JP2020001274A - Deodorant packaging material and deodorant package - Google Patents

Abstract

To provide a laminate which is excellent in production suitability, and exhibits a deodorant effect against an odor organic matter contained in the laminate, odor generated by decomposition of a sealant film-constituting resin at the time of treatment such as UV irradiation, and an odor component generated from contents of a packaging bag-filled body using the laminate over a long period of time; and a packaging material and a package using the laminate.SOLUTION: A deodorant laminate contains at least a base material layer 2, a deodorant adhesive layer 5 and a sealant layer 6, in which the deodorant adhesive layer is a layer that contains an adhesive and a deodorant body and is formed by a dry lamination method, the deodorant body contains one or types selected from the group consisting of hydrophobic zeolite having SiO/AlOmolar ratio of 30/1 to 8,000/1, a chemical adsorbent-carried inorganic porous body and an inorganic odor decomposer, the inorganic odor decomposer is formed by kneading or carrying a metal oxide or metal salt with an inorganic matter, and a content of the deodorant body in the adhesive layer containing the deodorant adhesive layer is 0.2 mass% or more and 30 mass% or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a dissolvable organic substance originally contained in a packaging material, and an odorous component generated from the packaging material during sterilization and sterilization treatment. A packaging material, which prevents an unpleasant odor and has an odor improving effect on odor components generated from the content itself, is excellent in long-term resistance to odor change, and produced using the packaging material. The present invention relates to a deodorized package.

  As a packaging material, a packaging material including an odor adsorbent that absorbs odor has been proposed (Patent Document 1). In such packaging materials, an odor adsorbent such as synthetic zeolite or activated carbon is kneaded into the resin material.

  However, such a packaging material has a problem of adsorbing not only an odor but also moisture in the air and desorbing the odor once adsorbed, so that a sufficient odor adsorption effect is obtained. Not.

  A packaging material containing an odor adsorbent obtained by supporting a chemical adsorbent on an inorganic porous material is also known (Patent Document 2), but a main adsorption target adsorbs an odor component having a specific functional group. In a situation where no resin material is selected, the amount of organic substances having no functional group cannot be suppressed, and the odor component cannot be sufficiently adsorbed.

Japanese Patent No. 2538487 JP 2014-233408 A

  The present invention solves the above-mentioned problems, is excellent in manufacturing suitability, and has an odorous organic substance originally contained in the laminate and a sterilization / sterilization treatment such as UV irradiation, hot pack, boiling, γ-ray irradiation, and EB irradiation. At this time, the odor generated by the decomposition of the resin constituting the laminate and the like, and the odor component generated from the content itself when a packaging bag filling body is produced using the laminate of the present invention, high adsorption or It is intended to provide a laminate which exhibits a deodorizing effect due to a decomposition action over a long period of time and is excellent in long-term odor resistance change to contents, and a packaging material and a package using the laminate. Aim.

  As a result of various studies, the present inventors have found that a laminate having at least a base material layer, a specific deodorizing adhesive layer, and a sealant layer achieves the above object.

That is, the present invention has the following features.
1. At least a substrate layer, a deodorant adhesive layer, a deodorant laminate including a sealant layer,
The deodorizing adhesive layer is a layer containing an adhesive and a deodorant and formed by a dry lamination method, and the deodorant has a SiO ₂ / Al ₂ O ₃ molar ratio of 30/1 to 8000. / 1, a hydrophobic zeolite, an inorganic porous material carrying a chemical adsorbent, and one or more selected from the group consisting of inorganic odor decomposers, wherein the inorganic odor decomposer comprises a metal oxide or a metal salt, The deodorant laminate, wherein the content of the deodorant in the adhesive layer including the deodorant adhesive layer is 0.2% by mass or more and 30% by mass or less.
2. The sealant layer contains a heat-sealable thermoplastic resin and the deodorant,
The said deodorant laminated body whose content rate of the said deodorant in the said sealant layer is 0.2 to 15 mass%.
3. The above-mentioned deodorant laminate, wherein the chemical adsorbent-supporting inorganic porous material contains one or more elements selected from the group consisting of copper, zinc, silver, platinum, iron, and cobalt.
4. The above-mentioned deodorized laminate, wherein the inorganic odor decomposer contains one or more elements selected from the group consisting of copper, zinc, silver, platinum, iron and cobalt.
5. The deodorant contains two or three selected from the group consisting of the hydrophobic zeolite, the inorganic porous material supporting a chemical adsorbent, and the inorganic odor decomposer, and the deodorant includes an adhesive layer including the deodorant adhesive layer. The above deodorant laminate, wherein the total content of the deodorant is 0.2% by mass or more and 20% by mass or less.
6. The deodorant contains two or three selected from the group consisting of the hydrophobic zeolite, the inorganic porous material supporting a chemical adsorbent, and the inorganic odor decomposer, and the total of the deodorant in the sealant layer is The said deodorant laminated body whose content is 0.2 to 10 mass%.
7. The above-mentioned deodorant laminate, wherein the base material layer contains a paper material.
8. The above-mentioned deodorant laminate further including an intermediate layer, wherein the intermediate layer includes one or more gas barrier layers selected from the group consisting of a metal foil, a metal deposited film, and a metal oxide deposited film.
9. Furthermore, the above-mentioned deodorant laminate containing an aluminum foil as an intermediate layer.
10. Further, the above-mentioned deodorant laminate, wherein the intermediate layer includes a barrier coat resin layer on the gas barrier layer.
11. A deodorant packaging material produced from the above deodorant laminate.
12. A deodorant package produced from the above deodorant packaging material.
13. A deodorant package for liquid contents produced from the above deodorant packaging material.
14． A deodorant packaging for alcoholic beverages produced from the above deodorant packaging material.

  The deodorant laminate of the present invention contains a specific deodorant and an adhesive, and has an adhesive layer formed by a dry lamination method, so that the odor is efficiently adsorbed or decomposed to deodorize. And excellent adhesiveness.

  The odor includes the decomposition of odorous organic substances originally contained in the laminate and the resin that constitutes the laminate during sterilization and sterilization of UV irradiation, γ-ray irradiation, EB irradiation, hot packs, boiling, etc. There is an odor generated by the deodorizing laminate of the present invention, and an odor due to an odor component generated from the content itself when a packing bag is produced using the deodorant laminate of the present invention. It is possible to suppress the odor from being transferred or remaining in the contents, and to suppress the change in the odor of the contents.

  In addition, since the odor once adsorbed is hard to be desorbed, the odor can be efficiently adsorbed and the odor can be decomposed, so that the deodorizing ability does not decrease and a high deodorizing effect can be exhibited for a long time.

  Therefore, the deodorant laminate of the present invention is suitable for use as a packaging material for foods, pharmaceuticals, and medical products, which is subjected to a sterilization / sterilization treatment. In particular, it has a high deodorizing effect on liquid contents, and particularly exerts a great effect on alcoholic beverages.

It is a schematic sectional drawing which shows an example about the layer structure of the deodorizing laminated body of this invention. It is a schematic sectional drawing which shows an example of another aspect about the layer structure of the deodorant laminated body of this invention. It is a schematic sectional drawing which shows an example of further another aspect about the layer structure of the deodorant laminated body of this invention. It is a figure which shows the adsorption mechanism with respect to an odor substance of a chemical adsorbent carrying inorganic porous body.

The deodorant laminate of the present invention, the deodorant packaging material produced using the deodorant laminate, and the deodorant package 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>
As shown in FIG. 1, the deodorant laminate of the present invention includes at least a substrate layer, a deodorant adhesive layer, and a sealant layer. Further, other layers such as an intermediate layer can be included as necessary.

