JP2020001272A - Deodorant laminate for liquid content and deodorant package for liquid content - Google Patents

Abstract

To provide a laminate for liquid contents which exhibits a deodorant effect due to high adsorption or decomposition action against an originally contained odor organic matter, odor generated at the time of sterilization/disinfection treatment and an odor component generated from contents themselves over a long period of time; and a packaging material and a package using the laminate.SOLUTION: A deodorant laminate 1 for liquid content contains at least a base material layer 2, an intermediate layer 4 and a sealant layer 6, in which the base material layer contains a polyolefin-based resin layer 2a and a paper layer 2b, the intermediate layer contains a barrier layer, the sealant layer contains a deodorant body and a heat sealable thermoplastic resin, the deodorant body contains one or two or more types selected from the group consisting of hydrophobic zeolite having SiO/AlOwith molar 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 total of the deodorant body in the sealant layer is 0.2 mass% or more and 15 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 A laminate for liquid contents, which exhibits a deodorizing effect due to a decomposition action over a long period of time and is excellent in long-term odor resistance to contents, and a packaging material and a package using the laminate. The purpose is to provide.

  As a result of various studies, the present inventors have found that at least, at least, a specific base material layer, an intermediate layer, and a laminate including a sealant layer containing a deodorant and a heat-sealable thermoplastic resin have the above object. To achieve.

That is, the present invention has the following features.
1. At least, a substrate layer, an intermediate layer, and a sealant layer, a deodorant laminate for liquid contents,
The base layer includes a polyolefin-based resin layer and a paper layer,
The intermediate layer includes a barrier layer,
The sealant layer contains a deodorant and a heat-sealable thermoplastic resin,
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 for a liquid content, wherein the total content of the deodorant in the sealant layer is 0.2% by mass or more and 15% by mass or less.
2. The deodorant is melt-kneaded with the thermoplastic resin in advance at a mass ratio of the deodorant / thermoplastic resin of 0.5 / 99.5 to 40/60.
2. The deodorant laminate for liquid contents according to 1 above.
3. The melt flow rate of the heat-sealable thermoplastic resin is 0.2 g / 10 min or more and 10.0 g / 10 min or less.
3. The deodorant laminate for liquid contents according to 1 or 2 above.
4. The sealant layer includes a deodorant sealant layer containing the deodorant, and a non-deodorant sealant layer not containing the deodorant,
The non-deodorant sealant layer is laminated in contact with one side and / or both sides of the deodorant sealant layer,
4. The deodorant laminate for liquid contents according to any one of the above 1 to 3.
5. 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.
5. The deodorant laminate for liquid contents according to any one of the above 1 to 4.
6. The inorganic odor decomposer contains one or more elements selected from the group consisting of copper, zinc, silver, platinum, iron, and cobalt.
6. The deodorant laminate for liquid contents according to any one of 1 to 5 above.
7. 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.
7. The deodorant laminate for liquid contents according to any one of 1 to 6 above.
8. A deodorant packaging material for alcoholic beverages produced from the deodorant laminate for liquid contents according to any one of the above 1 to 7.
9. 9. A deodorant packaging for alcoholic beverages, produced from the packaging material for deodorizing alcoholic beverages according to 8 above.

  Since the deodorant laminate of the present invention has a specific deodorant and a sealant layer containing a heat-sealable thermoplastic resin, the deodorant is efficiently adsorbed or decomposed to deodorize, and is excellent. Heat sealability can be exhibited.

  Odor includes the decomposition of the 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 deodorant laminate of the present invention, and an odor due to an odor component generated from the liquid content itself when a packing bag is prepared using the deodorant laminate of the present invention. It is possible to suppress the above-mentioned odor from being transferred to or remaining in the liquid contents, and suppress a 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.

  Furthermore, the deodorant laminate of the present invention is excellent in organic solvent resistance and gas barrier properties because the base layer includes a polyolefin-based resin layer and a paper layer, and the intermediate layer includes a barrier layer.

  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, an intermediate layer, and a sealant layer. Further, if necessary, as shown in FIGS. 2 and 3, another layer such as an intermediate layer or an adhesive layer can be included.

<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 by being molded into a film, or applied, impregnated or coated on paper or the like, and has excellent chemical or physical strength. preferable.

