JP2019177519A - Deodorizing film for heat sterilization treatment, and deodorizing packaging material and deodorizing package produced from the deodorizing film for heat sterilization treatment - Google Patents

Abstract

To provide a deodorizing film for a heat sterilization treatment, which exhibits an excellent deodorizing effect even when subjected to a heat sterilization treatment and includes a sealant layer in an outermost surface layer on at least one side, and a packaging material and a package using the deodorizing film.SOLUTION: The deodorizing film for a heat sterilization treatment includes at least a sealant layer in an outermost layer on one side, in which the sealant layer comprises a heat-sealing resin, a powdery hydrophobic zeolite and a powdery inorganic odor decomposing agent. The heat-sealing resin has a softening point of 110°C or higher and 175°C or lower; the hydrophobic zeolite has a SiO/AlOmolar ratio of 30/1 or more and 8000/1 or less; the inorganic odor decomposing agent is prepared by kneading or depositing a metal oxide or a metal salt in or on an inorganic substance; and the total content of the hydrophobic zeolite and the inorganic odor decomposing agent in the sealant layer is 0.3 mass% or more and 15 mass% or less.SELECTED DRAWING: Figure 1

Description

  The present invention is excellent in the deodorizing effect of odors, particularly sulfur-based odors, heat sealability, gas barrier properties, especially for retort foods and beverages, and a deodorizing film for heat sterilization treatment comprising a sealant layer on at least one outermost layer, And a packaging material and a package produced from the deodorizing film for heat sterilization treatment.

A retort food or drink packaged with a packaging material may generate a denatured odor from the packaging material and contents by heat sterilization.
The sources of modified odors in the contents are carbohydrates, fats and oils, proteins, etc. Among them, protein-modified odors, particularly sulfur-based odors, are often problematic.

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

  A packaging material containing an odor adsorbent formed by supporting an organic chemical adsorbent on an inorganic porous material is also known (Patent Document 2), but the main adsorption target adsorbs an odor component having a specific functional group. However, in a situation where a resin material is not selected, the amount of organic matter not having a functional group cannot be suppressed, and the odor component cannot be sufficiently adsorbed. Furthermore, the organic chemical adsorbent is weak at high temperature and the adsorption ability is impaired by the heat sterilization treatment, so that the sufficient adsorption effect cannot be exhibited.

  A packaging material containing a glass deodorant comprising an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkali earth-silicate glass containing a copper component is also known (patent) Document 3), which mainly adsorbs hydrophilic sulfides, and hydrophobic sulfides have low deodorizing ability.

Japanese Patent No. 2538487 JP 2014-233408 A JP 2017-025190 A

  In view of the above circumstances, the present invention provides a deodorizing film for heat sterilization treatment that includes a sealant layer on at least one outermost surface, which exhibits an excellent deodorizing effect even when subjected to heat sterilization treatment, and packaging using the same The object is to provide materials and packages.

The present inventors have found that a deodorizing film for heat sterilization treatment containing a heat-sealable resin, a specific hydrophobic zeolite, and a specific inorganic odor decomposing agent achieves the above object, and has completed the present invention. It came to do.

The present invention is characterized by the following points.
1. At least a deodorizing film for heat sterilization treatment including a sealant layer on the outermost layer on one side,
The sealant layer includes a heat-sealable resin, a powdery hydrophobic zeolite, and a powdered inorganic odor decomposer,
The softening point of the heat-sealable resin is 110 ° C. or higher and 175 ° C. or lower,
The hydrophobic zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 30/1 or more and 8000/1 or less,
The inorganic odor decomposing agent is a metal oxide or metal salt kneaded or supported on an inorganic substance,
The total content of the hydrophobic zeolite and the inorganic odor decomposer in the sealant layer is 0.3% by mass or more and 15% by mass or less.
Deodorizing film for heat sterilization treatment.
2. The treatment temperature of the heat sterilization treatment is 100 ° C. or more and 140 ° C. or less,
2. The deodorizing film for heat sterilization treatment according to the above 1, wherein the mass ratio of hydrophobic zeolite / inorganic odor decomposing agent is 10/90 or more and 95/5 or less.
3. The inorganic odor decomposing agent is formed from an inorganic odor decomposing agent composition containing at least copper (II) oxide, silicon oxide, and alkali metal oxide.
3. The deodorizing film for heat sterilization treatment according to 1 or 2 above.
4). The inorganic odor decomposer composition further includes a compound of one or more elements selected from the group consisting of copper, zinc, silver, iron, platinum, and gold.
4. A deodorizing film for heat sterilization treatment as described in 3 above.
5. The inorganic odor decomposer composition further comprises one or more alkaline earth metal oxides,
5. The deodorizing film for heat sterilization treatment according to 3 or 4 above.
6). The inorganic odor decomposer composition further contains boron oxide,
6. A deodorizing film for heat sterilization treatment according to any one of 3 to 5 above.
7). The deodorizing film for heat sterilization treatment according to any one of the above 1 to 6, wherein the heat sealable resin is a polypropylene resin.
8). A deodorizing packaging material for heat sterilization treatment produced from the deodorization film for heat sterilization treatment according to any one of 1 to 7 above.
9. 9. A deodorizing package for heat sterilization treatment produced from the deodorizing packaging material for heat sterilization treatment described in 8 above.

