JP2020157559A - Deodorant laminate - Google Patents

Abstract

To provide a deodorant package which is excellent in manufacturing suitability, prevents changes in taste and odor by an odor component generated by hydrolysis and fullness of the odor component when the content is a food product and a medicine, and is excellent in resistance to change in odor for a long period of time that prevents deterioration and deterioration resistance by moisture when the content is an electronic component, an electronic device and an industrial material.SOLUTION: A deodorant laminate 1 is composed of a base material layer 2 and a sealant layer 4, in which the sealant layer has a deodorant layer 5 and a hydrolysis suppression layer 6, the deodorant layer contains a deodorant and a polyolefin-based resin, the deodorant contains a chemical odor adsorbent and/or hydrophobic zeolite having a molar ratio of silica to alumina of 30/1 to 10,000/1, the hydrolysis suppression layer contains a hydrolysis inhibitor and a polyolefin-based resin, and the hydrolysis inhibitor contains a moisture-absorbing alkali metal compound and/or one or two or more selected from the group consisting of a moisture-absorbing alkali earth metal compound and hydrophilic zeolite having a ratio of silica to alumina of 1/1 to 20/1.SELECTED DRAWING: Figure 1

Description

The present invention prevents the contents packaged in the package from causing discoloration or odor, prevents the odorous components from filling the inside of the package and causing an offensive odor at the time of opening, and the contents are affected by moisture. Deodorant packaging laminates that prevent this from happening and have excellent long-term odor resistance changeability and moisture deterioration resistance of the contents, and deodorant packaging materials and deodorant packaging materials made from the deodorant packaging laminates. Regarding.

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

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

Further, a hygroscopic packaging material that suppresses the generation of an offensive odor due to hydrolysis of the contents is also known (Patent Document 3), but although it has an odor generation suppressing effect, the generated odor component remains as it is. However, a sufficient odor improving effect was not obtained.

Japanese Patent No. 2538487 JP-A-2014-233408 Japanese Unexamined Patent Publication No. 2006-327690

The present invention solves the above-mentioned problems, is excellent in manufacturing suitability, and when the content packaged in the package is a food or a pharmaceutical product, the odorous component generated by hydrolysis causes the content to be discolored. Prevents the generation of odors and gives an odor improving effect, prevents the odorous components from filling the inside of the package and feeling a strange odor when opened, and the contents of electronic parts, electronic devices, industrial materials, etc. In this case, it is an object of the present invention to provide a deodorant package which prevents deterioration and has excellent long-term odor resistance changeability and deterioration resistance due to moisture.

As a result of various studies, the present inventors have found that a laminate having at least a base material layer, a deodorant layer containing a specific deodorant, and a hydrolysis inhibitory layer containing a specific hydrolysis inhibitor is described above. Found to achieve the purpose of.

That is, the present invention is characterized by the following points.
1. 1. A deodorant laminate for packaging materials having a base material layer and a sealant layer.
The sealant layer has a deodorant layer and a hydrolysis inhibitory layer.
The deodorant layer contains a deodorant and a polyolefin resin, and contains
The deodorant contains a chemical odor adsorbent and / or a hydrophobic zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 30/1 to 10000/1.
The hydrolysis inhibitory layer contains a hydrolysis inhibitor and a polyolefin resin.
The hydrolysis inhibitor consists of a group consisting of a hygroscopic alkali metal compound and / or a hygroscopic alkaline earth metal compound and a hydrophilic zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 1/1 to 20/1. Contains one or more selected species,
The content of the deodorant in the deodorant layer is 0.5% by mass or more and 15% by mass or less.
A deodorant laminate characterized in that the content of the hydrolysis inhibitor in the hydrolysis inhibitor layer is 1% by mass or more and 50% by mass or less.
2. 2. The deodorant laminate further has a gas barrier layer between the base material layer, the deodorant layer and the hydrolysis inhibitory layer.
The gas barrier layer is one or more selected from the group consisting of a gas barrier resin film, a metal foil, a resin film with a metal vapor deposition layer, a resin film with a metal oxide vapor deposition layer, and a gas barrier resin coating film. Characteristic,
The deodorant laminate according to 1 above.
3. 3. The outer surface layer of the sealant layer is the deodorant layer or the hydrolysis inhibitory layer.
The deodorant laminate according to 1 or 2 above.
4. The outer surface layer of the sealant layer, or the outer surface layer of the sealant layer and the layer on the most base material side side contain a polyolefin resin and do not contain the deodorant and the hydrolysis inhibitor. It is a heat seal layer,
The deodorant laminate according to 1 or 2 above.
5. The polyolefin-based resin is LDPE and / or LLDPE having a density of 0.90 g / cm ³ or more and 0.94 g / cm ³ or less.
The deodorant laminate according to any one of 1 to 4 above.
6. A deodorant packaging material comprising the deodorant laminate according to any one of 1 to 5 above.
7. A deodorant packaging body, which is produced by using the deodorant packaging material described in 6 above.
8. A deodorant packaging bag made by using the deodorant packaging material described in 6 above.
9. A deodorant pouch bag made by using the deodorant packaging material described in 6 above.