<Base layer>
The substrate layer in the present invention may include, but is not limited to, a thermoplastic resin, a paper material, and the like. Further, the base material layer may include one or two or more of the above layers.
Further, between each of the layers constituting the base material layer, an adhesive layer may be provided in order to improve the adhesiveness, or a desired surface treatment layer may be provided in advance on the surface of each layer as necessary. Can be.

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 or the like is optionally performed, and the corona treatment layer, ozone treatment A layer, a plasma treatment layer, an oxidation treatment layer, or the like can be formed and provided.
Alternatively, various coating agent layers such as a primer coating agent layer, an undercoat agent layer, an anchor coating agent layer, an adhesive layer, and a vapor-deposited anchor coating agent layer may be arbitrarily formed on the surface to form a surface treatment layer. .

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

The thickness of the base layer depends on the material, but is preferably 5 to 30 μm, more preferably 10 to 30 μm in the case of a resin film.
A film for a base material layer satisfying the above requirements is also commercially available, and as a film suitably used in the present invention, for example, a biaxially stretched PET film E5100 (12 μm thick) manufactured by Toyobo Co., Ltd. , One-sided corona treatment), biaxially stretched PET film E5200 (thickness 12 μm, both-sided corona treatment), and a biaxially stretched nylon film ONBC (15 μm thickness, both-sided corona treatment) manufactured by Unitika Ltd.

(Thermoplastic resin of the base layer)
The thermoplastic resin used for the base material layer is used in the form of a film or used by coating, impregnating, coating, etc. on paper, etc., and has excellent chemical or physical strength, It is preferable that the thermoplastic resin be a thermoplastic resin that can withstand the conditions for forming an oxide vapor-deposited film and that can be favorably retained without impairing the properties of the metal oxide vapor-deposited film.

Examples of such a resin include a polyolefin resin such as a polyethylene resin or a polypropylene resin, a cyclic polyolefin resin, a polystyrene resin, an acrylonitrile-styrene copolymer (AS resin), and an acrylonitrile-butadiene-styrene copolymer. (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, polyamide resin such as various nylons, polyurethane resin, acetal resin, cellulose resin, etc. Of various resins.

In the present invention, it is preferable to use a polyester resin, a polyolefin resin, or a polyamide resin film or sheet among the above resins.
In the present invention, the thermoplastic resin used for the substrate layer can be formed into a film by various known and commonly used film forming methods.

For example, using one kind of resin, a method of forming a film using a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, and using two or more kinds of resins. A method of forming a multilayer co-extrusion film, a method of mixing two or more kinds of resins before forming a film, and forming a film by the above-described film forming method, and the like. Further, a film stretched in a uniaxial or biaxial direction using a tenter method, a tube ramamer method, or the like can be used.
Alternatively, one or more resins may be coated and dried on a paper material or a resin film, or a resin melted by a T-die method or the like may be laminated.

  In addition, the thermoplastic resin, when forming the film, for example, the workability of the film, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release, flame retardant, Various plastic compounding agents and additives can be added for the purpose of improving and modifying the antifungal property, electric properties, strength, etc., and the amount of addition can be from a very small amount to several tens%. They can be arbitrarily added according to the purpose.

  In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, a modifying resin, and the like are used. be able to.

(Paper material)
When the deodorant laminate of the present invention constitutes a liquid content paper container, particularly when the liquid content contains alcohol, a paper material can be used as a basic material constituting the paper container. .
As the paper material, those having moldability, bending resistance, rigidity, stiffness, strength and the like can be used. For example, strong size bleached or unbleached paper material, or pure white roll paper, kraft paper Various paper materials such as paper, paperboard, processed paper, milk base paper, and the like can be used. Further, these papers may be stacked in a plurality of layers.

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, it is 250 to 450 g / m ² .

<Adhesive layer>
The adhesive layer in the deodorant laminate of the present invention can include a deodorant adhesive layer, and the adhesive layer is an adhesive layer consisting of only a deodorant adhesive layer, an adhesive layer consisting of a deodorant adhesive layer and a non-deodorant adhesive layer. Or an adhesive layer consisting only of a non-deodorant adhesive layer.

[Deodorant adhesive layer]
The deodorizing adhesive layer in the present invention is a layer containing an adhesive and a deodorant, and formed by a dry lamination (DL) method.

When the adhesive layer is formed by the dry lamination method, the adhesive layer can be formed at a lower temperature than the extrusion method, and a resin decomposition odor is generated from the adhesive itself contained in the adhesive layer. Is suppressed.
Since the adhesive layer is formed by the dry lamination method, it is easy to increase the content of the deodorant in the deodorant adhesive layer, and even if the thickness is the same, a large amount of the deodorant is laminated. It is contained in the body and can enhance the deodorant effect.

  Known adhesives for dry lamination can be used as the adhesive contained in the deodorizing adhesive layer.

  The adhesive may be of a thermosetting type, an ultraviolet curing type, an electron beam curing type, or the like, and may be in any form of an aqueous type, a solution type, an emulsion type, a dispersion type, and the like. , Powder, and solid, and the bonding mechanism may be any of a chemical reaction type, a solvent evaporation type, a hot-melt type, and a hot-pressure type.

  Examples of components that form such an adhesive layer include polyvinyl acetate adhesives such as polyvinyl acetate and vinyl acetate-ethylene copolymer, and copolymers of polyacrylic acid with polystyrene, polyester, and polyvinyl acetate. Polyacrylic acid adhesive, cyanoacrylate adhesive, ethylene and vinyl acetate, ethyl acrylate, acrylic acid, ethylene copolymer adhesive comprising a copolymer of monomers such as methacrylic acid, cellulose-based 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 resin Adhesive, reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber, Styrene - butadiene made of rubber or the like elastomeric adhesive, a silicone adhesive, an alkali metal silicate, but the low melting point glass inorganic adhesive made of such like, polyester-based adhesives are preferred.

The deodorizing adhesive layer may use any anchor coating agent. (Hereinafter, it is generally referred to as an adhesive.)
As the anchor coating agent, for example, an organic titanium-based, isocyanate-based, polyethyleneimine-based, acid-modified polyethylene-based, polybutadiene-based anchor coating agent, or the like can be used.

  The content of the deodorant in the adhesive layer including the deodorant adhesive layer is preferably 0.2% by mass or more and 0.25% by mass in order to obtain a good deodorizing effect as a package. More preferably. On the other hand, in order to obtain good adhesiveness, the content of the deodorant in the adhesive layer including the deodorant adhesive layer is preferably 30% by mass or less.

  When two or three kinds selected from the above group are used in combination as the deodorant, the content of the deodorant in the adhesive layer including the deodorant adhesive layer is reduced by improving the deodorant efficiency. Even when the content is 0.2% by mass or more and 20% by mass or less, a sufficient deodorizing effect can be obtained.

(Method of dispersing deodorant in adhesive)
As a method of kneading the deodorant and the adhesive, a known or commonly used kneading method can be applied.

It is also possible to mix the deodorant directly with the adhesive and knead it, or mix the deodorant with a thermoplastic resin at a high concentration and then melt knead it to produce a masterbatch, It is also possible to adopt a so-called master batch method in which the mixture is mixed with the adhesive at a ratio according to the content and melt-kneaded.

  In the present invention, when preparing the deodorant adhesive layer forming composition for dry lamination when forming the deodorant adhesive layer, the above method of directly mixing and kneading is preferable, and the deodorant sealant layer resin composition When preparing a product, the above-mentioned master batch method is preferable.

(Formation of deodorant adhesive layer)
The deodorizing adhesive layer is formed by a dry lamination method.
When performing dry lamination coating, for example, after applying and drying the deodorant adhesive layer forming composition on one layer, and laminating and laminating the other layer to be bonded, several hours to several hours at 30 to 120 ° C. By aging for days, the adhesive can be cured and laminated.