According to the present invention, a deodorizing film for heat sterilization treatment including a sealant layer on at least one outermost surface that exhibits an excellent deodorizing effect even when subjected to heat sterilization treatment on a package and contents, and A packaging material and a package produced from a deodorizing film for heat sterilization treatment including a sealant layer on at least one outermost layer can be obtained.
In addition, it can be sterilized at a high temperature to prevent the entry of oxygen and water vapor gas from the outside, and it can prevent the leakage of odors from the inside and the evaporation of moisture, enabling long-term storage of the contents. And

It is sectional drawing which shows one example of the deodorizing film for heat sterilization processes of this invention. It is sectional drawing which shows one example of another aspect of the deodorizing film for heat sterilization processes of this invention. It is sectional drawing which shows one example of another aspect of the deodorizing film for heat sterilization processes of this invention.

The present invention will be described below with reference to the drawings. However, the present invention is not limited to these specifically exemplified forms and various specifically described structures.
In each drawing, the size and ratio of members may be changed or exaggerated for easy understanding. For ease of viewing, unnecessary parts and repeated reference numerals may be omitted for explanation.
In the present invention, a film and a sheet are collectively referred to as a film.

  The present invention is a deodorizing film for heat sterilization treatment comprising a sealant layer on at least one outermost layer, and a packaging material and a package produced from the deodorizing film for heat sterilization treatment, wherein the sealant layer is a heat It contains a sealing resin, a powdery hydrophobic zeolite, and a powdered inorganic odor decomposing agent. The package can be used for a packaging container that is hermetically filled with food and drink as contents.

The treatment temperature for the heat sterilization treatment is preferably 100 ° C. or higher and 140 ° C. or lower.
The deodorizing film for heat sterilization treatment of the present invention functions as a sealant film by including a sealant layer on the outermost layer on one side, and has a SiO ₂ / Al ₂ O ₃ molar ratio of 30 that adsorbs a hydrophobic sulfur-based odor component. / 1 to 8000/1 hydrophobic zeolite and an inorganic odor decomposing agent that decomposes hydrophilic sulfur-based odor components, exhibiting a high deodorizing effect on a wide variety of sulfur-based odor components . The deodorizing effect is not lost by the heat sterilization treatment.

<Heat treatment>
In the present invention, the heat treatment includes a deodorizing film for heat sterilization treatment, a laminate, a packaging material, a heat treatment for producing the package, a heat treatment for the package contents, and the package and contents. The heat sterilization process to a thing is mentioned, The heating temperature changes also with each raw heat processing, the raw material structure of a laminated body, and a content composition.
When the heat treatment is performed at a high temperature, the resin component may be altered and the odor adsorbent may be deteriorated, and the influence of the temperature of each heat treatment must be considered.
In the present invention, the heat processing for the package contents is not particularly regarded as a problem in the present invention because the processing requiring high temperature is usually completed in the stage before filling the package.

In the film forming process, it is necessary to heat to a temperature at which the resin is sufficiently melted. The heating temperature varies depending on the resin. For example, in the case of a polyethylene resin, it is heated to 110 ° C. to 200 ° C. Is heated to 130 to 260 ° C.
Therefore, the film-forming process is easy to generate a denatured odor due to the alteration of the resin component, particularly in the heat processing for producing the laminate, the packaging material, and the package, and can be generated from the entire package. The content can be transferred.

  For example, when the resin component of the sealant layer is a polyethylene-based resin, the heat-sealing process when producing the package is heated to 90 ° C. to 200 ° C., and in the case of a polypropylene-based resin, 110 ° C. to 260 ° C. However, since the heating area is small, the heating time is short, and the contents are not in contact with each other, there is little generation of modified odor due to alteration of the resin component, and the contents There is little shift to.

  Regardless of the type of resin component of the package, the heat sterilization treatment for the package and the contents is usually performed within the range of 100 ° C. or more and 140 ° C. or less, particularly at 121 ° C. If the resin component has insufficient heat resistance, it can generate a modified odor from the resin component, and the modified odor from the resin component Since it can be generated from the entire package, it can be transferred to the contents.

<Configuration of deodorizing film for heat sterilization treatment of the present invention>
The deodorizing film for heat sterilization treatment of the present invention may be composed of a single layer or a multilayer structure of two or more layers, but at least the outermost layer on one side contains a heat-sealable resin.
Furthermore, in the case of a single layer structure, as shown in FIG. 1, the single layer contains a heat-sealable resin, a hydrophobic zeolite, and an inorganic odor decomposing agent. 2 and 3, the heat-sealable resin, the hydrophobic zeolite, and the inorganic odor decomposing agent may be simultaneously contained in the same one layer or two or more layers. Each may contain one or more of the group consisting of a heat-sealable resin, a hydrophobic zeolite, and an inorganic odor decomposing agent, and even if the multiple layers have the same composition, different compositions It may be a layer.