The gas adsorption package of the present invention is excellent in manufacturing suitability, and prevents deterioration of the contents packaged in the package due to moisture and odorous components generated by hydrolysis from causing discoloration or odor of the contents. When the content is food or pharmaceutical, it gives an odor improving effect, prevents the odor component from filling the inside of the package and feeling a strange odor when opened, and the content dislikes moisture. Electronic parts, electronic devices, In the case of industrial materials, deterioration can be prevented.
Then, since the odor and water once adsorbed are hard to be desorbed and are efficiently adsorbed, it is possible to provide a deodorant package that exhibits a high hygroscopic effect and a deodorant effect for a long period of time.
Therefore, the deodorant packaging of the present invention is suitable as a packaging application for dried foods, pharmaceuticals, medical products, electronic parts that dislike moisture, electronic devices, and industrial materials.

It is a schematic external view which shows an example of the deodorant packaging body of this invention. It is the schematic sectional drawing which shows an example about the layer structure of the deodorant packaging body of this invention. It is the schematic sectional drawing which shows an example of the other aspect about the layer structure of the deodorant packaging body of this invention. It is the schematic sectional drawing which shows an example of the other aspect about the layer structure of the deodorant packaging body of this invention. It is the schematic which shows the odor adsorption mechanism of the chemical odor adsorbent-supporting inorganic porous body in this invention.

In each figure, the size and ratio of the members may be changed or exaggerated for the sake of clarity. In addition, for the sake of readability, unnecessary parts for explanation and repeated codes may be omitted.
Further, in each figure, the uneven portion is illustrated as a pattern having clear corners, but the shape may have rounded corners.

The deodorant package of the present invention will be described in more detail below. The present invention will be described with reference to specific examples, but the present invention is not limited thereto.

<Layer structure of deodorant laminate>
The deodorant laminate for the packaging material of the present invention has a base material layer and a sealant layer.
Then, the deodorant laminate may further have a gas barrier layer between the base material layer, the deodorant layer and the hydrolysis inhibitory layer, if necessary.

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

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

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

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

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

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

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

<Sealant layer>
The sealant layer has a deodorant layer and a hydrolysis suppressing layer. The sealant layer may further have a heat seal layer, if necessary.
The outer surface layer of the sealant layer may be a deodorant layer or a hydrolysis inhibitory layer, or may be a heat seal layer. Further, the layer on the outermost base layer side of the sealant layer may be a heat seal layer.
Since the heat-sealing layer has excellent heat-sealing properties, when the outer surface layer of the sealant layer is a heat-sealing layer, the heat-sealing properties of the deodorant laminate can be improved.
Further, by forming the layer on the outermost base layer side of the sealant layer as a heat seal layer, the adhesive strength at the interface of the sealant layer inside the deodorant laminate can be increased.
The sealant layer can also contain lubricants, antioxidants, antiblocks and other additives.

(Method of forming and laminating the sealant layer)
In the present invention, the sealant layer or the film forming and laminating method of each layer constituting the sealant layer is not particularly limited, and a known or conventional film forming method or laminating method can be applied.
A sealant layer, a deodorant layer, a hydrolysis inhibitory layer, or a heat seal layer is extruded or co-extruded onto another layer by an extrusion coating method, or an adhesive layer is formed after film formation by an inflation method or a casting method. It can also be laminated via. Even in the case of the extrusion coating method, the layers may be laminated via an adhesive layer if necessary.
Alternatively, a film for a sealant layer, a deodorant layer, a hydrolysis suppression layer, and a heat seal layer that have been formed in advance is passed through an adhesive layer laminated by an extrusion coating method, a dry laminating method, a non-solvent laminating method, or the like. It may be laminated or bonded.

When laminating by the extrusion coating method, first, the resin composition forming the sealant layer, the deodorant layer, the hydrolysis suppression layer, the heat seal layer, etc. is heated and melted, and then the width direction required by the T-die is used. A sealant layer, a deodorant layer, and a hydrolysis suppressing layer are formed by expanding and stretching the resin to form a curtain (co), allowing the molten resin to flow down onto the surface to be laminated, and sandwiching the molten resin between a rubber roll and a cooled metal roll. , The heat seal layer and the like can be formed, laminated and bonded to the surface to be laminated, laminated and bonded between the layers, and the like at the same time.
The melt flow rate (MFR) of the resin component contained in the sealant layer when laminated by the extrusion coating method is preferably 0.2 to 50 g / 10 minutes, more preferably 0.5 to 30 g / 10 minutes. In this specification, MFR is a value measured by a method based on JIS K7210.
If the MFR is less than 0.2 g / 10 minutes or larger than 50 g / 10 minutes, the processing suitability tends to be inferior.