  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, polyethylene naphthalate, polyamide resin such as various nylons, polyurethane resin, acetal resin, cellulose resin, etc. Of various resins.

  In the present invention, among the above resins, it is preferable to use a film or a sheet of a polyester resin, a polyolefin resin, or a polyamide resin, and particularly preferable is a polyolefin resin.

  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>
In the present invention, as shown in FIG. 2, it is possible to bond each layer with an adhesive layer.

  The 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.

  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, inorganic adhesive or the like made of a low-melting glass.

  When performing dry lamination coating, for example, after applying and drying the resin composition for the adhesive layer 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.

  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 and the} like.

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 a deodorant.

  The deodorant sealant film of the present invention can exhibit excellent heat sealing properties when the sealant layer contains a heat sealable thermofacial resin, and exhibits excellent deodorizing properties by containing a deodorant. An odor effect can be exhibited.

  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.

  When the content of the deodorant is less than the above range, it is difficult to exert a sufficient deodorizing effect, and when 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.

  The content of the deodorant in the sealant layer including the deodorant sealant layer and the non-deodorant sealant layer is preferably from 0.2% by mass to 15% by mass.

  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.

[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]
(Dispersing method of deodorant)
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. 1, the deodorant laminate of the present invention includes an intermediate layer, and can impart various functions as needed.

  For example, as a barrier layer, a metal foil, a thermoplastic resin film on which a metal deposited film layer or a metal oxide deposited film layer is formed, and further, as shown in FIG. 2, a barrier coat resin layer on the metal deposited film layer Can also be 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 heat sealing method, for example, a known method such as a bar seal, a rotating roll seal, a belt seal, 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]
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.
[Adhesive for dry lamination]
Polyester adhesive 1: Adlock RU004 / H1 manufactured by Rock Paint Co., Ltd. [Heat-sealable thermoplastic resin, thermoplastic resin, EC adhesive]
・ 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 sealant layer master batch>
The thermoplastic resin and the deodorant were melt-blended at a ratio according to the formulation in Table 1 to obtain deodorant sealant layer masterbatches 1 to 9 (MB1 to 9).

<Preparation of deodorant sealant layer resin composition>
According to the compounding ratio described in Table 2, the heat-sealable thermoplastic resin and the deodorant sealant layer masterbatch were melt-blended to obtain deodorant sealant layer compositions 1 to 14.

[Example 1]
On one side of the paper substrate 1, Novatec LC600A, which is a low-density polyethylene resin as a polyolefin resin, was laminated to a thickness of 20 μm by an extrusion coating method which was melt-extruded with a T-die extruder.

  The other side of the paper substrate and the surface of the intermediate layer IB-PET-PIR barrier coat resin layer were melt extruded by a T-die extruder and laminated by extrusion coating to form a 20 μm thick EMAA. Bonding was performed with the system adhesive 1 to obtain a laminate precursor.

Next, using a heat-sealable thermoplastic resin Ultoxex 1520L for a non-deodorant sealant layer and a deodorant sealant layer resin composition 1 for a deodorant sealant layer, the following was performed by inflation film formation at 160 ° C. A three-layer system sealant film having a thickness of 40 μm was produced.
Non-deodorant sealant layer (10 μm) / deodorant sealant layer (20 μm) / non-deodorant sealant layer (10 μm)

Then, the polyester adhesive 1 was applied at a dry coating amount of 3.5 g / m ² on the IB-PET-PIR surface of the laminate precursor obtained above and dried, and the sealant film obtained above was dried. Lamination was performed by a dry lamination method to obtain a laminate having the following configuration, and various evaluations were performed. Table 3 shows the detailed configuration of the laminate and the evaluation results.
Polyolefin resin layer (20 μm) / paper layer (382 g / m ² ) / adhesive layer (20 μm) / IB-PET-PIR (12 μm) / adhesive layer (3.5 g / m ² ) / non-deodorant sealant layer (10 μm ) / Deodorant sealant layer (20 μm) / Non-deodorant sealant layer (10 μm)

[Examples 2 to 8]
A deodorant sealant layer resin composition was selected according to the description in Table 3 and operated in the same manner as in Example 1 to obtain a laminate precursor, a sealant film, and a laminate, and various evaluations were performed. Table 3 shows the detailed configuration of the laminate and the evaluation results.

