JP2023002308A - Laminated film, packaging bag, and package - Google Patents

Abstract

[Problem] To provide a laminated film, packaging bag, and package that can reduce retort odor and have good laminate strength. [Solution] The laminated film (50) is composed of a predetermined layer (10), an adhesive layer (20) containing an adhesive component and polyvalent metal particles or polyvalent metal compound particles mixed with the adhesive component, and a sealant layer (30) laminated in this order. The adhesive layer (20) contains agglomerates of polyvalent metal particles or polyvalent metal compound particles within an area of 500 μm x 500 μm, with the number of agglomerates of 9 μm or larger being 30 or less. [Selected Figure] Figure 1

Description

TECHNICAL FIELD The present invention relates to laminated films, packaging bags, and packages.

A packaging material used for packaging an object to be packaged is required to have a function of suppressing quality deterioration of the object to be packaged. For example, as a packaging material, there is known a packaging bag formed by pasting together a pair of laminated films. Such packaging bags are required to have excellent sealing performance in order to prevent quality deterioration of the packaged items.

Examples of packaged items include foodstuffs. When meat products and foods containing sulfur-containing amino acids such as egg products are boiled or retort sterilized, a peculiar odor may be generated. This odor is caused by sulfur compounds such as hydrogen sulfide generated by hydrolysis of sulfur-containing amino acids. Patent Documents 1 and 2 propose to provide a layer containing a polyvalent metal compound in a packaging bag in order to reduce such retort smell.

JP 2014-61682 A JP 2017-94533 A

However, the conventional techniques as described above have the following problems.
There are a wide variety of items to be packaged in packages, and the items to be packaged contain various components. Among these, a specific component may react with components constituting each layer of the laminated film forming the packaging bag, and affect the laminate strength. For example, the layer formed from the polyvalent metal compound of Patent Document 1 may affect the lamination strength between the layers of the laminated film depending on the components contained in the package.

The present invention has been made in view of the above problems, and provides a laminated film, a packaging bag, and a package that can reduce retort smell and have good lamination strength.

In order to achieve the above object, the present invention employs the following means.
That is, the laminated film according to the present invention includes a predetermined layer, an adhesive component, an adhesive layer containing polyvalent metal particles or polyvalent metal compound particles mixed in the adhesive component, and a sealant layer. , which are laminated in this order, and in the adhesive layer, aggregates formed by the polyvalent metal particles or the polyvalent metal compound particles in a range of 500 μm × 500 μm, the number of aggregates having a size of 9 μm or more is 30 or less.

Moreover, in the laminated film according to the present invention, the distance between the aggregates may be 100 μm or more.

Moreover, in the laminated film according to the present invention, the predetermined layer may be a base film having a barrier layer.

Moreover, in the laminated film according to the present invention, the base film may have a nylon layer.

Further, in the laminated film according to the present invention, the adhesive layer may contain 0.5% by mass or more and 10% by mass or less of the polyvalent metal particles or the polyvalent metal compound particles.

Further, in the laminated film according to the present invention, the polyvalent metal particles or the polyvalent metal compound particles may have an average particle size of 10 nm or more and 45 nm or less.

Further, in the laminated film according to the present invention, the polyvalent metal particles or the polyvalent metal compound particles may have a specific surface area of 1 m ² /g or more.

Moreover, in the laminated film according to the present invention, the adhesive layer may further contain a dispersant for dispersing the polyvalent metal particles or the polyvalent metal compound particles in the adhesive component.

Moreover, in the laminated film according to the present invention, the adhesive component may be a cured product of a two-component curing adhesive.

A packaging bag according to the present invention is a packaging bag formed by laminating films, and the film includes the laminated film described in any one of the above.

Moreover, the package which concerns on this invention is provided with the packaging bag as described above, and the to-be-packaged item accommodated in the said packaging bag.

Moreover, in the package according to the present invention, the item to be packaged may contain a sulfur compound.

According to the laminated film, the packaging bag, and the package according to the present invention, the retort odor can be reduced and the lamination strength is good.

BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing which shows an example of the laminated|multilayer film which concerns on the 1st Embodiment of this invention. FIG. 5 is a schematic cross-sectional view showing an example of a laminated film according to a second embodiment of the invention; FIG. 5 is a schematic cross-sectional view showing an example of a laminated film according to a third embodiment of the invention; FIG. 11 is a schematic front view showing an example of a packaging bag and a package according to a fourth embodiment of the present invention; It is a typical perspective view which shows the manufacturing method of the packaging bag which concerns on the 4th Embodiment of this invention. FIG. 11 is a schematic perspective view showing an example of a packaging bag and a package according to a fifth embodiment of the present invention; 11 is an example of an image of OM image observation of Comparative Example 3. FIG.

Embodiments of the present invention are described below with reference to the accompanying drawings. In all the drawings, even when the embodiments are different, the same or corresponding members are denoted by the same reference numerals, and common explanations are omitted. Positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings unless otherwise specified.
Hereinafter, when multiple preferred numerical ranges are exemplified under a specific numerical range, the combination of the upper limit value and the lower limit value is limited to the exemplified combination unless otherwise specified, as long as it is included in the preferred maximum numerical range not. For example, when x1<x2<x3<x4 and the preferred range of the amount X is "x1 or more and x4 or less" and "x2 or more and x3 or less", for example, "more than x1 and less than x4", Numerical ranges such as "x2 or more and x4 or less" and "x3 or more and x4 or less" are also preferable ranges.

[First embodiment]
A laminated film according to a first embodiment of the present invention will be described.
FIG. 1 is a schematic cross-sectional view showing an example of the laminated film according to the first embodiment of the invention.

A laminated film 50 of this embodiment shown in FIG. 1 includes a base film (predetermined layer) 10 , an adhesive layer 20 and a sealant layer 30 . The base film 10, the adhesive layer 20, and the sealant layer 30 in the laminated film 50 are laminated in this order. The base film 10, the adhesive layer 20, and the sealant layer 30 each have optical transparency to transmit visible light. For this reason, the laminated film 50 has a light transmitting portion through which visible light is transmitted in the thickness direction (vertical direction in the drawing). In the example shown in FIG. 1, the light transmitting portion is the entire laminate film 50 . Note that the laminated film 50 does not have to be provided with the light transmitting portion.
The light-transmitting portion of the laminated film 50 has a haze of 30% or less as measured according to the haze measurement method specified in JIS-K-7136. Hereinafter, the haze specified in JIS-K-7136 is simply referred to as "haze".

The base film 10 has a resin layer 12 and a barrier layer 14 . Note that the base film 10 does not have to include the barrier layer 14 .

The resin layer 12 is composed of, for example, a resin film.
Examples of resin films include polyester films made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.; polyolefin films made of polyethylene, polypropylene, etc.; polystyrene films; polyamides such as 66-nylon. polyacrylonitrile film; polyimide film; and engineering plastic films made of other engineering plastics.
As for the resin film constituting the resin layer 12, one of the above-described resin films may be used alone, or two or more thereof may be used in combination.
For example, the resin layer 12 may be configured by laminating a plurality of resin films of the same type.
The resin film may be either a stretched film or an unstretched film. The resin film may be a multilayer film in which at least one stretched film and at least one unstretched film are laminated.
The resin layer 12 may have a film that is optionally biaxially stretched. In this case, mechanical strength and dimensional stability can be improved.