When the inflation method is used, the melt flow rate (MFR) of the resin component contained in the sealant layer is preferably 0.2 to 10 g / 10 minutes, more preferably 0.2 to 9.5 g / 10 minutes.
If the MFR is less than 0.2 g / 10 minutes or larger than 10 g / 10 minutes, the processing suitability tends to be inferior.

[Heat seal layer]
The heat seal layer is a layer that does not contain a deodorant and the hydrolysis inhibitor but contains a polyolefin resin, and is a layer having excellent heat seal properties.

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

(Deodorants)
The deodorant is a compound having an action of deodorizing the content itself and the odorous substance generated by the hydrolysis of the content.
As the deodorant, a chemical odor adsorbent and / or a hydrophobic zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 30/1 to 10000/1 can be used. Furthermore, an odor-degradable metal compound may be used, if necessary.

The chemical odor adsorbent is a compound having a reactive functional group that chemically reacts with the content itself and the odorous substance generated by hydrolysis of the content, and for example, aldehydes, ketones, and carboxylic acids. It is a compound having a functional group having reactivity to bind to such as.
Examples of such a compound include an amino group-containing compound, a carboxyl group-containing compound, a hydroxyl group-containing compound, a carbonate, and a hydrogen carbonate.

Specific examples of the amino group-containing compound include alkylamines such as ethylenediamine, diethylenetriamine and triethylenetriamine, phenylamines such as metaphenylenediamine, polyamines such as tetramethylenediamine and tetraethylenepentamine, ethanolamine, piperazine and piperidine. And so on.

Specific examples of the carboxyl group-containing compound include 2-acrylamide-2-methylpropanesulfonic acid.

Specific examples of the hydroxyl group-containing compound include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, and iron hydroxide.
Specific examples of carbonates include metal carbonates such as sodium carbonate and calcium carbonate.
Specific examples of hydrogen carbonate include metallic hydrogen carbonate such as sodium hydrogen carbonate.
The chemical odor adsorbent can also be supported on the inorganic porous body and used as the chemical odor adsorbent-supporting inorganic porous body.

The adsorption mechanism of the chemical odor adsorbent on odorous substances will be described in more detail with reference to the specific examples of FIGS. 5A to 5B, but the present invention is not limited thereto. In FIGS. 5A to 5B, the chemical odor adsorbent is used by being supported on, for example, an inorganic porous body.
For example, when the odorous substance is a carboxylic acid-based odorous substance, as shown in FIG. 5A, for example, a compound having a hydroxyl group can be used as the chemical odor adsorbent. As a result, the carboxyl group and the hydroxyl group cause a chemical reaction to bond with each other, and the odorous substance is adsorbed.
When the odorous substance is an aldehyde, for example, a compound having an amino group can be used as the chemical odor adsorbent, as shown in FIG. 5 (b). As a result, the aldehyde group and the amino group cause a chemical reaction to bond with each other, and the odorous substance is adsorbed.

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

The shape of the agent inorganic porous body supported by the chemical odor adsorption may be any outer shape such as spherical, rod-shaped, or elliptical, and may be any form such as powder, lump, or granular, but in the resin. From the viewpoint of uniform dispersibility, kneading characteristics, film-forming property, etc. when dispersed in a powder, the powder form is preferable.
In the present invention, the average particle size of the agent-inorganic porous body supported by the chemical odor adsorption can be appropriately selected depending on the intended use, and the average particle size is 0.01 μm to 10 μm. Those are preferable. Here, the average particle size is a value measured by a dynamic light scattering method.
When the average particle size is smaller than 0.01 μm, aggregation of the agent-inorganic porous body supported by chemical odor adsorption 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 agent inorganic porous body supported by chemical odor adsorption tends to be inferior. Therefore, the agent inorganic porous body supported by chemical odor adsorption tends to be inferior. Most of them tend to be difficult to add, and the surface area is also reduced, so that a sufficient deodorizing effect may not be obtained.

The SiO ₂ / Al ₂ O ₃ molar ratio of the hydrophobic zeolite is preferably 30/1 to 10000/1, more preferably 35/1 to 9000/1, and even more preferably 40/1 to 8500/1.
Generally, the higher the SiO ₂ / Al ₂ O ₃ molar ratio, the higher the hydrophobicity of zeolite. As the hydrophobicity increases, it becomes difficult to adsorb highly polar water molecules, and conversely, the affinity with low-polarity odorous substances, hydrophobic gases, and lipophilic gases (including solvent-based gases) is high. Therefore, it becomes easy to adsorb these. Further, the zeolite surface is basic due to the effects of alkali metals such as Ca, Na and K and alkaline earth metals existing on the zeolite surface, and acid gas is easily adsorbed by the neutralization reaction.
In the present invention, hydrophobic zeolite having a molar ratio in the above range is preferably used from the viewpoint of the balance between the adsorption performance of odorous substances and the availability.
In addition, hydrophobic zeolite has high heat resistance and can maintain the adsorption effect of odorous substances even when exposed to a high temperature of 230 ° C. or higher.