  In the dry lamination method, it is easy to incorporate a liquid adhesive or a solvent into the deodorizing adhesive layer forming composition, and sufficiently reduce the viscosity of the deodorizing adhesive layer forming composition to exhibit high adhesiveness. It is possible to do.

[Non-deodorant adhesive layer]
The non-deodorant adhesive layer is an adhesive layer containing an adhesive but not containing a deodorant.
In the present invention, as shown in FIG. 2, it is also possible to bond the respective layers by using a non-deodorizing adhesive layer in combination.

  The non-deodorant adhesive layer may be a layer composed of an adhesive for dry lamination, an adhesive for EC (extrusion coating), an adhesive for non-solvent lamination, an optional anchor coating agent, and the like.

  When an adhesive for dry lamination is used, the configuration of the adhesive is the same as the configuration in which the deodorant is removed from the deodorant adhesive layer, and is used by laminating in the same manner.

  When using the adhesive for EC, the adhesive for extrusion coating is heated and melted, expanded and expanded in a required width direction with a T-die, extruded in a curtain shape, and the melt is allowed to flow down onto the layer to be bonded. Then, by sandwiching between a rubber roll and a cooled metal roll, formation of an adhesive layer, adhesion to an adhesion target layer, and lamination are simultaneously performed.

  Since the deodorizing adhesive layer is formed by the extrusion method, the deodorizing adhesive layer can be easily formed without a solvent, and generation of a solvent odor can be prevented.

As the EC adhesive, a known extrusion coat adhesive can be used.
For example, general-purpose polyethylene, thermoplastic resins such as polypropylene, methylpentene polymer, and acid-modified polyolefin-based resin, and mixtures thereof are suitable, but are not limited to these resins.

  When using a non-solvent laminating adhesive, apply a known non-solvent laminating adhesive to a layer without dispersing or dissolving it in a solvent, apply the adhesive itself to the layer, and dry the layer. After laminating, the adhesive is cured by aging at 30 to 120 ° C. for several hours to several days to laminate.

  As the anchor coating agent, for example, an organic titanium-based, isocyanate-based, polyethyleneimine-based, acid-modified polyethylene-based, polybutadiene-based anchor coating agent, or the like can be used.

Examples of the application means include a roll coat, a gravure roll coat, and a kiss coat, and the coating amount is preferably about 0.1 to 10 g / m ² (dry state). By setting the coating amount of the adhesive within the above range, good adhesiveness can be obtained.

<Deodorant>
In the present invention, Shonioitai is a compound which exhibits the deodorizing effect, SiO ₂ / Al ₂ O ₃ molar ratio is 30 / 1-8000 / 1 of hydrophobic zeolite, chemical adsorbent supported inorganic porous material, inorganic Contains one or more selected from the group consisting of odor decomposers.

[Hydrophobic zeolite]
Hydrophobic zeolite used in the present invention, SiO ₂ / Al ₂ O ₃ molar ratio is preferably from 30/1 to 8,000 / 1. In general, the higher the molar ratio of SiO ₂ / Al ₂ O ₃ , the higher the hydrophobicity of the zeolite.

  Even when the deodorant laminate of the present invention is exposed to 230 ° C. or higher, the hydrophobic zeolite maintains the effect of adsorbing odor components.

  The hydrophobic zeolite may have any external shape such as a sphere, a rod, and an ellipse, and may be in any form such as a powder, a lump, or a granule. From the viewpoints of dispersibility, kneading characteristics, film forming properties, and the like, powder is preferable.

  In the present invention, the average particle diameter of the hydrophobic zeolite can be appropriately selected from those having an arbitrary average particle diameter according to the intended use, but is preferably from 0.01 μm to 10 μm. Here, the average particle diameter is a value measured by a dynamic light scattering method.

  When the average particle size is smaller than 0.01 μm, aggregation of the hydrophobic zeolite tends to occur, 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 hydrophobic zeolite tends to be inferior, so that it tends to be difficult to add much hydrophobic zeolite, and the surface area further decreases. Therefore, there is a possibility that a sufficient deodorizing effect cannot be obtained.

  Since hydrophobic zeolite is hydrophobic, it is difficult for high-polarity water molecules and the like to be adsorbed. On the contrary, it has low polarity, affinity with odor molecules, hydrophobic gas, and lipophilic gas (including solvent-based gas). And it is easy to adsorb them. Furthermore, the surface of the zeolite exhibits basicity due to the effects of alkali metals and alkaline earth metals such as Ca, Na, and K existing on the surface of the zeolite, and the acid gas is easily adsorbed by the neutralization reaction.

[Chemical adsorbent-supported inorganic porous material]
In the present invention, a chemical adsorbent-supported inorganic porous material is a material in which a chemical adsorbent is supported on an inorganic porous material, and organic substances having elution, UV irradiation, γ-ray irradiation, EB irradiation, hot pack, boil It has a function of adsorbing odorous substances generated from the package during sterilization / sterilization processing.

  As the loading method, a known or commonly used loading method can be applied.For example, a solution containing a chemical adsorbent described below is impregnated into an inorganic porous material and dried to be loaded. it can.

In the present invention, by using a chemical adsorbent-supported inorganic porous body, the adsorption capacity per unit mass of the chemical adsorbent can be significantly increased, and the chemical adsorbent and the chemical adsorbent-supported inorganic porous body in the laminate are The content can be reduced. In addition, physical adsorption characteristics to the pores of the inorganic porous material can be expected.

  With these, high adhesive strength and seal strength can be obtained, and excellent adhesiveness, applicability and film forming property required for the adhesive layer can be maintained, and excellent heat sealability and film forming property required for the sealant layer can be maintained. Can be held.

  The inorganic porous body supporting a chemical adsorbent preferably contains one or more elements selected from the group consisting of copper, zinc, silver, platinum, iron and cobalt.

  The inorganic porous material carrying the chemical adsorbent may have any external shape such as a sphere, a rod, and an ellipse, and may be in any form such as a powder, a lump, or a granule. From the viewpoint of uniform dispersibility, kneading characteristics, and the like, powder is preferable.

  The chemical adsorbent-supporting inorganic porous material can be appropriately selected from those having an average particle diameter according to the intended use. In the present invention, in particular, those having an average particle diameter of 0.01 μm to 10 μm are preferable. 0.1 μm to 8 μm is more preferable, and 1 μm to 7 μm is further preferable. Here, the average particle diameter is a value measured by a dynamic light scattering method.

  When the average particle size is smaller than 0.01 μm, the inorganic porous material supporting the chemical adsorbent tends to aggregate, and the dispersibility tends to decrease.

  Further, when the average particle diameter is larger than 10 μm, the film-forming property is inferior, so that a large amount of the inorganic porous material supporting the chemical adsorbent tends to be hardly contained, and a sufficient adsorption effect may not be obtained. .

  Specific examples of commercially available products include NS-241 and NS-231 (inorganic porous material supporting an amino group-containing compound) manufactured by Toagosei Co., Ltd., and Dashlite M (amino group-containing compound manufactured by Sinanen Zeomic Co., Ltd.) A supported inorganic porous body), dashlite CZU (a copper-zinc-containing inorganic porous body supported by a chemical adsorbent) and the like can be used as suitable deodorants in the present invention.

(Inorganic porous material)
In the present invention, as the inorganic porous body, any inorganic compound having a large number of pores on its surface can be used, and examples thereof include zeolite, silicon dioxide, silicate, activated carbon, titania, and inorganic phosphates such as calcium phosphate. 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 having 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 sphere, a rod, and an ellipse, and may be in any form such as a powder, a lump, and a granule. After forming the inorganic porous material, a powder is preferable from the viewpoints of the film forming property, uniform dispersion, kneading characteristics, and the like.