It is more preferable that the resin layer 12 has one or both of a polyester film and a biaxially oriented polypropylene film, particularly from the viewpoint of achieving both strength and flexibility.
More preferably, the resin layer 12 has one or both of a polypropylene film and a polyethylene terephthalate film, particularly from the viewpoint of improving strength and reducing costs.
It is more preferable that the resin layer 12 has a nylon film, particularly from the viewpoint of improving the strength. Since nylon film is excellent in flexibility, pinholes are less likely to occur. Therefore, when a packaging bag using the laminated film 50 is used to form a package, it is possible to prevent pinholes from forming in the laminated film 50 and degrading the packaged object. Such an action is particularly useful when the item to be packaged is food.

The thickness of the resin layer 12 is not particularly limited and can be set according to the application or required properties. The thickness of the resin layer 12 may be, for example, 3 μm or more and 100 μm or less, and more preferably 6 μm or more and 50 μm or less.
The resin layer 12 may contain appropriate additives. Additives include at least one selected from fillers, antistatic agents, plasticizers, lubricants, antioxidants, and the like.

The surface 12a of the resin layer 12 is the surface that forms the outer surface of the laminated film 50 when forming the packaging bag.
The surface 12b of the resin layer 12 is the surface opposite to the surface 12a in the thickness direction, and is the bonding surface with the barrier layer 14 described later.
Appropriate surface treatment may be applied to the laminated film 50 . For example, the surface 12b may be subjected to an appropriate surface treatment to improve adhesion of the barrier layer 14. FIG. Examples of surface treatments include, for example, at least one treatment selected from chemical treatment, solvent treatment, corona treatment, plasma treatment, and ozone treatment.

The barrier layer 14 is a layer having barrier properties against at least oxygen and water vapor. The barrier layer 14 is laminated on the surface 12 b of the resin layer 12 .
The number of layers of the barrier layer 14 is not particularly limited as long as it includes at least one layer having barrier properties.
For example, when the barrier layer 14 is composed of a single layer, a deposited layer composed of an inorganic material, a barrier film composed of a resin having a barrier property, and the like can be cited.
For example, when the barrier layer 14 is composed of multiple layers, a barrier film, such as a resin film, the surface of which is coated with an inorganic substance having a barrier property can be used.
Inorganic substances that can be used for the barrier layer 14 include silica, aluminum, silicon, and the like. Such an inorganic material may be deposited on the surface of the resin layer 12 when forming the barrier layer 14 with a single layer.
Examples of barrier films that can be used for the barrier layer 14 include nylon-based barrier films and ethylene-vinyl alcohol-based barrier films. Such a barrier film may be laminated to the resin layer 12 by extrusion lamination, dry lamination, wet coating, or the like when forming the barrier layer 14 with a single layer.
For example, when a barrier film coated with an inorganic material is used as the barrier layer 14, silica, aluminum, silicon, or the like may be used as the inorganic material. In this case, the barrier film may be laminated on the resin layer 12 by dry lamination or the like.
As for the barrier layer 14, one type illustrated above may be used alone, or two or more types may be used in combination.

The layer thickness of the barrier layer 14 is not particularly limited. For example, when the barrier layer 14 is composed of a deposited layer, the layer thickness may be 5 nm or more and 100 nm or less.
The barrier layer 14 can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, a plasma chemical vapor deposition method (CVD), a dry lamination method, an extrusion lamination method, or the like.

The adhesion layer 20 is a layer that adheres the barrier layer 14 and a sealant layer 30 to be described later.
The adhesive layer 20 contains an adhesive component and polyvalent metal particles or polyvalent metal compound particles mixed with the adhesive component.

Examples of adhesive components include cured products such as urethane-based adhesives, polyester-based adhesives, polyamide-based adhesives, epoxy-based adhesives, and isocyanate-based adhesives.
The adhesive component in the adhesive layer 20 is more preferably made of a two-liquid curable adhesive in that it easily suppresses deterioration of polyvalent metal particles or polyvalent metal compound particles, which will be described later.
Such an effect of suppressing deterioration tends to appear more remarkably when a two-liquid curing urethane-based adhesive is used. Therefore, it is particularly preferable to use a urethane-based adhesive among the two-liquid curing adhesives.

Polyvalent metal particles are particles made of a metal that generates multivalent ions (hereinafter referred to as polyvalent metal). Polyvalent metal compound particles are particles formed of a polyvalent metal compound.
The polyvalent metal particles or polyvalent metal compound particles are used for the purpose of trapping substances that cause retort odors (hereinafter sometimes referred to as odor-causing substances) such as sulfur compounds in the adhesive layer 20 . Hydrogen sulfide, mercaptans, sulfur dioxide, sulfur trioxide and the like are examples of sulfur compounds that cause odors.
The principle of capturing odor-causing substances by polyvalent metal particles and polyvalent metal compound particles has not been theoretically elucidated, but it can be confirmed experimentally that they are effective in reducing odor-causing substances. .
The polyvalent metal particles and polyvalent metal compound particles mixed in the adhesive layer 20 are not particularly limited as long as they have a function of trapping compounds that cause retort smell and can stably exist inside the adhesive component of the adhesive layer 20. .

Examples of polyvalent metal particles include particles of alkaline earth metals such as beryllium, magnesium and calcium; particles of transition metals such as titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper and zinc; and particles of aluminum. etc. may be used.
The polyvalent metal particles may have an oxide film formed on their surfaces or may be coated so that they can stably exist inside the adhesive layer 20 .

Examples of polyvalent metal compound particles include particles of polyvalent metal oxides, hydroxides, carbonates, organic acid salts (eg, acetates), and inorganic acid salts. As polyvalent metal compound particles, for example, particles of ammonium complexes of polyvalent metal oxides, secondary to quaternary amine complexes of polyvalent metal oxides, or carbonates or organic acid salts thereof may be used.
It is more preferable to use polyvalent metal compound particles because they tend to exist more stably inside the adhesive layer 20 .
As the polyvalent metal compound particles, particles of zinc compounds, aluminum compounds, magnesium compounds and the like are more preferably used from the viewpoint of stability in the adhesive component and ease of production. From the viewpoints of ease of handling and cost, it is particularly preferable to use particles of zinc oxide, aluminum oxide, magnesium oxide, or the like as the polyvalent metal compound particles.

For simplicity, the polyvalent metal particles or polyvalent metal compound particles mixed in the adhesive component are sometimes referred to as "additive particles" below.
In the adhesive layer 20, one type or two or more types of additive particles can be used to be mixed in the adhesive component.

The content of the additive particles in the adhesive layer 20 is not particularly limited.
As the content of additive particles increases, the amount of odor-causing substances captured increases, so retort odors can be easily suppressed. On the other hand, when the content of the additive particles increases, the lamination strength of the adhesive layer 20 tends to decrease, and the transparency of the laminated film 50 may decrease.
For example, the content of the additive particles in the adhesive layer 20 is 0.5% by mass or more and 10% by mass in terms of easily achieving both the lamination strength of the adhesive layer 20 and the transparency of the laminated film and the effect of reducing the retort odor. % or less, and more preferably 1.5 mass % or more and 5 mass % or less.
If the content of the additive particles is less than 1% by mass, the effect of suppressing retort odor may be too low.
If the content of the additive particles exceeds 10% by mass, the lamination strength of the adhesive layer 20 may become too low, or the transparency of the laminated film may become too low.