In the case of a multilayer structure of two or more layers, a functional layer having various functions can be included as necessary. The functional layer may not contain any of heat-sealable resin, hydrophobic zeolite, and inorganic odor decomposing agent.
Furthermore, in the case of a multilayer structure of two or more layers, an adhesive layer may be present between the respective layers.

  In the present invention, the layer containing the heat-sealable resin and the hydrophobic zeolite or the inorganic odor decomposing agent in the sealant layer in the deodorizing film for heat sterilization treatment is the deodorizing layer, and the other layers are non-deodorizing. Also described as odor layer.

  Further, the deodorizing film for heat sterilization treatment of the present invention includes an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antiblocking agent, a flame retardant, a crosslinking agent, a colorant, a pigment, a lubricant, One or more kinds of various plastic compounding agents and additives such as a filler, a reinforcing agent and a modifying resin can be appropriately added. The addition amount can be arbitrarily added from a very small amount to several tens of percent depending on the purpose.

  The surface of each layer constituting the deodorizing film for heat sterilization treatment or the deodorizing film for heat sterilization treatment of the present invention can be subjected to corona treatment, flame treatment, ozone treatment, or the like, if necessary.

The thickness of the sealant layer is preferably 10 μm or more and 250 μm or less, and more preferably 30 μm or more and 150 μm or less.
If it is thinner than the above range, the odor component reducing performance tends to be insufficient, and the laminate strength after heat sealing tends to be insufficient. When it is thicker than the above range, the rigidity of the laminate becomes too strong, and the workability and the feeling of use of the package are likely to deteriorate.
The thickness of the deodorant layer is preferably 7 μm or more and 250 μm or less, and more preferably 10 μm or more and 150 μm or less.

  In the present invention, in order to improve the adhesion to the surface of the deodorizing film for heat sterilization treatment and the surface of each layer constituting the deodorization film for heat sterilization treatment, a desired surface treatment layer is previously prepared as necessary. Can be provided.

For example, corona discharge treatment, ozone treatment, pretreatment such as low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. is optionally performed, corona treatment layer, ozone treatment A layer, a plasma treatment layer, an oxidation treatment layer, or the like can be formed and provided.
Alternatively, a primer coating agent layer, an undercoat agent layer, an anchor coating agent layer, an adhesive layer, a vapor deposition anchor coating agent layer, and the like can be arbitrarily formed to form a surface treatment layer.

Examples of the various coating agent layers include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, and polyolefins such as polyethylene and polypropylene. It is possible to use a resin composition whose main component is a vehicle resin or a copolymer or modified resin thereof, a cellulose resin, or the like.

[Heat sealable resin]
In the present invention, the heat-sealable resin is a resin that can be melted by heat and fused to each other. The temperature of the heat sealing process varies depending on the heat sealing resin used.
Furthermore, the heat-sealable resin is a resin that can sufficiently disperse the hydrophobic zeolite and / or the inorganic odor decomposing agent.
In order to apply a heat sterilization treatment of 100 ° C. or higher and 140 ° C. or lower, the softening point of the heat-sealable resin is preferably 110 ° C. or higher and 175 ° C. or lower.

  Examples of the heat-sealable resin preferably used in the present invention include propylene homopolymer, copolymer of propylene and unsaturated carboxylic acid, copolymer of propylene and unsaturated carboxylic acid ester, propylene / α -Polypropylene resins such as olefin copolymers, random copolymers or block copolymers of ethylene-propylene copolymers.

As said unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc. are mentioned, It can copolymerize using these 1 type (s) or 2 or more types.
Examples of the unsaturated carboxylic acid ester include acrylic acid ester, methacrylic acid ester, maleic anhydride ester, and fumaric acid ester, and these can be copolymerized using one or more of them.
Among the heat-sealable resins, polypropylene resins are preferably used from the viewpoint of heat resistance.
Heat seal processing means that when manufacturing a packaging container, wrap the packaging material in two or prepare two packaging materials, face each other with their sealant layers facing each other, and melt their peripheral edges And fusing each other. The heating temperature varies depending on the resin.

As a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal can be used.
When a polypropylene resin is used as the heat sealable resin, the heat seal temperature is preferably 110 ° C. or higher and 260 ° C. or lower.

[Hydrophobic zeolite]
In the present invention, the hydrophobic zeolite contained in the sealant layer exhibits a high odor adsorbing ability and has a SiO ₂ / Al ₂ O ₃ molar ratio of 30/1 to 8000/1 in order to suppress moisture adsorption. Are preferred. In general, the higher the SiO ₂ / Al ₂ O ₃ molar ratio of zeolite, the higher the hydrophobicity.