  The inorganic porous material can be appropriately selected from those having an arbitrary average particle size depending on the application. In order to achieve the above average particle size of the inorganic porous material supporting a chemical adsorbent, the inorganic porous material has an average particle size of 0. It is preferably from 01 μm to 10 μm, more preferably from 0.1 μm to 8 μm, even more preferably from 1 μm to 7 μm.

(Chemical adsorbent)
In the present invention, the chemical adsorbent has a reactive functional group which causes a chemical reaction with an eluting organic substance or an odorous substance generated by decomposition of a resin during sterilization / sterilization treatment, and has the inorganic function. It is a compound that can be supported on a porous body.

  More specifically, UV irradiation, γ-ray irradiation, EB irradiation, hot packs, various functional aldehydes, ketones, carboxylic acids and other reactive groups that are generated during sterilization / sterilization treatment of boiling, etc. Is a compound having

  Examples of such a compound include compounds having an amino group, for example, alkylamine, polyamines such as tetramethylenediamine, ethanolamine, piperidine, compounds having a basic functional group such as a hydroxyl group, for example, sodium hydroxide, hydroxide, and the like. Hydroxides such as potassium, magnesium hydroxide and iron hydroxide, carbonates such as sodium carbonate, sodium hydrogen carbonate and calcium carbonate, hydrogen carbonates and amide group-containing compounds such as 2-acrylamido-2-methylpropanesulfonic acid Is mentioned.

  In the present invention, examples of the chemical adsorbent exhibiting particularly excellent adsorption effects include compounds having an amino group, such as polyamines such as ethylenediamine, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, piperazine, and metaphenylenediamine. However, it is not limited to these.

The adsorption mechanism of the chemical adsorbent for the eluting organic substances and odor substances will be described in more detail with reference to specific examples of FIGS. 4A and 4B, but the present invention is not limited to these.
For example, when the substance to be adsorbed is an acid-based odorous substance, as shown in FIG. 4 (a), a chemical adsorbent supported by, for example, a compound having a hydroxyl group supported on an inorganic porous material as a chemical adsorbent An inorganic porous body can be used. As a result, the carboxyl group and the hydroxyl group cause a chemical reaction and bond, and the substance to be adsorbed is adsorbed.
When the substance to be adsorbed is an aldehyde, as shown in FIG. 4 (b), a chemical adsorbent-supported inorganic porous material obtained by, for example, supporting a compound having an amino group on an inorganic porous material is used as the chemical adsorbent. The body can be used. As a result, the aldehyde group and the amino group cause a chemical reaction to be bonded, and the substance to be adsorbed is adsorbed.

  At this time, by the chemical adsorption, the substance to be adsorbed once adsorbed is not desorbed, and the odor can be efficiently adsorbed.

  Furthermore, unlike a physical adsorbent, in which odor and water vapor are adsorbed on the same adsorption site, the chemical adsorbent of the present invention binds to a specific functional group of the chemical adsorbent because the substance to be adsorbed has an odor adsorption capacity. Is not easily affected by various substances that lower the water content, such as water vapor.

[Inorganic odor decomposer]
The inorganic odor decomposer in the present invention is obtained by kneading or supporting a metal oxide or a metal salt on an inorganic substance, and preferably comprises at least copper (II) oxide, silicon oxide, and an alkali metal oxide. It is formed from an inorganic odor decomposer composition containing

  The inorganic odor decomposer according to the present invention is capable of decomposing sulfur-based malodorous substances by exerting a catalytic action to accelerate the decomposition reaction of sulfur-type malodorous substances by ionizing metal components and the like held in the inorganic odor decomposers. It has an odor effect. Among sulfur-based malodorous substances, it has a particularly high deodorizing effect on hydrophilic compounds such as hydrogen sulfide.

The inorganic odor decomposer composition preferably further contains one or more elements selected from the group consisting of copper, zinc, silver, platinum, gold, iron and cobalt as the above-mentioned ionizing component, and in particular, , Copper, zinc, and silver. Each element is preferably contained in the inorganic odor decomposer composition as a metal, a metal oxide, a metal ion, a metal complex, or the like.

As the metal oxide, _{e.g., 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, Co 3 O _{4 and the} like.

  In addition, the inorganic odor decomposer composition, if necessary, further contains boron oxide to adjust the chemical performance and physical performance, and may further contain an alkaline earth metal oxide, aluminum oxide, and the like. .

  The powdery inorganic odor decomposer is prepared by mixing each raw material to prepare an inorganic odor decomposer composition, melting and homogenizing in the same manner as general-purpose glass production such as bottle glass, and then pulverizing after cooling. Can be obtained.

  Inorganic odor decomposers can promote the decomposition reaction of sulfur-based malodorous substances as catalysts, and can increase the deodorizing capacity compared to conventional technologies that rely on surface area using chemical adsorption and physical adsorption. The odor effect can be stably exhibited over a long period of time.

  The content of copper (II) oxide (CuO) in the inorganic odor decomposer composition is preferably 0.01 to 23 mol%, more preferably 1 to 13 mol%, and still more preferably 4 to 13 mol%. When the amount is less than the above range, the deodorizing effect tends to be hardly exerted, and when the amount is more than the above range, metallic copper is easily precipitated, which is not preferable.

Silicon oxide (SiO ₂ ) is the main component forming the structural skeleton of the inorganic odor decomposer. The content of silicon oxide in the inorganic odor decomposer composition is preferably 46 to 70 mol%, more preferably 51 to 70 mol%.

  If the amount is less than the above range, the chemical durability and water resistance of the inorganic odor decomposer tend to be insufficient, and the deodorizing effect by the catalytic action of copper (II) oxide is liable to decrease. If the amount is larger than the above range, the melting point and the melt viscosity of the inorganic odor decomposer are too high, and the inorganic odor decomposer tends to be heterogeneous.

The alkali metal oxide is one or more selected from the group consisting of Li ₂ O, Na ₂ O, and K ₂ O, and is a component that lowers the melting point and melt viscosity of the inorganic odor decomposer.

  The content of the alkali metal oxide in the inorganic odor decomposer composition is preferably from 10 to 33 mol%, more preferably from 12 to 24 mol%, even more preferably from 12 to 20 mol%.

  If the amount is less than the above range, the effect of lowering the melting point and melt viscosity of the inorganic odor decomposer tends to be insufficient. If the amount is larger than the above range, the chemical durability and water resistance of the inorganic odor decomposer tend to be insufficient, and the deodorizing effect tends to decrease.

  The alkaline earth metal oxide is at least one selected from the group consisting of MgO, CaO, SrO, and BaO, and is a component contained in the inorganic odor decomposer composition as required. It has the effect of improving the chemical durability of the agent.

When the alkaline earth metal oxide is contained in the inorganic odor decomposer composition, the content of the alkaline earth metal oxide in the inorganic odor decomposer composition is preferably from 2 to 10 mol%, more preferably from 2 to 7 mol%.
Is more preferred.

  When the amount is less than the above range, it is difficult to sufficiently exert the effect containing the alkaline earth metal, and when the amount is more than the above range, the melting point and the melt viscosity of the inorganic odor decomposer are too high to be heterogeneous. Easy to be.

Boron oxide (B ₂ O ₃ ) has the effect of lowering the melting point and melt viscosity of the inorganic odor decomposer and chemically stabilizing the inorganic odor decomposer.

  When boron oxide is contained in the inorganic odor decomposer composition, the content of boron oxide in the inorganic odor decomposer composition is preferably from 5 to 20 mol%, more preferably from 8 to 17 mol%.

  When the amount is less than the above range, it is difficult to sufficiently exert the effect containing boron oxide, and when the amount is more than the above range, the chemical durability and water resistance of the inorganic odor decomposer tend to be insufficient. In addition, the deodorizing effect tends to decrease.