The shape of the hydrophobic zeolite may be any outer shape such as spherical, rod-shaped, or elliptical, and may be any shape such as powder, lump, or granular, but when dispersed in the resin, From the viewpoint of uniform dispersibility, kneading characteristics, film forming property, etc., the powder form is preferable.
In the present invention, the average particle size of the hydrophobic zeolite can be appropriately selected depending on the intended use, but the average particle size is preferably 0.01 μm to 10 μm. Here, the average particle size is a value measured by a dynamic light scattering method.
When the average particle size is smaller than 0.01 μm, the hydrophobic zeolite tends to aggregate and the dispersibility 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 a large amount of the hydrophobic zeolite, and the surface area also decreases. In addition, there is a possibility that a sufficient deodorizing effect cannot be obtained.

The odor-degradable metal compound is a metal compound having an action of chemically decomposing an odorous substance.
The odor-degradable metal compound exerts a deodorizing effect by ionizing the metal atoms retained in the odor-degrading metal compound and exerting a catalytic action that promotes the decomposition reaction of the odorous substance.
The odor-degradable metal compound also has a high deodorizing effect on sulfur-based odorous substances.

The odor-degradable metal compound is preferably an oxide and / or salt of one or more elements selected from the group consisting of copper, zinc, silver, platinum, gold, iron and cobalt.
Examples of the metal oxide include CuO, Cu ₂ O, ZnO, Ag ₂ O, PtO ₂ , Au ₂ O ₃ , FeO, Fe ₃ O ₄ , Fe ₂ O ₃ , CoO, Co ₂ O ₃ , and Co ₃ O. _4th grade can be mentioned. Among these, CuO (copper oxide (II) oxide) and ZnO are preferable.

Since the odor-degradable metal compound promotes the decomposition reaction of the odorous substance as a catalyst, the deodorizing capacity can be increased as compared with the case where it depends on the surface area by using chemisorption or physisorption, and the deodorizing effect. Can be stably exerted over a long period of time.

The particle size distribution of the odor-degradable metal compound preferably has a weight average particle size of 1 μm or more and 30 μm or less, and D ₉₆ of 40 μm or less. Here, the average particle size is a value measured by measuring the particle size distribution by a dynamic light scattering method, and D ₉₆ means a particle size in which the integrated value when cumulatively distributed corresponds to 96% by mass.
When the average particle size is smaller than 1 μm, the odor-degradable metal compound tends to aggregate, and the dispersibility in the sealant layer tends to decrease. Further, when the average particle size 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 odor-degradable metal compounds, and the surface area is also reduced, which is sufficient. It may be difficult to obtain the deodorizing effect.
If D ₉₆ exceeds 40 μm, uniform dispersion in the resin tends to be difficult, and the film-forming property may deteriorate.
The odor-degradable metal compound can also be used by kneading or supporting it on an inorganic substance.

(Dispersion method of deodorant)
As a method of dispersing the deodorant in the deodorant-dispersed resin, a known or conventional kneading method can be applied.
The deodorant can be directly mixed with the deodorant dispersion resin and kneaded, or the deodorant is mixed with the thermoplastic resin at a high concentration and then melt-kneaded (melt blended) to form a masterbatch. It can also be produced by a so-called masterbatch method in which the resin is mixed with a deodorant dispersion resin for a deodorant layer and melt-kneaded at a ratio according to the target content rate.
In the case of the masterbatch method, even a combination of a deodorant and a resin, which tends to cause aggregation, can be efficiently and uniformly dispersed.

The content of the deodorant in the masterbatch is preferably 0.5% by mass or more and 40% by mass or less, and more preferably 1% by mass or more and 20% by mass or less. If it is less than the above range, the degree of freedom of the content of the deodorant or the hydrolysis inhibitor in the layer tends to be small, and if it is more than the above range, it tends to be difficult to obtain excellent dispersibility.

Examples of the thermoplastic resin used in the masterbatch include, but are not limited to, general-purpose polyethylene, polypropylene, methylpentene polymer, polyolefin-based resins such as acid-modified polyolefin-based resins, and mixtures of these resins.
At this time, the thermoplastic resin in the masterbatch may be the same as or different from the deodorant dispersion resin in the deodorant layer, and different types of resins may be heat-sealed in the deodorant layer depending on the purpose. It is possible to combine them within a range that does not significantly adversely affect the properties and film-forming properties.
For example, if the same resin as the deodorant dispersion resin in the deodorant layer is used for the masterbatch, the deodorant layer tends to be homogeneous, and has good film-forming property, heat-sealing property, interlayer adhesive strength, and deodorant. It is possible to efficiently obtain odor.