It is more preferable that the distribution of the additive particles in the adhesive layer 20 is less uneven. For example, if the distribution of the additive particles concentrates in a specific region due to aggregation, etc., the transparency of the laminated film 50 tends to be uneven. The uneven distribution of the additive particles in the adhesive layer 20 also causes a decrease in haze and a decrease in lamination strength.
In particular, in the adhesive layer 20, if a large aggregate of additive particles is formed, it becomes grainy and conspicuous. In particular, when granular unevenness is closely arranged, streak unevenness is formed and becomes more conspicuous. For example, when the laminated film 50 is used in a packaging bag and the light-transmitting portion is used to allow the objects to be packaged in the packaging bag to be visible from the outside, it is preferable that granular unevenness and streak unevenness are not visible.

For example, from the viewpoint of improving the laminate strength of the adhesive layer 20, the number of aggregates of additive particles of 9.0 μm or more is preferably 30 or less in the range of 500 μm×500 μm. Also, the distance between aggregates is preferably 100 μm or more.
Here, "aggregate" is used in a broad sense, and means an apparent mass when observed with a microscope or the like in the thickness direction. No particular distinction is made between whether the apparent clumps are formed by aggregation of additive particles or appear clumped due to the high distribution density seen in the thickness direction in a certain region.

For example, it is believed that the additive particles trap odor-causing substances that permeate the adhesive layer 20 by adsorbing them.
In order for the additive particles to efficiently capture odor-causing substances, it is more preferable that the additive particles have a larger specific surface area. Here, the specific surface area represents the surface area per unit mass of the additive particles. For example, the specific surface area of the additive particles may be 1 m ² /g or more, more preferably 5 m ² /g or more.
When the specific surface area increases, the particle size of the additive particles becomes too small, and, for example, they tend to scatter in the environment, so care must be taken when handling them. From the viewpoint of facilitating handling of the additive particles in the manufacturing process, the specific surface area of the additive particles may be 100 m ² /g or less, more preferably 50 m ² /g.

If the average particle size of the additive particles as primary particles is too large, aggregates exceeding 9.0 μm are likely to be formed. However, if the additive particles have a relatively small average particle size, the maximum size of the aggregates will change depending on the mixing method in the manufacturing process, and the correlation between the average particle size and the maximum size of the aggregates will be weak.
Hereinafter, unless otherwise specified, the average particle size of the additive particles as primary particles is simply referred to as the average particle size of the additive particles. The average particle size is calculated from the following general formula by determining the area circle equivalent diameter from an image of the powder magnified 50,000 to 200,000 times with a transmission electron microscope (TEM). The average particle size is represented by the formula: sum of area equivalent circle diameters of measured particles/number of measured particles (the number of measured particles is at least 100).
The average particle size of the additive particles is not particularly limited.
For example, if the average particle size of the additive particles is less than 5 nm, the manufacturing cost may increase and the handling in the manufacturing process may become difficult.
For example, when the average particle diameter of the additive particles exceeds 100 nm, the specific surface area becomes small, which may reduce the effect of trapping odor-causing substances.

In order to reduce the size of aggregates of additive particles in the adhesive component, the adhesive layer 20 contains 1 part by mass or more and 50 parts by mass or less of a dispersant with respect to 100 parts by mass of the additive particles. may
The type of dispersant is not particularly limited as long as it can disperse the additive particles in the liquid adhesive component for forming the adhesive component.
For example, dispersants include (poly)ester salts, polyether phosphates, alkyl sulfates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfosuccinates, alkyldiphenylether disulfonates, alkyl Phosphates, aromatic phosphates, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, alkylallyl sulfates, polyoxyethylene alkyl phosphates, sorbitan alkyl esters, glycerin fatty acid esters, Sorbitan fatty acid ester, sucrose fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan alkyl ester, polyoxyethylene alkylallyl ether, polyoxyethylene derivative, polyoxyethylene sorbitol fatty acid ester, polyoxy fatty acid ester, polyoxyethylene alkylamine, chloride Examples include vinyl-vinyl acetate copolymers. These dispersants may be used alone or in combination of two or more.

The lamination strength of the adhesive layer 20 is measured according to JIS Z 0238:1998 by a T-peel method (crosshead speed: 300 mm/min) using a Tensilon tensile tester.
The lamination strength of the adhesive layer 20 may be, for example, 6 N/15 mm width or more, and more preferably 7 N/15 mm width or more.

The thickness of the adhesive layer 20 is not particularly limited as long as the laminated film 50 has good lamination strength when formed into a packaging bag and has a good effect of reducing odor-causing substances.
The thickness of the adhesive layer 20 may be, for example, 0.01 μm or more and 5 μm or less, and more preferably 0.03 μm or more and 3 μm or less.
If the thickness of the adhesive layer 20 is less than 0.01 μm, the laminate strength may decrease and the amount of odor-causing substances captured may be too small.
If the thickness of the adhesive layer 20 exceeds 5 μm, the laminated film 50 may become too thick.

The sealant layer 30 is a layer for bonding the laminated film 50 to another laminated film by thermal fusion. The sealant layer 30 is not particularly limited as long as it can be melted by heat and fused together with the sealant layer of another laminated film.
Examples of materials for the sealant layer 30 include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, and ethylene-acrylic acid. Resins such as copolymers, ethylene-methyl acrylate copolymers, ethylene-methacrylic acid copolymers, and ethylene-propylene copolymers can be mentioned. As for the resin used for the sealant layer 30, any one of the exemplified resins may be used alone, or two or more thereof may be used in combination.
For example, when forming a package for boiling sterilization or retort sterilization using the laminated film 50, the sealant layer 30 more preferably contains unstretched polypropylene resin from the viewpoint of maintaining sufficient adhesion.

The sealant layer 30 may be laminated on the adhesive layer 20 while the resin composition is formed into a film by extrusion lamination, or a film sheet may be attached to the adhesive layer 20 .
The thickness of the sealant layer 30 may be, for example, 10 μm or more and 150 μm or less, and more preferably 30 μm or more and 80 μm or less.

Next, an example of a method for manufacturing the laminated film 50 will be described.
First, the base film 10 is prepared by laminating the barrier layer 14 on the resin film forming the resin layer 12 .
After that, the adhesive layer 20 and the sealant layer 30 are laminated in this order on the barrier layer 14 of the base film 10 .
Dry lamination, for example, may be used as the lamination method.
For example, a coating liquid is prepared by mixing additive particles with an adhesive that forms the adhesive component of the adhesive layer 20 after curing, and the coating liquid is applied to the surface of the barrier layer 14 of the base film 10 by a dry lamination machine. Then, the resin film forming the sealant layer 30 and the base film 10 are thermocompression bonded using hot rolls.
The coating method of the coating liquid is not particularly limited. For example, the coating liquid can be applied using a coater such as a roll coater, a reverse roll coater, a gravure coater, a micro gravure coater, a knife coater, a bar coater, a wire bar coater, a die coater, a dip coater and a spin coater.
A non-sol laminator can be used as the lamination method, and a coating liquid mixed with non-sol adhesive additive particles can also be used as the adhesive component of the adhesive layer 20 .