  Boron oxide has the effect of lowering the melting point and melt viscosity of the inorganic odor decomposer in the same manner as the alkali metal oxide, so it is preferable to consider the content of the total amount of boron oxide and alkali metal oxide, The total content of boron oxide and alkali metal oxide in the decomposing agent composition is preferably 15 to 50 mol%, more preferably 21 to 39 mol%.

  If the amount is less than the above range, the effect of lowering the melting point and melt viscosity of the inorganic odor decomposer tends to be insufficient. If the amount is larger than the above range, the inorganic odor decomposer tends to be non-uniform, the water resistance of the inorganic odor decomposer tends to be insufficient, and the deodorizing effect tends to decrease.

Aluminum oxide (Al ₂ O ₃ ) is a component contained in the inorganic odor decomposer composition as needed, and has an effect of improving the homogeneity of the inorganic odor decomposer and improving the chemical durability.

  When aluminum oxide is contained in the inorganic odor decomposer composition, the content of aluminum oxide in the inorganic odor decomposer composition is preferably from 0.1 to 6 mol%, more preferably from 0.1 to 5.5 mol%. Is more preferable, and 0.1 to 4.5 mol% is further preferable.

  When the amount is less than the above range, it is difficult to sufficiently exert the effect containing aluminum oxide, and when the amount is more than the above range, the melting point and the melt viscosity of the inorganic odor decomposer tend to be too high to be inhomogeneous. .

In addition to the above components, trace components such as TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , P ₂ O ₅ , Cs ₂ O, Rb ₂ O, TeO ₂ , BeO, GeO ₂ , Bi ₂ O ₃ , La ₂ O ₃ , Y ₂ O ₃ , WO ₃ , MoO ₃ , Sb ₂ O ₃ , SnO _2, etc.

The particle size distribution of the inorganic odor decomposer is preferably a powder having a weight average particle size of 1 μm or more and 30 μm or less, and _D96 of 40 μm or less. Here, the average particle diameter is a value measured by performing a particle size distribution measurement by a dynamic light scattering method, and D ₉₆ means a particle diameter corresponding to an integrated value of 96 mass% when cumulatively distributed.

  When the average particle size is smaller than 1 μm, the aggregation of the inorganic odor decomposer tends to occur, and the dispersibility in the sealant layer tends to decrease. When the average particle diameter is larger than 30 μm, the film forming property of the sealant layer tends to be inferior, so that it tends to be difficult to add many inorganic odor decomposers, and the surface area also decreases. It may be difficult to obtain the odor effect.

If D ₉₆ exceeds 40 [mu] m, it tends to become difficult uniform dispersion of the heat-sealable resin is, film formability may be deteriorated.

<Sealant layer>
The sealant layer in the present invention contains a heat-sealable thermoplastic resin. And preferably, it can contain a deodorant.

  The deodorant sealant film of the present invention can exhibit excellent heat sealability when the sealant layer contains the heat sealable thermofacial resin, and has a deodorant effect by containing a deodorant. Can be increased.

  As the deodorant contained in the sealant layer, the deodorant in the deodorant adhesive layer can be used. In one laminate, the deodorant having the same composition is used in the deodorant adhesive layer and the sealant layer. Also, deodorants having different compositions may be used.

  As shown in FIGS. 1 and 2, the sealant layer may be only a deodorant sealant layer containing a deodorant, or may be only a non-deodorant sealant layer containing no deodorant. Thus, a multilayer structure of a deodorant sealant layer and a non-deodorant sealant layer may be used.

  Non-deodorant sealant layer. It is preferable that the deodorant sealant layer is in contact with and laminated on one side and / or both sides of the deodorant sealant layer because the seal strength and the interlayer adhesive strength can be improved.

  When the package is manufactured, the innermost layer in contact with the contents of the package may be a deodorant sealant layer or a non-deodorant sealant layer. When the non-deodorant sealant layer is the innermost layer, the sealing strength of the package can be improved, and when the deodorant sealant layer is the innermost layer, the interlayer adhesive strength in the package can be improved.

In the deodorant sealant layer, the deodorant is selected from the group consisting of a hydrophobic zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 30/1 to 8000/1, an inorganic porous material carrying a chemical adsorbent, and an inorganic odor decomposer. One or two or more types, and the total content of deodorants in the sealant layer including the deodorant sealant layer and the non-deodorant sealant layer is 0.2% by mass or more and 15% by mass. The following is preferred.

  If it is less than the above range, it is difficult to exert a sufficient deodorizing effect, and if it is more than the above range, it becomes difficult to exhibit good film-forming properties and heat sealing properties.

  When two or three selected from the above group are used in combination as the deodorant, the content of the deodorant in the sealant layer including the deodorant sealant layer is reduced by improving the deodorant efficiency. A sufficient deodorizing effect can be obtained even when the content is not less than 0.2% by mass and not more than 10% by mass.

[Heat-sealable thermoplastic resin]
Specific examples of the heat-sealable thermoplastic resin include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear (linear) low-density polyethylene (LLDPE), and ethylene-acetic acid. Low elution of vinyl copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylic acid copolymer, ethylene-propylene copolymer, etc. , And mixtures of these resins, but are not limited to these resins.

Among the above, polyethylene is preferred in that it is resistant to sterilization and sterilization treatments such as UV and has a property of being hardly decomposed, and among the polyethylenes, LLDPE is more preferred.

  In addition, the sealant layer can include lubricants, antioxidants, antiblocking agents, and other additives.

  The heat-sealable thermoplastic resin contained in the sealant layer preferably has excellent pinhole resistance due to bending when formed into a film by itself.

  Since the package may cause pinholes due to repeated fatigue bending due to vibrations during the packaging process and during transportation, pinholes are particularly resistant to packaging materials for food and medical supplies. is important.

  The pinhole resistance of the heat-sealable thermoplastic resin contained in the sealant layer is determined, for example, by measuring the pinhole of a 50 μm-thick film made of the heat-sealable thermoplastic resin alone after 5000 times of Gelboflex at 23 ° C. The number of occurrences is preferably 0, or 1 or more and 160 or less.

  When the number of pinholes generated in the film is within the above range, a package that can withstand practical use can be produced in applications requiring pinhole resistance.

[Non-deodorant sealant layer]
The non-deodorant sealant layer in the sealant layer in the present invention is a sealant layer containing a heat-sealable thermoplastic resin but not containing a deodorant.

[Deodorant sealant layer]
The deodorant sealant layer is a sealant layer containing a deodorant and a heat-sealable thermoplastic resin.

  The deodorant sealant layer may have a multilayer structure composed of layers having the same or different types of heat sealable thermoplastic resin as the main component and types and content of deodorants.

  Further, although not shown, the deodorant sealant layer may be composed of three or more layers having the same or different types of heat-sealable thermoplastic resin as the main component and types and contents of deodorants.

  In the deodorant sealant layer, the deodorant may be uniformly dispersed in the layer, or may be dispersed with a concentration gradient.

  For example, the particles may be dispersed with an increasing concentration gradient from the inner surface to the outer surface when the package is formed, and this configuration improves the heat sealability. Conversely, it may be dispersed with a decreasing concentration gradient from the inner surface to the outer surface when the package is formed, and this configuration improves the interlayer adhesive strength.

  Further, the deodorant sealant layer may be dispersed with a decreasing concentration gradient from the center in the thickness direction of the deodorant sealant layer toward both surfaces. With this configuration, the heat sealing property and the interlayer adhesive strength are improved.

  If the deodorant sealant layer has a thickness of 5 μm or more, it is possible to form a film. However, in order to obtain good film forming properties, heat sealing properties, interlayer adhesion strength and deodorization properties, it is preferably 10 μm to 200 μm.