[Hydration suppression layer]
The hydrolysis inhibitory layer is a layer containing a hydrolysis inhibitor and a polyolefin resin, and is a layer that suppresses hydrolysis of the contents by absorbing moisture.
The hydrolysis inhibitory layer may have a single layer structure, or may have two or more layers having the same or different composition.

(Hydrolyzant)
The hydrolysis inhibitor is a compound having hygroscopicity for suppressing hydrolysis of the contents. Since water is essential for hydrolysis of the contents, the hydrolysis inhibitor absorbs moisture to reduce the amount of water, so that the progress of hydrolysis can be suppressed and the generation of odorous substances can be suppressed. Further, in the case of electronic parts, electronic devices, industrial materials and the like whose contents dislike moisture, deterioration can be suppressed.
As the hydrolysis inhibitor, one or more selected from the group consisting of hygroscopic alkali metal compounds, hygroscopic alkaline earth metal compounds, and hydrophilic zeolites can be used.

The content of the hydrolysis inhibitor in the hydrolysis inhibitor layer is preferably 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 50% by mass or less. If it is less than the above range, the effect of the hydrolysis inhibitor is difficult to be exhibited, and if it is more than the above range, the film-forming property is likely to deteriorate.

As the hygroscopic alkali metal compound or the hygroscopic alkaline earth metal compound, specifically, Li ₂ O, Na ₂ O, K ₂ O, MgO, CaO, BaO, LiCl, and LiOH are preferable, and among these, MgO , CaO is more preferred.

The SiO ₂ / Al ₂ O ₃ molar ratio of the hydrophilic zeolite is preferably 1/1 to 20/1, more preferably 1.5 / 1 to 10/1, and even more preferably 2/1 to 5/1.
Generally, the lower the SiO ₂ / Al ₂ O ₃ molar ratio, the higher the hydrophilicity of zeolite. The higher hydrophilicity makes it easier to adsorb highly polar water molecules, and conversely, the affinity with less polar odorous substances, hydrophobic gases, and lipophilic gases (including solvent-based gases) is low. It becomes difficult to adsorb these.
In the present invention, hydrophilic zeolite having a molar ratio in the above range is preferably used in view of the balance between hygroscopic performance and availability.
Further, the hydrophilic zeolite has high heat resistance, can maintain the hygroscopic effect even when exposed to a high temperature of 230 ° C. or higher, and can be used for high-temperature lamination of 230 ° C. or higher by extrusion.

The shape of the hydrolysis inhibitor may be any outer shape such as spherical, rod-shaped, elliptical, etc., and may be any shape such as powder-like, lump-like, or granular, but when dispersed in the resin. From the viewpoint of uniform dispersibility, kneading characteristics, film forming property, etc., powdery form is preferable.
In the present invention, the average particle size of the hydrolysis inhibitor can be appropriately selected depending on the intended use, but the average particle size is preferably 0.01 μm to 10 μm. Here, the average particle size is a value measured by a dynamic light scattering method.
When the average particle size is smaller than 0.01 μm, the hydrolysis inhibitor tends to aggregate and the dispersibility tends to decrease. Further, when the average particle size is larger than 10 μm, the film-forming property of the layer containing the hydrolysis inhibitor tends to be inferior, so that it tends to be difficult to add a large amount of the hydrolysis inhibitor, and the surface area is further reduced. Therefore, there is a possibility that a sufficient moisture absorbing effect cannot be obtained.

(Dispersion method of hydrolysis inhibitor)
As a method for dispersing the hydrolysis inhibitor in the hydrolysis inhibitor dispersion resin, a known or conventional kneading method can be applied.
The hydrolysis inhibitor can be directly mixed with the hydrolysis inhibitor dispersion resin and kneaded, or the hydrolysis inhibitor is mixed with the thermoplastic resin at a high concentration and then melt-kneaded (melt blend). It is also possible to prepare a masterbatch, mix it with a hydrolysis inhibitor dispersion resin for a hydrolysis inhibitor layer at a ratio according to a target content, and melt-knead it, that is, a so-called masterbatch method.
In the case of the masterbatch method, even a combination of the hydrolysis inhibitor and the hydrolysis inhibitor dispersion resin, which tends to cause aggregation, can be efficiently and uniformly dispersed.