The hydrophobic zeolite in the present invention has a high adsorptive ability for lower hydrocarbons and sulfur-based odor components, particularly hydrophobic compounds such as dimethyl sulfide, and even when exposed to 230 ° C. or higher, The odor adsorption ability is not lost, and the adsorption effect of the odor component can be exhibited.
Hydrophobic zeolite may have any outer shape such as a spherical shape, a rod shape, an elliptical shape, and may have any shape such as a powder shape, a lump shape, and a granular shape. From the viewpoint of uniform dispersion in the resin, kneading characteristics and the like, a powder form is preferable.

In the present invention, the average particle size of the hydrophobic zeolite can be appropriately selected from those having an average particle size depending on the application, but those having an average particle size of 0.01 μm to 10 μm are preferable. Here, the average particle diameter is a value measured by a dynamic light scattering method.
When the average particle diameter is smaller than 0.01 μm, aggregation of the hydrophobic zeolite tends to occur and the dispersibility in the sealant layer tends to be lowered. In addition, when the average particle size is larger than 10 μm, the film forming property of the sealant layer tends to be inferior, so that it is difficult to add a large amount of hydrophobic zeolite, and the surface area is further reduced. There is a possibility that the effect cannot be obtained.

The content of the hydrophobic zeolite in all the sealant layers is preferably 0.1% by mass or more and 15% by mass or less.
If it is 0.1% by mass or more, it is possible to exert a sufficient odor adsorption effect, but in order to obtain a good odor adsorption effect as a package, it is more preferably 0.3% by mass or more. More preferably, the content is 0.5% by mass or more.
On the other hand, the content is preferably 15% by mass or less and more preferably 10% by mass or less in order to obtain good film forming properties and heat sealability.

[Inorganic odor decomposer]
The inorganic odor decomposing agent in the present invention is a material in which a metal oxide or metal salt is kneaded or supported on an inorganic substance, and preferably at least copper (II) oxide, silicon oxide, alkali metal oxide, Formed from an inorganic odor decomposing agent composition.
The inorganic odor decomposing agent in the present invention has a catalytic action that promotes the decomposition reaction of sulfur-based malodorous substances by ionizing metal components and the like held in the inorganic odor decomposing agent, thereby eliminating the odor-degrading substances against sulfur-based malodorous substances. It has an odor effect. Among sulfur-based malodorous substances, the deodorizing effect on hydrophilic compounds such as hydrogen sulfide is particularly high.

It is preferable that the inorganic odor decomposing agent composition further contains a compound of one or more elements selected from the group consisting of copper, zinc, silver, platinum, gold, and iron as the above-mentioned ionizing component. It is preferable to contain a compound of one or more elements selected from the group consisting of copper, zinc and silver.
Further, the inorganic odor decomposing agent composition may further contain boron oxide, and may further contain an alkaline earth metal oxide, aluminum oxide, or the like, as necessary, in order to adjust chemical performance and physical performance. .

Powdered inorganic odor decomposing agent is prepared by mixing each raw material to prepare an inorganic odor decomposing agent composition, and melting and homogenizing it by a conventional method similar to the production of general-purpose glass such as bottle glass, and then pulverizing it after cooling. Can be obtained.
Inorganic odor decomposing agent promotes the decomposition reaction of sulfur-based malodorous substances as a catalyst, so that it can increase the deodorizing capacity compared to the conventional technology that depends on the surface area using chemical adsorption and physical adsorption, and the The odor effect can be exhibited stably over a long period of time.

  The content of copper oxide (II) (CuO) in the inorganic odor decomposing agent 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 exhibited, and when the amount is more than the above range, metallic copper is liable to precipitate, which is not preferable.

Silicon oxide (SiO ₂ ) is a main component that forms the structural skeleton of the inorganic odor decomposing agent. 46-70 mol% is preferable and, as for content of the silicon oxide in an inorganic odor decomposer composition, 51-70 mol% is more preferable.
When the amount is less than the above range, the chemical durability and water resistance of the inorganic odor decomposing agent are likely to be insufficient, and the deodorizing effect due to the catalytic action of copper (II) oxide tends to be lowered. When it is more than the above range, the melting point and melt viscosity of the inorganic odor decomposing agent are too high, and the inorganic odor decomposing agent 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 decomposing agent.
10-33 mol% is preferable, as for content of the alkali metal oxide in an inorganic odor decomposer composition, 12-24 mol% is more preferable, and 12-20 mol% is further more preferable.
When the amount is less than the above range, the effect of lowering the melting point and melt viscosity of the inorganic odor decomposing agent tends to be insufficient. When it is more than the above range, the chemical durability and water resistance of the inorganic odor decomposing agent tend to be insufficient, and the deodorizing effect tends to be lowered.

  The alkaline earth metal oxide is one or more selected from the group consisting of MgO, CaO, SrO, and BaO, and is a component contained in the inorganic odor decomposing agent composition as necessary, and decomposes the inorganic odor. Has the effect of improving the chemical durability of the agent.

