratios to obtain Masterbatch 1 (MB1).
Novatec LC600A 90 parts by mass Mizuka Sieves EX-122 10 parts by mass

[Preparation of master batches 2-11]
According to the formulation shown in Table 2, the master batches 2 to 10 (MB2 to 10) were obtained by melt blending in the same manner as in the master batch 1.

[Example 1]
(Preparation of film for sealant layer)
A film for a sealant layer having a thickness of 50 μm was obtained by inflation film formation at 160 ° C. using Ultozex 1520L, which is a low-eluting LLDPE.

(Preparation of resin composition for odor adsorption adhesive layer)
The master batch 1 obtained above and Novatec LC520, which is a general-purpose LDPE, were dry-blended at the following ratios to obtain an odor-adsorbing adhesive layer resin composition.
Masterbatch 1 30 parts by mass Novatec LC520 70 parts by mass

(Preparation of odor adsorption laminate)
The AC agent 1 was applied to one side of the paper material 1 and dried so that the applied amount after drying was 0.3 g / m ² to form an AC layer.
EMAA-based adhesive 1 is extruded on the side surface of the AC layer of the PET film 1, and Novatec LC600A, which is LDPE, is extruded on the surface opposite to the AC layer by the EC (extrusion coating, extrusion temperature: 280 ° C.) method. The aluminum-deposited film 1, which is a gas barrier film, was laminated so that the aluminum-deposited layer was in contact with the EMAA-based adhesive 1, and was pressurized with a roll to obtain a laminate precursor.
The odor-adsorbing adhesive layer resin composition obtained above was extruded on one surface of the aluminum vapor-deposited film of the laminate precursor obtained above by the EC (extrusion coating, extrusion temperature: 280 ° C.) method to obtain the above. The sealant layer film was laminated and pressed with a roll to be laminated to obtain an odor adsorption laminate having the following layer structure.
Base material layer [LDPE layer (20 μm) / paper layer (382 g / m ² )] / adhesive layer (20 μm) / gas barrier film layer (12 μm) / AC layer (0.3 g / m ² ) / odor adsorption adhesive Layer (15 μm) / Sealant layer (50 μm)
Next, various evaluations were performed on the obtained deodorant laminate.

<Examples 2 to 15, Comparative Examples 1 to 3>
The structure of the sealant layer was changed to the contents described in Tables 4 to 6, and the same operation as in Example 1 was carried out to obtain a deodorant laminate or a laminate, which was 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>
[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

1 Deodorant laminate, deodorant packaging material 2 Base material layer 2a Base material protection layer 2b Paper material layer 3 Gas barrier layer 4 Odor adsorption adhesive layer 5 Sealant layer

Claims (7)

At least, it is a deodorant laminate having a structure in which a base material layer, a gas barrier layer, an odor adsorbing adhesive layer, and a sealant layer are laminated in this order.
The base material layer has a paper material and a base material protective layer that covers one side surface of the paper material.
The odor-adsorbing adhesive layer is a layer formed by the extraction coating method, and contains a polyolefin resin and an odor-adsorbing agent.
The odor adsorbent is an inorganic chemical odor adsorbent and / or a hydrophobic zeolite having a SiO ₂ / AL ₂ O ₃ molar ratio of 30/1 or more and 10000/1 or less.
The base material protective layer is a layer formed by an extraction coating method and contains a polyolefin-based resin.
The sealant layer contains low elution polyethylene and contains
A deodorant laminate for a liquid paper container, characterized in that the content of the elution TOC of the low-eluting polyethylene is 1.5 ppm or more and 250 ppm or less. 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 content of the odor adsorbent in the odor adsorbing adhesive layer is 0.5% by mass or more and 15% by mass.
The deodorant laminate according to claim 1 or 2. The odor-adsorbing adhesive layer is a layer laminated at 250 ° C. or higher and 350 ° C. or lower by an extraction coating method.
The deodorant laminate according to any one of claims 1 to 3. The density of the low-eluting polyethylene is 0.90 g / cm ³ or more and 0.94 g / cm ³ or less.
The deodorant laminate according to any one of claims 1 to 4. A deodorant packaging material for a liquid paper container, which is produced from the deodorant laminate according to any one of claims 1 to 5. A deodorant liquid paper container made from the deodorant packaging material according to claim 6.

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