When preparing the coating liquid, it is possible to mix the additive particles with the adhesive that forms the adhesive component and sufficiently stir the additive particles so that the aggregate size of the additive particles is 9.0 μm or less. more preferred. By stirring, the additive particles are dispersed in the coating liquid.
In order to reduce the size of aggregates of additive particles, it is more preferable to add a dispersant to the coating liquid. The dispersant may be added directly to the adhesive together with the additive particles, but after forming a particle dispersion by dispersing the additive particles and the dispersant in a solvent, the particle dispersion and the adhesive are mixed, It is more preferable to prepare the coating liquid by stirring. In this case, the dispersion of the additive particles in the coating liquid is promoted.
The additive particles are more preferably subjected to a physical fibrillation treatment for making the additive particles finer in a state in which the additive particles, the dispersant and the solvent are mixed. This promotes refinement and dispersion of the additive particles in the coating liquid.
Physical fibrillation processes include high-pressure homogenizers, ultra-high-pressure homogenizers, ball mills, roll mills, cutter mills, planetary mills, jet mills, attritors, grinders, juicer mixers, homomixers, ultrasonic homogenizers, nanogenizers, and underwater counterimpingers. Mechanical processing can be mentioned.

By performing a dispersion treatment for dispersing the finely divided additive particles in the coating liquid using one or more of the means described above, the growth of aggregates in the coating liquid can be suppressed.
The dispersion treatment also suppresses the generation of precipitates in the coating liquid, so that the additive particles can be efficiently dispersed in the coating liquid.
After the coating liquid is prepared, it is more preferable to perform a filtration treatment before coating.

Since the laminated film 50 includes the barrier layer 14 having barrier properties against oxygen and water vapor, the oxygen and water vapor that have passed through the resin layer 12 are suppressed from passing through the adhesive layer 20 and the sealant layer 30 . Therefore, it is possible to prevent oxygen, water vapor, etc. from entering the packaging bag. As a result, the deterioration of the packaged item caused by at least one of oxygen and water vapor can be suppressed in the package containing the packaged item in the packaging bag formed of the laminated film 50 . Deterioration of polyvalent metal particles or polyvalent metal compound particles caused by at least one of oxygen and water vapor permeating from the outside can be similarly suppressed.

Since the laminated film 50 has the adhesive layer 20 containing polyvalent metal particles or polyvalent metal compound particles between the base film 10 and the sealant layer 30, the sulfur compound permeated into the adhesive layer 20 through the sealant layer 30. It can adsorb odor-causing substances such as For this reason, in a package containing an object to be packaged in a packaging bag formed by the laminated film 50, as odor-causing substances such as sulfur compounds derived from the object to be packaged permeate the adhesive layer 20, polyvalent metal particles or Captured by polyvalent metal compound particles. As a result, it is possible to reduce the retort odor in the package.
The inclusion of polyvalent metal particles or polyvalent metal compound particles suppresses a decrease in lamination strength of the adhesive layer 20 . Since the polyvalent metal particles or polyvalent metal compound particles are mixed with the adhesive component of the adhesive layer 20, the polyvalent metal particles or polyvalent metal compound particles are mixed with components such as acetic acid and amino acids contained in the package. Reaction and deterioration can also be suppressed. Therefore, the effect of reducing odor-causing substances and the laminate strength are less likely to decrease over time.

As described above, according to the laminated film 50 of the present embodiment, it is possible to provide a laminated film that can reduce retort odor and has good lamination strength.

[Second embodiment]
A laminated film according to a second embodiment of the present invention will be described.
FIG. 2 is a schematic cross-sectional view showing an example of the laminated film according to the second embodiment of the invention.

A laminated film 60 of the present embodiment shown in FIG. 2 includes a base film (predetermined layer) 10A in place of the base film 10 in the laminated film 50 of the first embodiment.
10 A of base films are provided with the adhesion layer 16 and the intermediate|middle layer 18 in this order between the barrier layer 14 and the adhesion layer 20. As shown in FIG. The following description will focus on the differences from the first embodiment.

The adhesive layer 16 is a layer that bonds the barrier layer 14 and the intermediate layer 18 together.
The adhesive layer 16 is made of one or more of the materials exemplified as adhesive components in the adhesive layer 20 . The adhesive layer 16 may be made of the same material as the adhesive layer 20 in the laminated film 60, or may be made of a different material.
The adhesive layer 16 may contain no additive particles or may contain additive particles.
When the adhesive layer 16 contains additive particles, the laminated film 60 is an example of a case where a plurality of adhesive layers containing additive particles are provided.

When the adhesive layer 16 contains additive particles, the type, content, specific surface area, layer thickness, and average particle size of the additive particles in the adhesive layer 16 are not particularly limited.
For example, the type, content, specific surface area, layer thickness, and average particle size of the additive particles in the adhesive layer 16 are the same types and suitable numerical ranges as those exemplified for the adhesive layer 20 in the laminated film 50. is more preferable.
The same applies to the type, content, specific surface area, layer thickness, and average particle size of the adhesive layer 20 in the laminated film 60 .

When the adhesive layer 16 contains additive particles, the maximum diameter and distribution of aggregates of the additive particles in the laminated film 60 are not particularly limited.
More preferably, each of the adhesive layers 20 and 16 in the laminated film 60 has a maximum diameter of aggregates of additive particles in the laminated film 60 within a preferred range of the adhesive layer 20 in the laminated film 50 .
More preferably, the distribution of aggregates of additive particles in the laminated film 60 is within the preferred range of the adhesive layers 20 and 16 in the laminated film 60 , respectively, of the adhesive layer 20 in the laminated film 50 .

The intermediate layer 18 is a resin layer arranged between the barrier layer 14 and the sealant layer 30 . Intermediate layer 18 is adhered to barrier layer 14 via adhesive layer 16 and to sealant layer 30 via adhesive layer 20, respectively.
A material for the intermediate layer 18 is not particularly limited.
The type of intermediate layer 18 can be appropriately selected according to the application of the laminated film 60 . For example, at least one of oxygen barrier properties, water vapor barrier properties, mechanical strength, bending resistance, puncture resistance, impact resistance, abrasion resistance, cold resistance, heat resistance, chemical resistance, and light-shielding resistance If a resin film with excellent properties is selected, the properties are improved in the laminated film 60 .
For example, suitable materials for the intermediate layer 18 include nylon, polyethylene terephthalate, polyamide, polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyvinyl alcohol, ethylene-propylene copolymers, and ethylene-vinyl acetate copolymer saponified materials. A film or a resin film having a deposited layer can be used.
For example, by using nylon as the intermediate layer 18, the flexibility is improved, and even when a large external force is applied, the occurrence of pinholes can be suppressed. Therefore, when a packaging bag using the laminated film 50 is used to form a package, it is possible to prevent pinholes from forming in the laminated film 60 and degrading the package. Such an action is particularly useful when the item to be packaged is food.