The content of the hygroscopic alkali metal compound in the masterbatch is preferably 0.5% by mass or more and 65% by mass or less, and more preferably 1% by mass or more and 60% by mass or less.
The content of the hygroscopic alkaline earth metal compound in the masterbatch is preferably 0.5% by mass or more and 65% by mass or less, and more preferably 1% by mass or more and 60% by mass or less.
The content of hydrophilic zeolite in the masterbatch is preferably 0.5% by mass or more and 65% by mass or less, and more preferably 1% by mass or more and 60% by mass or less. If it is less than the above range, the degree of freedom of the content of the deodorant or the hydrolysis inhibitor in the layer tends to be small, and if it is more than the above range, it tends to be difficult to obtain excellent dispersibility.
Examples of the thermoplastic resin used in the masterbatch include, but are not limited to, general-purpose polyethylene, polypropylene, methylpentene polymer, polyolefin-based resins such as acid-modified polyolefin-based resins, and mixtures of these resins.

At this time, the thermoplastic resin in the masterbatch may be the same as or different from the hydrolysis inhibitor dispersion resin in the hydrolysis inhibitor layer, and different types of resins may be hydrolyzed depending on the purpose. It is possible to combine layers within a range that does not significantly adversely affect the heat sealability and film forming property.
For example, if the same resin as the hydrolysis inhibitor dispersion resin in the hydrolysis inhibitor layer is used for the masterbatch, the hydrolysis inhibitor layer tends to be homogeneous, and has good film-forming property, heat-sealing property, and interlayer adhesion. It is possible to efficiently obtain strength and hydrolysis inhibitory property.

(Polyolefin resin)
The polyolefin resin contained in the deodorant layer and / or the hydrolysis inhibitory layer is preferably one having excellent dispersibility and heat sealability of the deodorant and / or the hydrolysis inhibitor.
Specific examples of the polyolefin resin include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), and ethylene-vinyl acetate common weight. Low-elution products such as coalesced, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methylmethacrylic acid copolymer, ethylene-propylene copolymer, etc. And a mixture of their resins.
Among the above, polyethylene-based resins are preferable, and among polyethylene-based resins, LDPE and / or LLDPE are more preferable, and LDPE and / or LLDPE having a density of 0.90 g / cm ³ or more and 0.94 g / cm ³ or less are preferable. LLDPE is more preferred.

<Gas barrier layer>
The gas barrier layer prevents water vapor, oxygen, etc. from permeating from the outside to the inside of the deodorant package and further to the contents in the deodorant package produced by using the deodorant laminate of the present invention. It is a layer that suppresses the formation of odorous substances due to hydrolysis and oxidation of the contents, and can suppress deterioration due to moisture.
As the gas barrier layer, one or more selected from the group consisting of a gas barrier resin film, a metal foil, a resin film with a metal vapor deposition layer, a resin film with a metal oxide vapor deposition layer, and a gas barrier resin coating film may be used. it can.
As the gas barrier resin film, a known and publicly available resin film having a gas barrier property can be used. For example, as the gas barrier film, specifically, a resin film made of a resin such as PET, polybutylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, and the above-mentioned base film. A vapor-deposited film in which a vapor-deposited film such as a silica vapor-deposited film or an alumina vapor-deposited film is provided on at least one of the surfaces of the above, and a metal foil such as an aluminum foil can be used, but the present invention is not limited thereto.
The metal foil is preferably an aluminum foil, the resin film with a metal vapor deposition layer is preferably a resin film with an aluminum vapor deposition film, the resin film with a metal oxide vapor deposition layer is preferably a resin film with an aluminum oxide vapor deposition film, and a gas barrier resin coating is used. As the film, a coating film containing a solgel method hydrolyzed polycondensate formed from a metal alkoxide and a water-soluble polymer is preferable.

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

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

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

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

<Deodorant packaging bag>
The deodorant packaging bag of the present invention is a bag-shaped bag as a form of the deodorant packaging body of the present invention.
As a bag-making method, for example, the deodorant sealant layer of the deodorant sealant film and the hydrolysis-suppressing sealant layer of the hydrolysis-suppressing sealant film are overlapped with each other facing each other, and the peripheral end portions thereof are, for example, a side seal type, two. Heat according to the heat seal form such as one-sided seal type, three-way seal type, four-sided seal type, envelope-attached seal type, gassho-attached seal type (pillow seal type), fold-attached seal type, flat-bottom seal type, square-bottom seal type, gusset type, etc. It can be manufactured by sealing.
As a heat sealing method, for example, known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, and ultrasonic sealing can be applied.

<Deodorant pouch bag>
The deodorant pouch bag of the present invention is a pouch bag-shaped bag as a form of the deodorant packaging bag of the present invention.

<Raw materials>
Details of the raw materials used in the examples are as follows.
[Deodorants]
(Chemical odor adsorbent-supported inorganic porous body)
-Kesmon NS-241: An amino group-containing compound-supporting inorganic porous body manufactured by Toagosei Co., Ltd. Average particle size 3.5 μm.
-Kesmon NS-80E: manufactured by Toagosei Co., Ltd., hydroxyl group-supported zirconium, average particle diameter of 2 μm.