When the alkaline earth metal oxide is included in the inorganic odor decomposer composition, the content of the alkaline earth metal oxide in the inorganic odor decomposer composition is preferably 2 to 10 mol%, and 2 to 7 mol%. Is more preferable.
If the amount is less than the above range, it is difficult to sufficiently exert the effect of containing the alkaline earth metal oxide. If the amount is more than the above range, the melting point and melt viscosity of the inorganic odor decomposing agent are too high to be inhomogeneous. It is easy to become.

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.

The content of boron oxide in the inorganic odor decomposer composition when boron oxide is contained in the inorganic odor decomposer composition is preferably 5 to 20 mol%, more preferably 8 to 17 mol%.
If the amount is less than the above range, it is difficult to sufficiently exhibit the effect of containing boron oxide. If the amount is more than the above range, the chemical durability and water resistance of the inorganic odor decomposer are likely to be insufficient. In addition, the deodorizing effect tends to decrease.

Since boron oxide has the effect of lowering the melting point and melt viscosity of the inorganic odor decomposing agent in the same manner as the alkali metal oxide, 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 decomposer composition is preferably 15 to 50 mol%, more preferably 21 to 39 mol%.
When the amount is less than the above range, the effect of lowering the melting point and melt viscosity of the inorganic odor decomposing agent tends to be insufficient. If it is more than the above range, the inorganic odor decomposer tends to be heterogeneous, the water resistance of the inorganic odor decomposer tends to be insufficient, and the deodorizing effect tends to be lowered.

Aluminum oxide (Al ₂ O ₃₎ is a component contained in the inorganic odor decomposing agent composition optionally with enhanced homogeneity of the inorganic odor decomposing agents, to improve the chemical durability effect.

In the case where aluminum oxide is contained in the inorganic odor decomposing agent composition, the content of aluminum oxide in the inorganic odor decomposing agent composition is preferably 0.1 to 6 mol%, preferably 0.1 to 5.5 mol%. Is more preferable, and 0.1 to 4.5 mol% is more preferable.
If the amount is less than the above range, it is difficult to sufficiently exert the effect of containing aluminum oxide. If the amount is more than the above range, the melting point and the melt viscosity of the inorganic odor decomposing agent are too high and are likely to be inhomogeneous. .

In addition to the above components, as a minor component, ZnO, SrO, BaO, 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 , Fe ₂ O ₃ , Sb ₂ O ₃ , SnO _{2 and the} like can also be contained.

The particle size distribution of the inorganic odor degrading agent is preferably a powder having 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 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 inorganic odor decomposing agent is likely to aggregate and the dispersibility in the sealant layer tends to be lowered. In addition, 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 is difficult to add a large amount of the inorganic odor decomposing agent, and the surface area is further reduced. It may be difficult to obtain an 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.

The content of the inorganic odor decomposing agent in the entire sealant layer is preferably 0.1% by mass or more and 15% by mass or less.
If it is 0.1% by mass or more, it is possible to exert a sufficient deodorizing effect, but in order to obtain a good deodorizing effect, it is more preferably 0.3% by mass or more, and preferably More preferably, it is 5 mass% or more.
On the other hand, the content is preferably 15% by mass or less and more preferably 10% by mass or less in order to obtain good film forming properties and heat sealability.

  Further, the mass ratio of hydrophobic zeolite / inorganic odor decomposing agent is preferably 10/90 or more and 95/5 or less, more preferably 20/80 or more and 85/15 or less, and 30/70 or more and 70/30 or less. Further preferred.

<Adhesive layer>
In the deodorizing film for heat sterilization treatment of the present invention, the adhesive layer is a layer included as necessary. Moreover, an adhesive layer can also be included when producing a laminated body in combination with a base material layer.
1-3, the adhesive layer is not shown, but can be included between the layers.

  For the adhesive layer, it is preferable to use an adhesive for dry lamination, and examples thereof include a urethane adhesive, a vinyl adhesive, an acrylic adhesive, an epoxy adhesive, and an ester adhesive.

<Method for producing deodorizing film for heat sterilization treatment>
As a method for producing and laminating each layer constituting the deodorizing film for heat sterilization treatment, for example, using one resin composition, extrusion method, cast molding method, T-die method, cutting method, inflation method, etc. A method for forming a film using a film forming method, a method for forming a multilayer co-extrusion film using two or more resin compositions, and mixing the two or more resin compositions before forming the film. Film formation, lamination, or film formation and lamination can be performed at the same time by appropriately selecting from a method for forming a film by a method, a dry lamination method, a sand lamination method, or the like.
The same method can be applied to the case where the deodorizing film for heat sterilization treatment of the present invention is laminated on another film layer to produce a laminate.

<Deodorizing packaging material for heat sterilization>
Using the deodorizing film for heat sterilization treatment of the present invention, for example, pasting with a base film, etc., surface treatment as necessary, cutting, etc., deodorizing packaging material for heat sterilization treatment Obtainable.