The laminated film 60 of the present embodiment is formed in the same manner as the laminated film 50 except that the base film 10A is formed by laminating the adhesive layer 16 and the intermediate layer 18 on the barrier layer 14 instead of the base film 10. can be manufactured.
Especially when the adhesive layer 16 contains additive particles, the adhesive layer 16 can be manufactured in the same manner as the adhesive layer 20 in the first embodiment.

The laminated film 60 of the present embodiment has the same configuration as the laminated film 50 of the first embodiment except that the adhesive layer 16 and the intermediate layer 18 are laminated between the barrier layer 14 and the adhesive layer 20. Therefore, it is possible to provide a laminated film that can reduce retort odor and have good lamination strength.
In particular, since the laminated film 60 includes the intermediate layer 18 , the properties of the laminated film 60 can be improved according to the properties of the intermediate layer 18 .
Furthermore, when the adhesive layer 16 contains polyvalent metal particles or polyvalent metal compound particles, there are two layers for trapping odor-causing substances, so the effect of reducing odor-causing substances can be improved.

[Third Embodiment]
A laminated film according to a third embodiment of the present invention will be described.
FIG. 3 is a schematic cross-sectional view showing an example of the laminated film according to the third embodiment of the invention.

A laminated film 70 of the present embodiment shown in FIG. 3 includes a base film (predetermined layer) 10B instead of the base film 10A in the laminated film 70 of the second embodiment. The laminate film 70 includes a resin layer 12, an adhesive layer 16, an intermediate layer 18, an adhesive layer 16B, and an intermediate layer 18B, which are laminated in this order. In the following, the points different from the second embodiment will be mainly described.

The adhesive layer 16 is a layer that bonds the resin layer 12 and the intermediate layer 18 together. The adhesive layer 16B is a layer that bonds the intermediate layer 18 and the intermediate layer 18B.
The adhesive layers 16 and 16B are made of one or more of the materials exemplified as adhesive components in the adhesive layer 20 . The adhesive layers 16 and 16B may be made of the same material as the adhesive layer 20 in the laminated film 70, or may be made of a different material.
The adhesive layers 16 and 16B may contain no additive particles or may contain additive particles.
In the case where the adhesive layers 16 and 16B contain additive particles, the laminated film 70 is an example of having a plurality of adhesive layers containing additive particles.

When additive particles are contained in the adhesive layers 16, 16B, the type, content, specific surface area, layer thickness, and average particle size of the additive particles in the adhesive layers 16, 16B are not particularly limited.
For example, the type, content, specific surface area, layer thickness, and average particle size of the additive particles in the adhesive layers 16 and 16B are the same as those exemplified for the adhesive layer 20 in the laminated film 50, and the preferred numerical ranges. is more preferable.
The same applies to the type, content, specific surface area, layer thickness, and average particle size of the adhesive layer 20 in the laminated film 70 .

When additive particles are contained in adhesive layers 16 and 16B, the maximum diameter and distribution of aggregates of additive particles in laminated film 70 are not particularly limited.
More preferably, each of the adhesive layers 16 and 16B in the laminated film 70 has a maximum diameter of aggregates of additive particles in the laminated film 70 within a preferred range of the adhesive layer 20 in the laminated film 50 .
More preferably, the distribution of aggregates of additive particles in laminated film 70 is within the preferred range of adhesive layers 16 and 16B in laminated film 70 for adhesive layer 20 in laminated film 50 .

The intermediate layer 18 is a resin layer arranged between the resin layer 12 and the intermediate layer 18B. The intermediate layer 18 is adhered to the resin layer 12 via the adhesive layer 16 and to the intermediate layer 18B via the adhesive layer 16B.
A material for the intermediate layer 18 is not particularly limited.
The type of intermediate layer 18 can be appropriately selected according to the application of the laminated film 70 . For example, at least one of oxygen barrier properties, water vapor barrier properties, mechanical strength, bending resistance, puncture resistance, impact resistance, abrasion resistance, cold resistance, heat resistance, chemical resistance, and light-shielding resistance If a resin film with excellent properties is selected, the properties are improved in the laminated film 70 .
For example, suitable materials for the intermediate layer 18 include nylon, polyethylene terephthalate, polyamide, polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyvinyl alcohol, ethylene-propylene copolymers, and ethylene-vinyl acetate copolymer saponified materials. A film or a resin film having a deposited layer can be used.
For example, by using nylon as the intermediate layer 18, the flexibility is improved, and even when a large external force is applied, the occurrence of pinholes can be suppressed. Therefore, when a packaging bag using the laminated film 70 is used to form a package, it is possible to prevent pinholes from forming in the laminated film 70 and degrading the package. Such an action is particularly useful when the item to be packaged is food.

Intermediate layer 18B is a layer disposed between intermediate layer 18 and sealant layer 30 . The intermediate layer 18B is adhered to the intermediate layer 18 via the adhesive layer 16B and to the sealant layer 30 via the adhesive layer 20, respectively.
For example, an aluminum film foil can be used as the intermediate layers 18, 18B. Aluminum film foil has the property of blocking light and making it difficult for gases and liquids to pass through. Therefore, when a packaging bag using the laminated film 70 is used to form a package, it is possible to prevent deterioration of the packaged item. In addition, since the odor is not released, it is possible to prevent the odor from escaping and the flavor from deteriorating. Such an action is particularly useful when the item to be packaged is food.

According to the laminated film 70 of the present embodiment, it is possible to provide a laminated film that can reduce retort odor and has good lamination strength.

[Fourth embodiment]
A packaging bag and package according to a fourth embodiment of the present invention will be described.
FIG. 4 is a schematic front view showing an example of a packaging bag and package according to a fourth embodiment of the present invention.

As shown in FIG. 4 , the package 200 of this embodiment includes the packaging bag 100 of this embodiment and an item to be packaged 110 housed inside the packaging bag 100 .
The packaging bag 100 includes a seal portion 101 formed by pasting together the peripheral edges of a pair of laminated films 50 cut into a substantially rectangular shape, and an accommodating portion 102 formed between the pair of laminated films 50 surrounded by the sealed portion 101. , provided. That is, the packaging bag 100 is sealed by the sealing portions 101 at the side ends, the lower end and the upper end.
The accommodation portion 102 forms an accommodation space sandwiched between the pair of laminated films 50 and surrounded by the seal portion 101, and stores an object 110 to be packaged such as food, for example.
For example, the package 200 may be a retort food product obtained by heat sterilizing a food item 110 and sealing it with a packaging bag 100 .

The pair of laminated films 50 are formed by cutting the laminated film 50 of the first embodiment into appropriate sizes.
A pair of laminated films 50 are overlaid so that the respective sealant layers 30 face each other. Each sealant layer 30 is heat-sealed to the outer periphery of a pair of laminated films 50 . Thereby, a seal portion 101 is formed.

The packaging bag 100 has opening means 120 . For example, the unsealing means 120 has a pair of easy-to-open processed portions 124 formed on the seal portion 101 at the side end, and a half-cut line 121 that serves as a path for cutting between the pair of easy-to-open processed portions 124 . .
The easy-open processing part 124 is not particularly limited as long as it has a configuration that allows the packaging bag 100 to be easily opened. For example, the easy-to-open processed portion 124 may be formed by a scar group consisting of a collection of fine concave portions formed on the surface of the seal portion 101 . For example, the easy-to-open processed portion 124 may be a notch penetrating through the edge of the seal portion 101 in the thickness direction. The shape of the notch is not particularly limited, and may be, for example, a V-shaped, U-shaped, or I-shaped notch.
For example, the half-cut lines 121 can be formed by laser processing.