(Hydrophobic zeolite]
-Mizuka Sieves EX-122: Made by Mizusawa Industrial Chemicals, Inc. SiO ₂ / AL ₂ O ₃ molar ratio = 32/1, average particle size 2.5 to 5.5 μm.
-Silton MT400: Made by Mizusawa Industrial Chemicals, Inc. SiO ₂ / AL ₂ O ₃ molar ratio = 400/1, average particle diameter 5-7 μm.
-Silton MT-8000: Made by Mizusawa Industrial Chemicals, Inc. SiO ₂ / AL ₂ O ₃ molar ratio = 8000/1, average particle diameter 0.8 μm.

[Hydrolyzant]
(Hygroscopic alkaline earth metal compound)
-Calcium oxide: Manufactured by High Purity Chemical Laboratory Co., Ltd. Average particle size 5 μm.
-Magnesium oxide: Made by Konoshima Chemical Co., Ltd. Starmag PSF-150, average particle size 0.6 μm.
(Hydrophilic zeolite)
・ Mizuka Sieves 5AP: Made by Mizusawa Industrial Chemicals, Inc. SiO ₂ / AL ₂ O ₃ molar ratio = 2/1, average particle diameter 5 μm.

[Other]
-PET film 1: Espet T4012 manufactured by Toray Film Processing Co., Ltd. Film thickness: 12 μm.
-Aluminum foil 1: 7 μm thick.
DL Adhesive 1: Dry Laminating Adhesive RU004 / H-1 manufactured by Rock Paint Co., Ltd.
-Embedded film 1: PET film with single-sided aluminum oxide vapor deposition layer manufactured by Dai Nippon Printing Co., Ltd., IB-PET-PIR. 12 μm thick.
-LDPE1: Novatec LC600A manufactured by Japan Polyethylene Corporation.
-LLDPE1: Evolu SP2020 manufactured by Prime Polymer Co., Ltd. MFR: 2.3 g / 10 minutes, density: 0.916 g / cm ³ .

<Masterbatch>
The masterbatch was adjusted as follows.
(Adjustment of masterbatch 1)
LDPE1 and Kesmon NS-241, which is an inorganic porous body carrying a chemical odor adsorbent, were melt-blended at the following ratios to obtain Masterbatch 1 (MB1).
LDPE1 90 parts by mass Kessmon NS-241 10 parts by mass

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

[Example 1]
(Adjustment of resin composition for deodorant layer)
MB1 and LLDPE1 were dry-blended at the following mass ratio to obtain a resin composition for a deodorant layer.
Masterbatch 1 83.3 parts by mass LLDPE1 16.7 parts by mass

(Preparation of resin composition for hydrolysis inhibitory layer)
MB9 and LLDPE1 were dry-blended at the following mass ratio to obtain a resin composition for a hydrolysis inhibitory layer.
Masterbatch 9 66.7 parts by mass LLDPE1 33.3 parts by mass

(Preparation of sealant film)
The resin composition for the deodorant layer, the resin composition for the hydrolysis suppression layer, and LLDPE1 for the heat seal layer obtained above were laminated by inflation film formation at 160 ° C. to obtain a sealant film having the following three layers. ..
Heat seal layer (10 μm) / deodorant layer (30 μm) / hydrolysis suppression layer (30 μm)

(Preparation of deodorant laminate)
Next, the obtained sealant film, the PET film 1 for the base material layer, and the aluminum foil 1 for the gas barrier layer were dry-laminated via DL adhesive 1 (coating amount 3.5 g / m ² ). It was bonded at a drying temperature of 70 ° C.) to obtain a deodorant laminate having the following layer structure.
Base material layer (12 μm) / adhesive layer (3.5 g / m ² ) / gas barrier layer (7 μm) / adhesive layer (3.5 g / m ² ) / sealant layer [heat seal layer (10 μm) / deodorant layer (30 μm) ) / Hydrolysis inhibitory layer (30 μm)]

(Making a deodorant packaging bag)
The deodorant laminate prepared above was cut into a size of 20 x 20 cm, the sealant surfaces were overlapped, and the three end portions were heat-sealed using a heat seal tester (manufactured by Tester Sangyo Co., Ltd .: TP-701-A). A deodorant packaging bag was prepared.
Then, various evaluations were carried out using the deodorant laminate and the deodorant packaging bag.

<Examples 2 to 23, Comparative Examples 1 and 2>
According to the configurations of the sealant layer and the gas barrier layer shown in Tables 3 to 7, MB and the gas barrier layer material are selected, and the resin composition for the deodorant layer and the resin composition for the hydrolysis inhibitory layer are prepared, and the same as in Example 1. By operating in the same manner, a sealant film was prepared, a deodorant laminate and a deodorant packaging bag were obtained, and evaluated in the same manner.