[Formation of deodorant sealant layer or non-deodorant sealant layer]
(Method of dispersing deodorant in heat-sealable thermoplastic resin)
As a method of kneading the deodorant and the heat-sealable thermoplastic resin, a known or commonly used kneading method can be applied.
It is also possible to mix the deodorant directly with the heat-sealable thermoplastic resin and knead it, or mix the deodorant with the thermoplastic resin at a high concentration and then melt-knead (melt blend) the master batch. It is also possible to use a so-called masterbatch method in which this is mixed and melt-kneaded with a heat-sealable thermoplastic resin at a ratio according to the target content.

The content of the hydrophobic zeolite in the master batch is preferably 0.5% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 20% by mass or less.
The content of the inorganic porous material supporting the chemical adsorbent in the master batch is preferably 0.5% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 20% by mass or less.
The content of the inorganic odor decomposer in the master batch is preferably 0.5% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 20% by mass or less.

  In the case of the masterbatch method, even a combination of a deodorant and a heat-sealable thermoplastic resin, which easily causes aggregation, can be efficiently and uniformly dispersed.

  At this time, the thermoplastic resin in the masterbatch may be the same as or different from the heat-sealable thermoplastic resin in the deodorant sealant layer. It is possible to combine types of plastic resins.

  For example, if the deodorant and the heat-sealable thermoplastic resin are melt-mixed in advance, when they are mixed or melt-kneaded with the heat-sealable thermoplastic resin again, they are homogeneous and have good film-forming properties and heat-sealing properties. It is possible to efficiently obtain the interlayer adhesive strength and the deodorant property.

  Examples of the thermoplastic resin used for the masterbatch include, but are not limited to, general-purpose polyethylene, polypropylene, methylpentene polymers, polyolefin-based resins such as acid-modified polyolefin-based resins, and mixtures of these resins.

  The thermoplastic resin preferably has a heat-sealing property equivalent to that of the heat-sealable thermoplastic resin in the present invention, but is used within a range that does not greatly affect the heat-sealing property or film-forming property of the entire sealant layer. be able to.

(Method of forming and laminating sealant layer)
In the present invention, a method of forming and laminating each layer in the sealant layer is not particularly limited, and a known or commonly used film forming method and laminating method can be applied.

  Laminating a deodorant sealant layer or a non-deodorant sealant layer on another layer by an extrusion coating method, optionally via an adhesive layer, and, for example, a plurality of deodorant sealant layers and a non-deodorant sealant layer Can also be formed by co-extrusion using an inflation method or a casting method.

  In the case of lamination by the extrusion coating method, first, the resin composition forming the deodorant sealant layer or the resin composition forming the non-deodorant sealant layer is heated and melted, and the width direction required by the T die is used. The molten resin is allowed to flow down onto the surface to be laminated, and is sandwiched between a rubber roll and a cooled metal roll to form a deodorant sealant layer or a non-deodorant sealant layer. Adhesion to the lamination surface and lamination are performed simultaneously.

When laminated by the extrusion coating method, the melt flow rate (MFR) of the heat-sealable thermoplastic resin contained in the deodorant sealant layer and the non-deodorant sealant layer may be 0.2 to 50 g / 10 minutes. Preferably, it is more preferably 0.5 to 30 g / 10 minutes. In this specification, the MFR is a value measured by a method based on JIS K7210.
If the MFR is less than 0.2 g / min, or more than 50 g / min, it is difficult to obtain an effective form in terms of appropriate processing.

When using the inflation method, the melt flow rate (MFR) of the heat-sealable thermoplastic resin contained in the deodorant sealant layer and the non-deodorant sealant layer is preferably 0.2 to 10 g / 10 minutes, More preferably, it is 0.2 to 9.5 g / 10 minutes.
If the MFR is less than 0.2 g / 10 min or more than 10 g / 10 min, the workability tends to be poor.

  Alternatively, the deodorant sealant layer and the non-deodorant sealant layer formed in advance may be laminated via an adhesive layer by an adhesive, an extrusion coating method, a dry lamination method, a non-solvent lamination method, or the like. .

<Intermediate layer>
As shown in FIG. 2, the deodorant laminate of the present invention can include an intermediate layer for imparting various functions as needed.

  For example, as the barrier layer, a thermoplastic resin film having a metal foil, a metal deposited film layer or a metal oxide deposited film layer formed thereon, or a barrier coat resin layer on the metal deposited film layer may be further included.

  By including the barrier layer as described above, the gas barrier properties of the laminate can be improved, the effect of preventing the oxidation of the content and the dissipation of the flavor component is increased, and the effect of maintaining the flavor of the content can be enhanced. it can.

  In particular, it is important to maintain the taste of liquid beverages and alcoholic beverages, etc., and exert a great effect.

  Furthermore, the film for the intermediate layer, which satisfies the above requirements, is commercially available, and a film preferably used in the present invention is, for example, a PET film in which alumina is vapor-deposited on one side by a PVD method. And IB-PET-PIR (thickness: 12 μm) and IB-ON-UB (thickness: 15 μm), which are manufactured by Dai Nippon Printing Co., Ltd.

<Deodorant packaging material>
The deodorant packaging material of the present invention is produced from the deodorant laminate of the present invention.If necessary, a known print layer or another layer or another laminate is laminated by a known method. Can be used.

<Deodorant package>
The deodorant package of the present invention is obtained by, for example, forming a bag of the deodorant packaging material of the present invention, and bending the packaging material or two sheets so that the surfaces having good heat sealability face each other. Overlapping, the peripheral end thereof is, for example, a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, a gasket-attached seal type (pillow seal type), a pleated seal type, and a flat bottom seal type It can be manufactured by heat sealing using a heat sealing form such as a square bottom seal type, a gusset type, or the like.
As a method of heat sealing, for example, a bar seal, a rotating roll seal, a belt seal,
Known methods such as an impulse seal, a high frequency seal, and an ultrasonic seal can be applied.
The deodorant package of the present invention can be used as a deodorant package for liquid content for filling the liquid content, and in particular, can be used as a deodorant package for liquor whose liquid content is liquor. .

<Liquid contents>
In the present invention, the liquid contents refer to all kinds of liquids such as drinking water, juices, alcoholic beverages, infusions for infusions, seasoning liquids such as soy sauce and sauces, soups, honeys, sauces and dressings.
Further, alcoholic beverages include beverages containing ethyl alcohol, such as sake, shochu, beer, low-malt beer, wine, and Western liquors, seasoning liquids such as mirin, and alcoholic beverages having a low alcohol concentration or non-alcohol.