A method of manufacturing the packaging bag 100 and the package 200 will be described.
FIG. 5 is a schematic perspective view showing a method of manufacturing a packaging bag according to the fourth embodiment of the invention.

A pair of laminated films 50 cut according to the outer shape of the packaging bag 100 are prepared.
After that, as shown in FIG. 5, the sealant layers 30 of the laminated films 50 are opposed to each other, and the sealant layers 30 of the lower ends and side ends of the laminated films 50 are heat-sealed.
As a result, seal portions 101 are formed at the lower end and side ends. A housing portion 102 is formed inside each laminated film 50 surrounded by the sealing portion 101 in a U-shape.
The upper end of the packaging bag 100 is formed with an opening that communicates with the housing portion 102 .
After that, the package 110 is filled from the upper end of the unsealed packaging bag 100 . Thereafter, the sealant layers 30 of the laminated film 50 facing each other at the upper end portions are heat-sealed to form the seal portion 101 also at the upper end portions. Thus, a package 200 as shown in FIG. 4 can be manufactured.

In the packaging bag 100 of this embodiment, the containing portion 102 is formed of the laminated film 50 similar to that of the first embodiment.
Since each laminated film 50 has the barrier layer 14, it is possible to suppress oxygen and water vapor permeating from the outside to the inside, and to suppress deterioration of the members inside the barrier layer 14 and the package 110 caused by oxygen and water vapor. .
Each laminated film 50 contains polyvalent metal particles or polyvalent metal compound particles in the adhesive layer 20 on the inner side (package side) of the barrier layer 14 . For this reason, it is possible to adsorb, for a long period of time, substances that cause retort odors, such as sulfur compounds, generated from the object 110 to be packaged. Therefore, the packaging bag 100 can prevent the causative substances of the retort odor from accumulating inside the object to be packaged 110 in the containing portion 102 from accumulating in the object to be packaged 110 within the containing portion 102 .
As a result, it is possible to reduce the retort odor that occurs when the package 200 is opened.
Depending on the type, the object to be packaged 110 may contain a component (degradation-causing component) that degrades the polyvalent metal particles or polyvalent metal compound particles and deteriorates the retort odor trapping action. For example, acids such as acetic acid contained in various foods tend to degrade polyvalent metal particles or polyvalent metal compound particles.
In the present embodiment, the polyvalent metal particles or polyvalent metal compound particles are mixed in the adhesive component and covered with the adhesive component. Since the chemical reaction with the component is suppressed, the polyvalent metal particles or polyvalent metal compound particles are less likely to deteriorate.

As described above, according to the packaging bag 100 and the package 200 of the present embodiment, since the laminated film 50 of the first embodiment is provided, retort smell can be reduced as in the first embodiment. It is possible to provide a packaging bag and a package having good lamination strength. Even if the laminated film 60 of the second embodiment or the laminated film 70 of the third embodiment is used instead of the laminated film 50, the same effects can be obtained.

[Fifth embodiment]
A packaging bag and package according to a fifth embodiment of the present invention will be described.
FIG. 6 is a schematic perspective view showing an example of a packaging bag and package according to a fifth embodiment of the present invention.

As shown in FIG. 6, a package 210 of this embodiment includes a packaging bag 150 and an object to be packaged 110 similar to that of the fourth embodiment.
The packaging bag 150 is a standing pouch comprising a pair of laminated films 50 and a bottom tape adhered to the lower end of each laminated film 50 . The bottom tape 152 is composed of a laminated film having a layer structure similar to that of the laminated film 50 .

The packaging bag 150 and package 210 of this embodiment are configured in the same manner as the packaging bag 100 and package 200 of the fourth embodiment, except that they are formed in the shape of a standing pouch by including a bottom tape 152. be done.
The packaging body 210 is made by manufacturing a packaging bag 150 having an opening at the upper end by a well-known standing pouch manufacturing method using a pair of laminated films 50 and a bottom tape 152, and then filling the object 110 to be packaged from the upper end. It can be manufactured by forming a seal portion 101 by sealing the upper end portion.

The packaging bag 150 and package 210 of the present embodiment include the laminated film 50 as in the fourth embodiment, and thus have the same effects as in the fourth embodiment. Even if the laminated film 60 of the second embodiment or the laminated film 70 of the third embodiment is used instead of the laminated film 50, the same effects can be obtained.

In each of the above-described embodiments, an example in which the entire laminated films 50 and 60 serve as a light transmitting portion has been described.
However, by providing a printed layer on an appropriate portion of the laminated films 50 and 60 and forming a light shielding portion on a portion of the laminated films 50 and 60, a light transmitting portion is formed on a portion of the laminated films 50 and 60. may be formed.
For example, when the packaging bag 100 is formed from a pair of laminated films 50 as in the fourth embodiment, one or both of the paired laminated films 50 may have a light-shielding portion formed of a printed layer.
For example, in the laminated films 50 and 60, the printed layer may be provided between the resin layer 12 and the barrier layer 14.
The printing layer is, for example, a layer composed of ink made by adding various pigments, plasticizers, desiccants, stabilizers, etc. to binder resins such as urethane, acrylic, nitrocellulose, or rubber. be. Characters, patterns, and the like can be displayed on the printed layer. As the printing method, for example, known printing methods such as offset printing, gravure printing, flexographic printing, silk screen printing, and inkjet printing can be used.
The surface 12b of the resin layer 12 forming the print layer may be previously subjected to corona treatment or ozone treatment as a pretreatment. In this case, the adhesion between the printed layer and the resin layer 12 can be improved.

The layer structure of the laminated film in the first and second embodiments is an example. For example, the laminated film may include any layer or thin film between the adhesive layer 20 and the sealant layer 30 or between the resin layer 12 and the barrier layer 14 as long as the function of the laminated film is not significantly impaired. .

In the description of the second embodiment above, the polyvalent metal particles or polyvalent metal compound particles are contained in both the adhesive layer 20 of the laminated film 60 and the adhesive layers 20 and 16 of the laminated film 60. I have explained, with an example. However, the polyvalent metal particles or polyvalent metal compound particles may be contained only in the adhesive layer 16 .

In the description of the second embodiment, an example in which the intermediate layer is one layer has been described. However, the laminated film may contain two or more intermediate layers.

The resin layer 12, the adhesive layer 16, the intermediate layer 18, the adhesive layer 16, the barrier layer 14 containing aluminum, the adhesive layer 20, and the sealant layer 30 may be laminated in this order.
The resin layer 12, the adhesive layer 16, the barrier layer 14 containing aluminum, the adhesive layer 20, and the sealant layer 30 may be laminated in this order.
The barrier layer 14, the adhesive layer 16, the intermediate layer 18, the adhesive layer 20, and the sealant layer 30 may be laminated in this order.
The resin layer 12, the adhesive layer 16, the intermediate layer 18, the adhesive layer 20, and the sealant layer 30 may be laminated in this order.
The intermediate layer 18, the adhesive layer 20, and the sealant layer 30 may be laminated in this order.
The resin layer 12, the adhesive layer 20, and the sealant layer 30 may be laminated in this order.
The intermediate layer 18, the barrier layer 14, the adhesive layer 20, and the sealant layer 30 may be laminated in this order.