[Example 9]
A laminate precursor, a sealant film, and a laminate were obtained in the same manner as in Example 1, except that the deodorant sealant film was changed to a single-layer structure having a thickness of 40 μm using the deodorant sealant layer resin composition 9. Various evaluations were conducted. Table 3 shows the detailed configuration of the laminate and the evaluation results.

[Examples 10 to 11, 14 to 17]
As in Example 1, a laminate precursor and a deodorant sealant layer resin composition according to the description in Table 3 were selected to produce a sealant film.
Next, the obtained laminate precursor and the sealant film were formed into an adhesive layer having a thickness of 15 μm by an extrusion coating method using Novatec LC600A, and bonded to obtain a laminate. Carried out. Table 3 shows the detailed configuration of the laminate and the evaluation results.

[Example 12]
The same procedure as in Example 10 was followed, except that the other side of the paper base material and the surface of the intermediate layer opposite to the IB-PET-PIR barrier coat resin layer surface were adhered to obtain a laminate precursor. , A sealant film and a laminate were obtained, and various evaluations were performed. Table 3 shows the detailed configuration of the laminate and the evaluation results.

Example 13
A laminate precursor, a sealant film, and a laminate were obtained in the same manner as in Example 10 except that the aluminum foil 1 was used for the intermediate layer, and various evaluations were performed. Table 3 shows the detailed configuration of the laminate and the evaluation results.

[Comparative Example 1]
A laminate precursor was produced in the same manner as in Example 1.
Next, on the IB-PET-PIR surface of the obtained laminate precursor, Ultoxex 1520L was laminated by extrusion lamination as a sealant layer to obtain a laminate, and various evaluations were performed in the same manner as in Example 1. . Table 3 shows the detailed configuration of the packaging material and the evaluation results.

[Comparative Example 2]
A laminate was obtained in the same manner as in Comparative Example 1 except that the deodorant sealant layer resin composition 10 was used as the sealant layer, and various evaluations were performed as in Example 1. Table 3 shows the detailed configuration of the packaging material and the evaluation results.

<Evaluation>
[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 excellent seal strength and excellent odor concentration reduction.

  However, in Comparative Example 1 in which the sealant layer did not contain a deodorant, although the seal strength was excellent, the odor concentration hardly decreased, and Comparative Example 2 in which the deodorant content of the sealant layer was too high was heat-sealed. Sex was poor.

DESCRIPTION OF SYMBOLS 1 Deodorant laminated body for liquid contents 2 Base layer 2a Polyolefin resin layer 2b Paper layer 3 Adhesive layer 4 Intermediate layer 4a Deposited film support layer 4b Deposited film layer 4c Metal foil layer 6 Sealant layer 6a Non-deodorant sealant layer 6b Deodorant sealant layer 7 Barrier coat resin layer 20 Chemically adsorbent-supported inorganic porous material

Claims (9)

At least, a substrate layer, an intermediate layer, and a sealant layer, a deodorant laminate for liquid contents,
The base layer includes a polyolefin-based resin layer and a paper layer,
The intermediate layer includes a barrier layer,
The sealant layer contains a deodorant and a heat-sealable thermoplastic resin,
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 for a liquid content, wherein the total content of the deodorant in the sealant layer is 0.2% by mass or more and 15% by mass or less. The deodorant is melt-kneaded with the thermoplastic resin in advance at a mass ratio of the deodorant / thermoplastic resin of 0.5 / 99.5 to 40/60.
The deodorant laminate for liquid contents according to claim 1. The melt flow rate of the heat-sealable thermoplastic resin is 0.2 g / 10 min or more and 10.0 g / 10 min or less.
The deodorant laminate for liquid contents according to claim 1 or 2. The sealant layer includes a deodorant sealant layer containing the deodorant, and a non-deodorant sealant layer not containing the deodorant,
The non-deodorant sealant layer is laminated in contact with one side and / or both sides of the deodorant sealant layer,
The deodorant laminate for liquid contents according to any one of claims 1 to 3. 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 for liquid contents according to any one of claims 1 to 4. 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 for liquid contents according to any one of claims 1 to 5. 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 for liquid contents according to any one of claims 1 to 6.   A deodorant packaging material for alcoholic beverages, produced from the deodorant laminate for liquid contents according to any one of claims 1 to 7.   An alcoholic deodorant package produced from the alcoholic beverage deodorant packaging material according to claim 8.

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