<Deodorized packaging for heat sterilization>
Using the deodorizing packaging material for heat sterilization treatment of the present invention, for example, making a bag so that the outermost layer on one side containing the heat-sealable resin becomes the innermost layer, and deodorizing packaging for heat sterilization treatment such as a packaging bag The body can be made.

  To manufacture a packaging bag, fold the above-mentioned deodorizing packaging material for heat sterilization or prepare two deodorizing packaging materials for heat sterilization, and put the sealant layers facing each other. For example, a standing pouch type, 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 palm-attached seal type (pillow seal type), a pleated seal type, Various types of packaging bags can be obtained by heat sealing using a flat bottom sealing type, a square bottom sealing type, a gusset type or the like.

  In the present invention, the contents to be sealed and packed in the packaging bag include retort foods and drinks and fresh foods, for example, drinks such as liquor, fruit juice drinks, beverages such as mineral water, liquid seasonings such as soy sauce and sauces. Fresh foods such as liquid food and drink such as food, curry, stew and soup.

<Raw materials>
The main raw materials used in the examples of the present invention are as follows.
[Film for substrate layer]
PET film 1: thickness 12 μm T-4102 manufactured by Toyobo Co., Ltd. Single-sided corona treatment. [Film for functional layer]
Nylon film 1: manufactured by Unitika, biaxially stretched nylon film, product number: emblem ONBC, film thickness: 15 μm.
[adhesive]
-Adhesive 1: DL (dry laminate) adhesive. Rock bond JRU-77T / Adlock H-7 manufactured by Rock Paint Co., Ltd .; blending ratio 10/1.
[Hydrophobic zeolite]
Hydrophobic zeolite 1: Shiruton MT100 manufactured by Mizusawa Chemical Co., Ltd. SiO ₂ / Al ₂ O ₃ molar ratio = 100/1, average particle size = 3 to 4.5 μm.
Hydrophobic zeolite 2: Shilton MT400 manufactured by Mizusawa Chemical Co., Ltd. SiO ₂ / Al ₂ O ₃ molar ratio = 400/1, average particle diameter = 5 to 7 μm.
Hydrophobic zeolite 3: Shiruton MT2000 manufactured by Mizusawa Chemical Co., Ltd. SiO ₂ / Al ₂ O ₃ molar ratio = 2000/1, average particle diameter = 2-4 μm.
Hydrophobic zeolite 4: Mizusuka Sieves EX-122 manufactured by Mizusawa Chemical Co., Ltd. SiO ₂ / Al ₂ O ₃ molar ratio = 32/1, average particle size = 2.5 to 5.5 μm.
Hydrophobic zeolite 5: Shiruton MT-8000 manufactured by Mizusawa Chemical Co., Ltd. SiO ₂ / Al ₂ O ₃ molar ratio = 8000/1, average particle diameter = 0.8 μm.
Hydrophilic zeolite 1: Mizusuka Sieves Y-420 manufactured by Mizusawa Chemical Co., Ltd. SiO ₂ / Al ₂ O ₃ molar ratio = 5/1, average particle diameter = 5 μm.
[Heat sealable resin]
Heat-sealable resin 1: Wintech WFX4M manufactured by Nippon Polypro Co., Ltd. Propylene / α containing 90% by mass or more of propylene in the raw material? Olefin copolymer. MFR 7 g / 10 min, Vicat softening point 110 ° C.
Heat-sealable resin 2: PC480A manufactured by Sun Allomer. Block-polypropylene, MFR 2 g / 10 min, melting point 165 ° C.
Heat-sealable resin 3: LDPE, LC522 manufactured by Nippon Polyethylene Co., Ltd. MFR 4 g / 10 min, Vicat softening point 96 ° C.

[Adjustment of inorganic odor decomposition agent]
(Preparation of inorganic odor decomposing agent 1)
The following raw materials are mixed to prepare the inorganic odor decomposing agent composition 1, which is melted and homogenized by a conventional method similar to the production of general glass such as bottle glass, pulverized after cooling, and decomposed into a powdery inorganic odor Agent 1 was obtained.
Copper (II) oxide 16 parts by mass Silicon dioxide 64 parts by mass Na ₂ O 20 parts by mass

When each mole% of the above-mentioned copper oxide (II) CuO, silicon dioxide SiO ₂ , and sodium oxide Na ₂ O is calculated as a mole ratio% with the respective molecular weights being 79.55, 60.09, and 61.98, respectively. 12.7%, 67.0%, 20.3%.
When the particle size distribution of the obtained powdery inorganic odor degrading agent 1 was measured, the weight average particle size was 8 μm, and D ₉₆ by weight was 20 μm. Table 1 shows the particle size distribution and the measurement results.

(Preparation of inorganic odor degrading agent 2-3)
The raw materials were mixed in the formulation shown in Table 1, and the same operation as in the inorganic odor decomposing agent 1 was performed to obtain powdery inorganic odor decomposing agents 2-3. The measurement results of the particle size distribution are shown in Table 1.
The molecular weights of sodium oxide CaO and boron oxide B ₂ O ₃ were calculated to be 56.08 and 69.62, respectively.