The sealant layer 30 may be configured similarly to the resin layer 12 .

It may be configured to impart a light-shielding property by light-shielding printing.
The solid print layer may be provided on the resin layer 12 or the barrier layer 14 . For example, when the resin layer 12, the adhesive layer 16, the intermediate layer 18, the adhesive layer 20, and the sealant layer 30 are laminated in this order, the solid print layer provided on the resin layer 12 is made of resin It is positioned between layer 12 and adhesive layer 16 .
Further, for example, when the resin layer 12, the barrier layer 14, the adhesive layer 16, the intermediate layer 18, the adhesive layer 20, and the sealant layer 30 are laminated in this order, the A solid print layer is positioned between the barrier layer 14 and the adhesive layer 16 .

In the above-described fourth embodiment, the example in which the packaging bag 100 and the package 200 are formed using a pair of laminated films 50 has been described.
However, as shown in FIGS. 4 and 5, instead of the pair of laminated films 50, a pair of laminated films 60 and 70 may form the packaging bag 100A and the package 200A.
The packaging bag 100A and the package 200A can be manufactured in the same manner as the packaging bag 100 and the package 200 except that the pair of laminated films 60 are used instead of the pair of laminated films 50. FIG.
Since the packaging bag 100A and the package 200A are provided with the pair of laminated films 60, they have the same function as the laminated films 60.

In the above-described fourth embodiment, the example in which the packaging bag 150 and the packaging body 210 are formed using a pair of laminated films 50 has been described.
However, as shown in FIG. 6, instead of the pair of laminated films 50, a pair of laminated films 60 and 70 may be used to form the packaging bag 150A and the package 210A.
The packaging bag 150A and the packaging body 210A can be manufactured in the same manner as the packaging bag 150 and the packaging body 210, except that the pair of laminated films 50 is replaced with the pair of laminated films 60. FIG.
Since the packaging bag 150A and the package 210A are provided with the pair of laminated films 60, they have the same function as the laminated films 60.

In the above-described fourth and fifth embodiments, an example in which a pair of laminated films 50 is used to form a packaging bag and a package has been described. However, as long as the laminated film 50 is used in the peripheral portion of a portion of the packaging bag and package, the laminated film in the other peripheral portion may have a different layer configuration from the laminated film 50 .
For example, if the polyvalent metal particles or polyvalent metal compound particles contained in one laminated film 50 can suppress the retort odor, other laminated films may contain polyvalent metal particles or polyvalent metal compound particles. may not be contained.

In the fourth and fifth embodiments described above, the packaging bag is a four-sided bag and a standing pouch, but the shape of the packaging bag is not limited to these, and other known bag shapes are possible. may
For example, the shape of the packaging bag may be a two-sided bag, a three-sided bag, or a two-sided bag.
For example, the packaging bag may include a fastener made of synthetic resin that can be repeatedly sealed by fitting a spout or a band-shaped protrusion with a band-shaped groove.

The packaging bag may have one or a plurality of functions such as retort packaging, boiling packaging, and microwave packaging.

In the fourth and fifth embodiments described above, the item to be packaged 110 is described as an example of foodstuffs, but the item to be packaged 110 is not limited to foodstuffs.

The items to be packaged 110 may be curry, oden, noodle soup, seasoning liquid, pasta sauce, side dishes, soup, kamameshi mix, and pet food.

Next, Examples 1 to 31 of the embodiment of the present invention will be described together with Comparative Examples 1 to 20. The configurations of Examples 1 to 22 and Comparative Examples 1 to 14 are configurations of the second embodiment of the present invention. The configurations of Examples 23-31 and Comparative Examples 15-20 are configurations of the third embodiment of the present invention.
First, the particle dispersion liquids used for producing the laminated films of Examples 1 to 31 and Comparative Examples 1 to 20 will be collectively described. Each particle dispersion was used to produce an adhesive containing polyvalent metal compound particles.
The following [Table 1] shows the composition and dispersion treatment of the particle dispersions used in the production of the laminated films of Examples 1 to 31 and Comparative Examples 1 to 20.

[Particle dispersion liquid 11Aa]
As shown in [Table 1], the particle dispersion 11Aa was prepared by dispersing fine particles of zinc oxide (ZnO), which is a polyvalent metal oxide (hereinafter referred to as zinc oxide particles), in ethyl acetate.
Particle Dispersion 11Aa was prepared as follows.
First, zinc oxide particles were added to ethyl acetate as a solvent to form a mixed solution. As the zinc oxide particles, FINEX-30 (trade name; manufactured by Sakai Chemical Industry Co., Ltd.) having an average particle size of 35 nm was used. The amount of FINEX (registered trademark)-30 added was such that the solid content concentration of the mixed liquid was 30% by mass.
After that, dispersing agent A containing polyester acid amide amine salt, alkylcyclohexane, and propylene glycol monomethyl ether acetate was added to the mixed liquid. Dispersant A is a dispersant containing amide amic acid, which is a high-molecular-weight polyester acid, as a main component.
The amount of the dispersant A added was 5 parts by mass based on 100 parts by mass of the solid content of the zinc oxide particles in the mixture.
This mixed solution was subjected to dispersion treatment using a planetary ball mill (described as "bead mill" in [Table 1]).
As a result, a particle dispersion liquid 11Aa in which zinc oxide particles were dispersed in the solvent was prepared.

[Particle dispersion liquid 11Ba]
Particle dispersion 11Ba was prepared in the same manner as particle dispersion 11Aa, except that the amount of dispersant added was 40 parts by mass.

[Particle dispersion liquid 11Ca]
Particle dispersion 11Ca was prepared in the same manner as particle dispersion 11Aa, except that the amount of the dispersant added was 20 parts by mass.

[Particle Dispersions 12Aa and 12Ba]
Particle Dispersion Liquid 12Aa was prepared in the same manner as Particle Dispersion Liquid 11Aa, except that Dispersant B containing phosphoric acid ester was used instead of Dispersant A as a dispersant. Dispersant B is a polyether phosphate compound-based dispersant.
Particle dispersion 12Ba was prepared in the same manner as particle dispersion 12Aa, except that the amount of dispersant added was 40 parts by mass.

[Particle Dispersions 13Aa and 13Ba]
Particle dispersion 13Aa is the same as particle dispersion 11Aa, except that instead of dispersant A, vinyl chloride/vinyl acetate copolymer, acetone, and methanol-containing dispersant C are used as the dispersant. Prepared by Dispersant C is a dispersant containing vinyl chloride-vinyl acetate copolymer resin as a main component.
Particle Dispersion Liquid 13Ba was prepared in the same manner as Particle Dispersion Liquid 13Aa, except that the amount of the dispersant added was 40 parts by mass.