<Summary of results>
The deodorant laminates and deodorant packaging bags of Examples 1 to 22 showed good film-forming property, bag-forming property, heat-sealing property, deodorizing effect, and relative humidification lowering effect.
Comparative Example 1 which does not have the deodorant layer and the hydrolysis inhibitory layer shows an insufficient deodorant effect and a relative humidification lowering effect, and shows the deodorant content in the deodorant layer and the hydrolysis inhibitory layer. In Example 2, the content of the hydrolysis inhibitor was too high, and the film-forming property and the bag-forming property were insufficient.

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

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

[Heat sealability]
The deodorant laminate is cut into 10 cm x 10 cm pieces, the two sheets are overlapped with the sealant layer surfaces facing each other, and a 1 cm x 10 cm area is formed using a heat seal tester (manufactured by Tester Sangyo Co., Ltd .: TP-701-A). A sample was prepared in which the ends were heat-sealed, not heat-sealed and not adhered, and were bifurcated.
This sample was cut into strips with a width of 15 mm, each bifurcated end was mounted on a tensile tester, and the tensile strength (N / 15 mm) was measured to determine pass / fail.
(Heat seal condition)
Temperature: 160 ° C
Pressure: 1 kgf / cm ²
Time: 1 second (tensile strength test conditions)
Test speed: 300 mm / min Load range: 50 N
(Pass / fail criteria)
◯: 30N / 15mm or more, passed.
X: Less than 30 N / 15 mm and failed.

[Deodorant performance, relative humidity]
1000 ml of deodorant laminate cut to 20 x 20 cm and adjusted in concentration with air with relative humidity of 80% or more, and temperature / humidity data logger (T & D Co., Ltd., TR-72wf). Was placed in a gas sampling bag (IB-PET-PIR 12 μm / adhesive layer / ONy 15 μm / adhesive layer / LLDPE film 60 μm), and the odor change after being left for 2 days was measured by sensory evaluation, and the relative humidity was measured by a temperature / humidity data logger. .. The odor component was adjusted so that acetaldehyde was 200 ppm and acetic acid was 30 ppm.
The evaluation criteria for odor sensory evaluation are as follows: ・ 1 = odor unchanged from the initial stage ・ 2 = odor was slightly alleviated from the initial stage ・ 3 = odor was significantly alleviated compared to the initial stage ・ 4 = totally Does not smell

1 Deodorant laminate 2 Base material layer 3 Gas barrier layer 4 Sealant layer, Sealant film 5 Deodorant layer 6 Hydrolysis suppression layer 7 Heat seal layer

Claims (9)

A deodorant laminate for packaging materials having a base material layer and a sealant layer.
The sealant layer has a deodorant layer and a hydrolysis inhibitory layer.
The deodorant layer contains a deodorant and a polyolefin resin, and contains
The deodorant contains a chemical odor adsorbent and / or a hydrophobic zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 30/1 to 10000/1.
The hydrolysis inhibitory layer contains a hydrolysis inhibitor and a polyolefin resin.
The hydrolysis inhibitor consists of a group consisting of a hygroscopic alkali metal compound and / or a hygroscopic alkaline earth metal compound and a hydrophilic zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 1/1 to 20/1. Contains one or more selected species,
The content of the deodorant in the deodorant layer is 0.5% by mass or more and 15% by mass or less.
A deodorant laminate characterized in that the content of the hydrolysis inhibitor in the hydrolysis inhibitor layer is 1% by mass or more and 50% by mass or less. The deodorant laminate further has a gas barrier layer between the base material layer, the deodorant layer and the hydrolysis inhibitory layer.
The gas barrier layer is one or more selected from the group consisting of a gas barrier resin film, a metal foil, a resin film with a metal vapor deposition layer, a resin film with a metal oxide vapor deposition layer, and a gas barrier resin coating film. Characteristic,
The deodorant laminate according to claim 1. The outer surface layer of the sealant layer is the deodorant layer or the hydrolysis inhibitory layer.
The deodorant laminate according to claim 1 or 2. The outer surface layer of the sealant layer, or the outer surface layer of the sealant layer and the layer on the most base material side side contain a polyolefin resin and do not contain the deodorant and the hydrolysis inhibitor. It is a heat seal layer,
The deodorant laminate according to claim 1 or 2. The polyolefin-based resin is LDPE and / or LLDPE having a density of 0.90 g / cm ³ or more and 0.94 g / cm ³ or less.
The deodorant laminate according to any one of claims 1 to 4. A deodorant packaging material comprising the deodorant laminate according to any one of claims 1 to 5. A deodorant packaging body, which is produced by using the deodorant packaging material according to claim 6. A deodorant packaging bag made by using the deodorant packaging material according to claim 6. A deodorant pouch bag made by using the deodorant packaging material according to claim 6.

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