<Preparation of master batch for sealant layer>
[Preparation of Masterbatch 1]
The following raw materials were melt blended to obtain a master batch 1 for the deodorant layer.
10 parts by mass of hydrophobic zeolite 1 90 parts by mass of heat-sealable resin 1 [Preparation of master batches 2 to 12]
According to the composition of Table 2, the same operation as in Masterbatch 1 was performed to obtain Masterbatch 2-12.

<Deodorization film for heat sterilization treatment and packaging material using the same, production and evaluation of packaging>
[Example 1]
The master batch 1, the master batch 8, and the heat-sealable resin 1 were melt blended at the following ratios to produce a deodorant layer resin composition.
Masterbatch 1 41.65 parts by mass Masterbatch 8 8.35 parts by mass Heat-sealable resin 1 50 parts by mass

Using the obtained resin composition for deodorant layer and heat-sealable resin 1, inflation film formation was performed at 200 ° C., and non-deodorant layer 1 (12 μm) / deodorant layer (36 μm) / non-deodorant layer A deodorizing film for heat sterilization treatment having a configuration of 2 (12 μm) was obtained. In the deodorizing film for heat sterilization treatment, the hydrophobic zeolite content is 2.5% by mass, and the inorganic odor decomposing agent content is 0.5% by mass.
After applying and drying the adhesive 1 on the corona-treated surface side of the PET film 1, the nylon film 1 is pasted, and further the adhesive 1 is applied to the nylon film 1 and dried, and the heat sterilization treatment obtained above A deodorizing film was attached to obtain a film-like laminate, and various evaluations were performed. Table 3 shows the detailed configuration and evaluation results of the laminate.

(Schematic layer structure of laminate 1)
PET film 1 (12 μm) / adhesive 1 layer (4 μm) / nylon film 1 (15 μm) / adhesive 1 layer (4 μm) / deodorizing film for heat sterilization treatment (60 μm) (total thickness 95 μm)

[Examples 2 to 9, 15, 16 and Comparative Examples 3 to 5]
According to the structure of the laminated body of Tables 3-5, the resin composition for deodorizing layers was produced, it operated like Example 1, and the deodorizing film for heat sterilization processes was obtained. The contents of the hydrophobic zeolite and the inorganic odor decomposing agent in the deodorizing film for heat sterilization treatment are as shown in Tables 3 and 4.
And like Example 1, using the obtained deodorizing film for heat sterilization treatment, the film-form laminated body was obtained and various evaluation was performed. The detailed structure and evaluation result of a laminated body are shown in Tables 3-5.

[Example 10]
According to the structure of the laminated body of Table 2, 3, the resin composition for deodorizing layers is produced using the masterbatch 4, the masterbatch 12, and the heat-sealable resin 2, and this resin composition for deodorizing layers is used. Heating for a sealant layer having a structure of non-deodorant layer 1 (12 μm) / deodorant layer (36 μm) / non-deodorant layer 1 (12 μm) cast at 230 ° C. using heat sealable resin 2 A deodorizing film for sterilization treatment was obtained. In the deodorizing film for heat sterilization treatment, the content of hydrophobic zeolite is 2.5% by mass, and the content of the inorganic odor decomposing agent is 0.5% by mass.
And like Example 1, using the obtained deodorizing film for heat sterilization treatment, the film-form laminated body was obtained and various evaluation was performed. Table 3 shows the detailed configuration and evaluation results of the laminate.

[Examples 11 to 14, Comparative Example 2]
According to the structure of the laminated body of Tables 2-4, the resin composition for deodorizing layers is produced, it forms into an inflation film at 200 degreeC, The heat sterilization process for the sealant layers which consist only of a deodorizing layer (60 micrometers) A deodorizing film was obtained. The hydrophobic zeolite content and the inorganic odor decomposing agent content in the deodorizing film for heat sterilization are as shown in Tables 4 and 5.
And like Example 1, using the obtained deodorizing film for heat sterilization treatment, the film-form laminated body was obtained and various evaluation was performed. The detailed structure and evaluation results of the laminate are shown in Tables 4 and 5.

[Comparative Example 1]
The film was blown at 200 ° C. using only the heat-sealable resin 1 to obtain the deodorizing film for heat sterilization treatment for the sealant layer consisting of only the non-deodorizing layer 1 (60 μm). The hydrophobic zeolite content in the deodorizing film for heat sterilization treatment is 0% by mass.
And similarly to Example 1, using the obtained deodorizing film for heat sterilization treatment, the film-like laminated body was obtained and various evaluation was performed. Table 5 shows the detailed configuration and evaluation results of the laminate.