<Raw materials>
The details of the raw materials used in the examples are as follows.
[Base material layer]
-PET film 1: PET film manufactured by Toyobo Co., Ltd., Espet T4102. 12 μm thick.
And paperboard 1: having a basis weight of 380g / m ² paper substrate.
[Intermediate layer]
・ Aluminum foil 1: thickness 7 μm.
IB-PET-PIR: manufactured by Dai Nippon Printing Co., Ltd. Alumina-deposited PET film with barrier coat resin layer. 12 μm thick.
[Hydrophobic zeolite]
Mizuka Sieves EX-122: manufactured by Mizusawa Chemical Industry Co., Ltd. SiO ₂ / AL ₂ O ₃ molar ratio = 32/1, average particle size = 2.5-5.5 μm.
-Shilton MT400: manufactured by Mizusawa Chemical Industry Co., Ltd. SiO ₂ / AL ₂ O ₃ molar ratio = 400/1, average particle size = 5-7 μm.
-Shilton MT-8000: manufactured by Mizusawa Chemical Industry Co., Ltd. SiO ₂ / AL ₂ O ₃ molar ratio = 8000/1, average particle size = 0.8 μm.
[Chemical adsorbent-supported inorganic porous material]
・ Dashlight CZU1721: manufactured by Sinanen Zeomic Co., Ltd. Copper oxide / zinc oxide composite aluminosilicate, average particle size = 3-5 μm.
[Inorganic odor decomposer]
-Inorganic odor decomposer 1: manufactured by Ishizuka Glass Co., Ltd. Copper oxide kneaded glass, average particle size = 3-4 μm. [Adhesive for EC]
-EMAA-based adhesive 1: N0908C manufactured by Mitsui-Dupont Polychemical Co., Ltd.
-Novatec LC600A: manufactured by Nippon Polyethylene Corporation. LDPE, density = 0.918 g / cm ³ , MFR = 7.0.
[Adhesive for dry lamination]
Polyester adhesive 1: Adlock RU004 / H1 manufactured by Rock Paint Co., Ltd. Polyether adhesive 1: Adlock RU-3900 / H-789 manufactured by Rock Paint Co., Ltd.
[Heat-sealable thermoplastic resin]
・ Ultzex 1520L: manufactured by Prime Polymer Co., Ltd. LLDPE, density = 0.916 g / cm ³ , MFR = 2.3.
-Novatec LC600A: manufactured by Nippon Polyethylene Corporation. LDPE, density = 0.918 g / cm ³ , MFR = 7.0.

<Adjustment of deodorant adhesive layer forming composition>
The deodorizing adhesive layer forming composition was prepared by adjusting as follows.
Mizuka Sieves EX-122 was dispersed in the polyester adhesive 1 at the following ratio to obtain a deodorant adhesive layer forming composition 1.
Polyester adhesive 1 70 parts by mass Mizuka Sieves EX-122 30 parts by mass

[Adjustment of Deodorizing Adhesive Layer Forming Compositions 2 to 12]
According to the composition in Table 1, the deodorant was dispersed in the adhesive for dry lamination in the same manner as in the composition for forming a deodorant adhesive layer 1, to obtain a composition for forming a deodorant adhesive layer.

<Preparation of master batch for deodorant sealant layer>
A master batch for a deodorant sealant layer was prepared as follows.

[Preparation of master batch 1 (MB1) for deodorant sealant layer]
The following raw materials were melt-blended to obtain a master batch 1 (MB1) for a deodorant sealant layer.
Novatec LC600A 90 parts by mass Shilton MT400 10 parts by mass

[Adjustment of Masterbatches 2 to 4 (MB2 to 4) for Deodorant Sealant Layer]
According to the formulation in Table 2, similarly to Masterbatch 1 for deodorant sealant layer, thermoplastic resin and deodorant were melt-blended to obtain Masterbatches 2 to 4 (MB2 to 4) for deodorant sealant layer.

<Preparation of deodorant sealant layer composition>
[Preparation of Deodorant Sealant Layer Composition 1]
1520 L of Ultrazex, Masterbatch 1 (MB1), and Masterbatch 2 (MB2) were melt-blended at the following ratio to obtain a deodorant sealant layer composition 1.
ULTZEX 1520L 90 parts by mass MB1 5 parts by mass MB2 5 parts by mass

[Adjustment of Deodorant Sealant Layer Compositions 2 and 3]
According to the formulation in Table 3, similarly to the deodorant sealant layer composition 1, the heat-sealable thermoplastic resin and the masterbatch were melt-blended to obtain deodorant sealant layer compositions 2 and 3.

[Example 1]
A PET film 1 for the base material layer and an aluminum foil 1 for the intermediate layer are dry-laminated using the polyester adhesive 1 at a dry coating amount of 3.5 g / m ² to obtain a laminate having the following structure A precursor was obtained.
PET film 1 (12 μm) / Polyester adhesive 1 (3.5 g / m ² ) / Aluminum foil 1 (7 μm)

  Next, a sealant film for a non-deodorant sealant layer having a thickness of 40 μm was prepared by inflation film formation at 160 ° C. using 1520 L of a heat-sealable thermoplastic resin, Ultrazex 1520L.

One surface of the aluminum foil of the laminate precursor obtained above and a sealant film were laminated by a dry lamination method using the deodorant adhesive layer forming composition 1 at a dry coating amount of 3.5 g / m 2, and the following structure was adopted. The deodorant packaging material was obtained and various evaluations were performed. Table 5 shows the detailed configuration and evaluation results of the deodorant packaging material.
PET film 1 (12 μm) / polyester adhesive 1 (3.5 g / m ² ) / aluminum foil (7 μm) / deodorant adhesive layer (3.5 g / m ² ) / non-deodorant sealant layer (40 μm)

[Examples 2 to 8, 17]
A deodorizing adhesive layer forming composition was selected according to the description in Table 5, and the same operation as in Example 1 was performed to obtain a deodorant packaging material, and various evaluations were performed. Tables 5 to 7 show the detailed composition and evaluation results of the deodorant packaging material.
Shown in

[Example 9]
By operating in the same manner as in Example 1, a laminate precursor was obtained.
Next, Ulto-Zex 1520L which is a heat-sealable thermoplastic resin for the non-deodorant sealant layer, and the resin composition 1 for the deodorant sealant layer for the deodorant sealant layer, by inflation film forming at 160 ° C, A sealant film having the following configuration was produced.
Non-deodorant sealant layer 1 (10 μm) / deodorant sealant layer (20 μm) / non-deodorant sealant layer 3 (10 μm)

One side of the aluminum foil of the laminate precursor obtained above and the sealant film were opposed to each other, and the deodorizing adhesive layer forming composition 9 was laminated by a dry lamination method using a dry coating amount of 3.5 g / m ^2. The deodorant packaging material was obtained, and various evaluations were performed. Table 6 shows the detailed configuration and evaluation results of the deodorant packaging material.

[Example 10]
Except that the sealant film was prepared using the deodorant sealant layer resin composition 2 for the deodorant sealant layer, the same operation as in Example 1 was performed to obtain a deodorant packaging material, and various evaluations were performed. . Table 6 shows the detailed configuration and evaluation results of the deodorant packaging material.

[Example 11]
Novatec LC600A was laminated on one side of the paperboard 1 for the base material layer by extrusion coating to a thickness of 20 μm.
Dry lamination using the EMAA-based adhesive 1 at a dry coating amount of 3.5 g / m 2 with the surface of the paperboard 1 on which the LC600A is not laminated and the surface of the IB-PET-PIR barrier coat resin layer facing each other. The layers were laminated by a method to obtain a laminate precursor having the following structure.
Novatec LC600A (20 μm) / paperboard 1 / N0908C (3.5 g / m ² ) / IB-PET-PIR

Next, a sealant film having the following constitution was produced by inflation film formation at 160 ° C. using Ultoxex 1520L which is a heat-sealable thermoplastic resin for a non-deodorant sealant layer.
Non-deodorant sealant layer 1 (40 μm) / non-deodorant sealant layer 2 (20 μm) / non-deodorant sealant layer 3 (10 μm)

Using the IB-PET-PIR surface of the laminate precursor obtained above and one surface of the non-deodorant sealant layer of the sealant film, the deodorant adhesive layer forming composition 9 was used at a dry coating amount of 3.5 g / m ² . Then, lamination was performed by a dry lamination method to obtain a deodorant packaging material, and various evaluations were performed. Table 6 shows the detailed configuration and evaluation results of the deodorant packaging material.

[Examples 12 to 14]
A laminate precursor was obtained in the same manner as in Example 11.

Next, according to the structure of the sealant layer described in Tables 6 and 7, the same operation as in Example 11 was performed to obtain a sealant film.
Then, a deodorizing adhesive layer forming composition was selected according to the description in Table 5, and the same operation as in Example 11 was performed to obtain a deodorant packaging material, and various evaluations were performed. Tables 6 and 7 show the detailed configuration and evaluation results of the deodorant packaging material.