[Result Summary]
Examples 1 to 16 in which the deodorizing film for heat sterilization treatment of the present invention was prepared and used all showed good heat resistance, heat sealability, and reduction rate of odor concentration of hydrogen sulfide and dimethyl sulfide.
In the deodorizing film for heat sterilization treatment, the SiO ₂ / Al ₂ O ₃ molar ratio is 30/1 to 8000/1, which does not include the hydrophobic zeolite according to the present invention, and instead of the hydrophobic zeolite Comparative Example 3 containing hydrophilic zeolite in the sample showed an insufficient concentration reduction rate of hydrogen sulfide and / or dimethyl sulfide, and a heat-sealable resin having a softening point of less than 110 ° C. was used for the deodorizing film for heat sterilization treatment. Although the comparative example 4 was able to produce a laminated body, since it was inferior to heat resistance, subsequent evaluation was stopped. Further, in Comparative Example 2 in which the total content of the hydrophobic zeolite and the inorganic odor decomposing agent according to the present invention in the deodorizing film for heat sterilization treatment is too large, bag breakage occurs in the heat resistance evaluation due to a significant decrease in seal strength. I failed.

<Evaluation method>
[Particle size distribution]
Particle size distribution measuring apparatus LA-920: The particle size distribution of the particles was measured by using, for example, manufactured by Horiba, Ltd., and the average particle size and D ₉₆ in weight average were obtained.
[Heat-resistant]
Using the laminates obtained in the examples and comparative examples, a four-side sealed pouch (outside dimension: 13 cm × 17 cm) filled with 100 cc of water was prepared and subjected to heat sterilization treatment under the following conditions to deform the laminate components. And the presence or absence of alteration was confirmed. The presence or absence of alteration was visually observed.
Atmospheric pressure: 0.21 MPa
Temperature: 121 ° C
Treatment time: 30 minutes Criteria: A case where no wrinkles occurred on the pouch surface and no bag breakage was determined to be acceptable.

[Heat sealability]
In the heat resistance evaluation, if the seal part was not peeled off after the heat sterilization treatment, it was accepted, and if it was peeled off and the bag was broken, it was judged unacceptable.
[Density reduction rate]
Using the laminates obtained in Examples and Comparative Examples, a pouch bag (11 cm × 15 cm) heat-sealed on four sides was prepared, and the following evaluation gas was injected into the pouch bag with a syringe, After leaving at 25 ° C. for 2 days, the air in the pouch bag is collected with a syringe, the concentration of hydrogen sulfide and dimethyl sulfide is measured with GC and a detector tube, and each of hydrogen sulfide and dimethyl sulfide in the pouch bag is measured. The reduction rate of concentration was calculated.
(Evaluation gas)
Hydrogen sulfide: 25ppm
Dimethyl sulfide: 30ppm
Other ingredients: Air

1. 1. Deodorizing film for heat sterilization treatment Sealant layer 2a. Deodorant layer (heat sealable resin + hydrophobic zeolite + inorganic odor decomposing agent)
2b. Deodorant layer (containing heat-sealable resin + inorganic odor decomposing agent)
2c. Deodorant layer (containing heat-sealable resin + hydrophobic zeolite)
3. Non-deodorant layer (containing heat-sealable resin)

Claims (9)

At least a deodorizing film for heat sterilization treatment including a sealant layer on the outermost layer on one side,
The sealant layer includes a heat-sealable resin, a powdery hydrophobic zeolite, and a powdered inorganic odor decomposer,
The softening point of the heat-sealable resin is 110 ° C. or higher and 175 ° C. or lower,
The hydrophobic zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 30/1 or more and 8000/1 or less,
The inorganic odor decomposing agent is a metal oxide or metal salt kneaded or supported on an inorganic substance,
The total content of the hydrophobic zeolite and the inorganic odor decomposer in the sealant layer is 0.3% by mass or more and 15% by mass or less.
Deodorizing film for heat sterilization treatment. The treatment temperature of the heat sterilization treatment is 100 ° C. or more and 140 ° C. or less,
The mass ratio of hydrophobic zeolite / inorganic odor decomposer is 10/90 or more and 95/5 or less,
The deodorizing film for heat sterilization treatment according to claim 1. The inorganic odor decomposing agent is formed from an inorganic odor decomposing agent composition containing at least copper (II) oxide, silicon oxide, and alkali metal oxide.
The deodorizing film for heat sterilization treatment according to claim 1 or 2. The inorganic odor decomposer composition further includes a compound of one or more elements selected from the group consisting of copper, zinc, silver, iron, platinum, and gold.
The deodorizing film for heat sterilization processing of Claim 3. The inorganic odor decomposer composition further comprises one or more alkaline earth metal oxides,
The deodorizing film for heat sterilization processing of Claim 3 or 4. The inorganic odor decomposer composition further contains boron oxide,
The deodorizing film for heat sterilization treatment of any one of Claims 3-5.   The deodorizing film for heat sterilization treatment according to any one of claims 1 to 6, wherein the heat sealable resin is a polypropylene resin.   The deodorizing packaging material for heat sterilization processing produced from the deodorizing film for heat sterilization processing of any one of Claims 1-7.   A deodorant packaging body for heat sterilization treatment produced from the deodorization packaging material for heat sterilization treatment according to claim 8.

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