[Example 15]
A laminate was obtained in the same manner as in Example 11, except that the non-barrier coat resin layer surface of IB-PET-PIR was adhered to the base material layer.
Next, in the same manner as in Example 11, a sealant film was obtained, laminated with a laminate precursor, a deodorant packaging material was obtained, and various evaluations were performed. Table 7 shows the detailed configuration and evaluation results of the deodorant packaging material.

[Example 16]
A laminate precursor was obtained in the same manner as in Example 11, except that the IB-PET-PIR was changed to aluminum foil 1.
Next, in the same manner as in Example 11, a sealant film was obtained, laminated with a laminate precursor, a deodorant packaging material was obtained, and various evaluations were performed. Table 7 shows the detailed configuration and evaluation results of the deodorant packaging material.

[Comparative Example 1]
A sealant film was obtained by operating in the same manner as in Example 1 except that the deodorizing adhesive layer forming composition 1 was changed to RU004 / H1 to form a non-deodorizing adhesive without forming a deodorizing adhesive layer. The laminate was laminated with the laminate precursor to obtain a deodorant packaging material, and various evaluations were performed. Table 7 shows the detailed configuration and evaluation results of the deodorant packaging material.

[Comparative Example 2]
Except that a deodorant adhesive layer forming composition 11 was used instead of the deodorant adhesive layer forming composition 1, and a deodorant sealant layer composition 3 was used instead of Ultzex 1520L to produce a sealant film composed of a deodorant sealant layer. Was operated in the same manner as in Example 1 to obtain a deodorant packaging material, and various evaluations were performed. Table 7 shows the detailed configuration and evaluation results of the deodorant packaging material.

<Evaluation>
[Adhesiveness of adhesive layer]
The packaging materials obtained in the examples and comparative examples were cut to a width of 15 mm, and were attached to a tensile tester to measure the peel strength so as to form a T-shaped peel at the peel interface. The unit is [N / 15 mm].
(Tensile strength test conditions)
Test speed: 50mm / min Load range: 20N
(Pass / fail judgment criteria)
：: 3 N / 15 mm or more and passed.
×: less than 3 N / 15 mm, rejected.

[Heat sealability of sealant layer]
The packaging materials obtained in the examples and comparative examples were cut into 10 cm × 10 cm, folded in half and overlapped, and a heat seal tester (manufactured by Tester Sangyo Co., Ltd .: TP-701-A) was used to cover an area of 1 cm × 10 cm. The sample was heat-sealed, and the end portion was not heat-sealed and was not adhered, but was split into two parts.

This sample was cut into strips with a width of 15 mm, and each end divided into two branches was attached to a tensile tester, and the tensile strength (N / 15 mm) was measured to determine pass / fail.
(Heat sealing conditions)
Temperature: 160 ° C
Pressure: 1kgf / cm ²
Time: 1 second (tensile strength test conditions)
Test speed: 300mm / min Load range: 50N
(Pass / fail judgment criteria)
：: 30 N / 15 mm or more and passed.
X: Less than 30 N / 15 mm, rejected.

[Odor concentration]
The packaging materials (11 cm × 15 cm × 2 sheets) obtained in Examples and Comparative Examples are put in a pouch (13 cm × 17 cm) made with a gas sampling bag (Tedlar bag), and the following evaluation gas is injected into the pouch bag with a syringe. After the evaluation pouches were prepared for each evaluation gas and allowed to stand at 25 ° C. for 2 days, the air in each evaluation pouch bag was collected with a syringe, and the concentrations of dimethyl trisulfide, hydrogen sulfide, and acetaldehyde were measured by GC and a detection tube. And the respective concentrations of dimethyl trisulfide, hydrogen sulfide and acetaldehyde in the pouch bag were measured.
(Evaluation gas)
Dimethyl trisulfide: 35 ppm
Hydrogen sulfide: 25 ppm
Acetaldehyde: 30 ppm
Other components: air

<Result Summary>
All examples showed good adhesion of the adhesive layer, good seal strength of the sealant layer, and good reduction of odor concentration.
However, Comparative Example 1, which did not include the deodorant adhesive layer and the deodorant sealant layer, had excellent sealing strength, but hardly reduced the odor concentration. In Comparative Example 2 in which the adhesive layer and the sealant layer contained too much deodorant, the deodorizing effect was high, but the results showed that the adhesiveness of the adhesive layer and the heat sealability of the sealant layer were poor.

DESCRIPTION OF SYMBOLS 1 Deodorant laminated body 2 Base layer 3 Non-deodorant adhesive layer 4 Intermediate layer 4a Deposited film support layer 4b Deposited film layer 4c Metal foil layer 5 Deodorant adhesive layer (dry lamination method)
Reference Signs List 6 sealant layer 6a non-deodorant sealant layer 6b deodorant sealant layer 7 barrier coat resin layer 20 inorganic porous material supporting chemical adsorbent

Claims (14)

At least a substrate layer, a deodorant adhesive layer, a deodorant laminate including a sealant layer,
The deodorant adhesive layer contains an adhesive and a deodorant, and is a layer formed by a dry lamination method.
The deodorant is one or two selected from the group consisting of a hydrophobic zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 30/1 to 8000/1, an inorganic porous material carrying a chemical adsorbent, and an inorganic odor decomposer. Including more than species,
The inorganic odor decomposer is obtained by kneading or supporting a metal oxide or a metal salt on an inorganic substance,
The deodorant laminate, wherein the content of the deodorant in the adhesive layer including the deodorant adhesive layer is 0.2% by mass or more and 30% by mass or less. The sealant layer contains a heat sealable thermoplastic resin and the deodorant,
The content of the deodorant in the sealant layer is 0.2% by mass or more and 15% by mass or less;
The deodorant laminate according to claim 1. The chemical adsorbent-supported inorganic porous material contains one or more elements selected from the group consisting of copper, zinc, silver, platinum, iron, and cobalt.
The deodorant laminate according to claim 1. The inorganic odor decomposer contains one or more elements selected from the group consisting of copper, zinc, silver, platinum, iron, and cobalt.
The deodorant laminate according to any one of claims 1 to 3. The deodorant contains two or three selected from the group consisting of the hydrophobic zeolite, the inorganic porous material carrying the chemical adsorbent, and the inorganic odor decomposer,
The total content of the deodorant in the adhesive layer including the deodorant adhesive layer is 0.2% by mass or more and 20% by mass or less.
The deodorant laminate according to any one of claims 1 to 4. The deodorant contains two or three selected from the group consisting of the hydrophobic zeolite, the inorganic porous material carrying the chemical adsorbent, and the inorganic odor decomposer,
The total content of the deodorant in the sealant layer is 0.2% by mass or more and 10% by mass or less.
The deodorant laminate according to any one of claims 2 to 5.   The deodorant laminate according to any one of claims 1 to 6, wherein the base layer includes a paper material. In addition, including an intermediate layer,
The intermediate layer includes one or two or more gas barrier layers selected from the group consisting of a metal foil, a metal deposited film, a metal oxide deposited film,
The deodorant laminate according to any one of claims 1 to 7. Further, as an intermediate layer, including aluminum foil,
The deodorant laminate according to any one of claims 1 to 7. Furthermore, the intermediate layer includes a barrier coat resin layer on the gas barrier layer,
The deodorant laminate according to claim 8 or 9.   A deodorant packaging material produced from the deodorant laminate according to any one of claims 1 to 10.   A deodorant package produced from the deodorant packaging material according to claim 11.   A deodorant packaging for liquid contents, produced from the deodorant packaging material according to claim 11.   A deodorant packaging for alcoholic beverages produced from the deodorant packaging material according to claim 11.

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