[Particle Dispersions 14Aa, 14Ba, 14Ca]
In the particle dispersion liquid 14Aa, instead of FINEX-30 (registered trademark) having an average primary particle diameter of 35 nm, FINEX (registered trademark)-50 (product name; manufactured by Sakai Chemical Industry Co., Ltd.) was prepared in the same manner as the particle dispersion liquid 11Aa.
Particle Dispersion Liquid 14Ba was prepared in the same manner as Particle Dispersion Liquid 14Aa, except that the amount of the dispersant added was 40 parts by mass.
Particle Dispersion Liquid 14Ca was prepared in the same manner as Particle Dispersion Liquid 14Aa, except that the amount of dispersant added was 20 parts by mass.

[Particle Dispersions 15Aa and 15Ba]
Particle dispersion liquid 15Aa is the same as particle dispersion liquid 11Aa, except that FINEX (registered trademark)-20, which is zinc oxide particles having an average particle diameter of 60 nm as primary particles, is used instead of FINEX (registered trademark)-30. Prepared similarly.
Particle Dispersion Liquid 15Ba was prepared in the same manner as Particle Dispersion Liquid 15Aa, except that the amount of dispersant added was 40 parts by mass.

[Particle dispersions 100a, 200a, 300a, 400a]
Particle Dispersion 100a was prepared in the same manner as Particle Dispersion 11Aa, except that no dispersing agent was added.
Particle dispersion 200a is the same as particle dispersion 100a, except that aluminum oxide (Al2O3) particles (hereinafter referred to as aluminum oxide particles) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. are used instead of zinc oxide particles. Prepared by The average particle size of the aluminum oxide particles was 45 nm.
Particle dispersion 300a was prepared in the same manner as particle dispersion 100a, except that particles of magnesium oxide (MgO) manufactured by Stream Chemicals (hereinafter referred to as magnesium oxide particles) were used instead of zinc oxide particles. . The average particle size of the magnesium oxide particles was 20 nm.
Particle Dispersion 400a was prepared in the same manner as Particle Dispersion 100a, except that FINEX (registered trademark)-50 was used in place of FINEX (registered trademark)-30.

[Particle Dispersions 11Ab, 11Bb, 11Cb]
Particle dispersion liquid 11Ab was not subjected to dispersion treatment using a planetary ball mill, and the mixed liquid was stirred for 10 minutes using a stirring blade (described as "stirring only" in [Table 1]). Prepared in the same manner as Fluid 11Aa.
Particle Dispersion Liquid 11Bb was prepared in the same manner as Particle Dispersion Liquid 11Ab, except that the amount of dispersant added was 40 parts by mass.
Particle Dispersion Liquid 11Cb was prepared in the same manner as Particle Dispersion Liquid 11Ab, except that the amount of dispersant added was 20 parts by mass.

[Particle Dispersions 14Ab, 14Bb]
Particle Dispersion Liquid 14Ab was prepared in the same manner as Particle Dispersion Liquid 14Aa, except that dispersion treatment using a planetary ball mill was not performed and the mixed liquid was stirred for 10 minutes using a stirring blade.
Particle Dispersion Liquid 14Bb was prepared in the same manner as Particle Dispersion Liquid 14Ab, except that the amount of dispersant added was 40 parts by mass.

[Particle dispersions 100b, 200b, 300b, 400b]
The particle dispersion liquid 100b was prepared in the same manner as the particle dispersion liquid 100a, except that the dispersion treatment using the planetary ball mill was not performed and the mixed liquid was stirred for 10 minutes using a stirring blade.
The particle dispersion liquid 200b was prepared in the same manner as the particle dispersion liquid 200a, except that the dispersion treatment using the planetary ball mill was not performed and the mixed liquid was stirred for 10 minutes using a stirring blade.
Particle dispersion 300b was prepared in the same manner as particle dispersion 300a, except that dispersion treatment using a planetary ball mill was not performed and the mixture was stirred for 10 minutes using a stirring blade.
The particle dispersion liquid 400b was prepared in the same manner as the particle dispersion liquid 400a, except that the dispersion treatment using the planetary ball mill was not performed and the mixed liquid was stirred for 10 minutes using a stirring blade.

[Table 2] below shows the production conditions and evaluation results of Examples 1 to 31 and Comparative Examples 1 to 20.

[Example 1]
In Example 1, Toyobo Ester (registered trademark) film E5100 (trade name; manufactured by Toyobo Co., Ltd.), which is a biaxially oriented polyethylene terephthalate film, was used as the resin layer 12 . The E5100 was 12 μm thick, 500 m long and 600 mm wide.
One surface 12b of the resin layer 12 was corona-treated, and a barrier layer 14 made of SiOx was formed on the corona-treated surface 12b using a vacuum deposition machine.
Specifically, a vapor deposition material in which metal silicon powder and silicon dioxide powder are mixed is prepared, and a vapor deposition layer having an element ratio O/Si of 1.5 (x = 1.5) is formed on the surface 12b by a vacuum vapor deposition machine. Evaporation was carried out such that a was formed. The thickness of the barrier layer 14 was 50 nm.
After that, on the barrier layer 14, a dry lamination machine is used to apply a two-component curing type polyurethane adhesive A626/A50 (trade name; manufactured by Mitsui Chemicals, Inc.), followed by a 15 μm-thick nylon adhesive. Emblem (registered trademark) ON (trade name; manufactured by Unitika Ltd.), which is a film, was laminated. Thus, the adhesive layer 16 and the intermediate layer 18 were formed.

Using the particle dispersion liquid 11Aa, a coating liquid for forming the adhesive layer 20 was prepared as follows.
A626 and A50, which are two-component curable polyurethane adhesives, were mixed at a mass ratio of 8:1 and diluted with ethyl acetate to form an adhesive with a solid content concentration of 30% by mass. . After that, the particle dispersion liquid 11Aa is added to the adhesive, and the ratio of the solid content of the zinc oxide particles to the total mass of the solid content of the adhesive and the solid content of the zinc oxide particles is adjusted to 1.5% by mass. bottom.
Hereinafter, for the sake of simplicity, "the ratio of the solid content of the polyvalent metal compound particles to the total mass of the solid content of the adhesive and the solid content of the polyvalent metal compound particles" will be referred to as "the amount of particles in the coating liquid". [Table 2] is described as "amount of particles".
After that, the mixture of the adhesive and the particle dispersion liquid 11Aa was stirred with a stirring blade for 30 minutes. Thereafter, the mixed liquid was filtered through a membrane filter having a pore size of 3 μm to obtain coating liquid 11Aa used in Example 1. In the particle dispersion liquid 11Aa subjected to dispersion treatment, the zinc oxide particles were less likely to agglomerate, so most of the zinc oxide particles in the mixed liquid passed through the membrane filter.

After that, the intermediate layer 18 was coated with the coating liquid 11Aa using a dry lamination machine, and laminated with an 80 μm-thick polyolefin-based unstretched coextruded film as the sealant layer 30 .
Thus, a laminated film 60 having the laminated structure shown in FIG. 2 was obtained. That is, the laminated film 60 includes a sealant layer 30 made of a polyolefin-based unstretched coextruded film, an adhesive layer 20 containing zinc oxide particles, an intermediate layer 18 made of a nylon film, an adhesive layer 16 not containing zinc oxide particles, and a barrier layer. 14, and resin layer 12 in this order.
The particle amount of the zinc oxide particles in the adhesive layer 20 was 1.5% by mass, the same as the particle amount in the coating liquid.

After that, the laminate film 60 of Example 1 was pasted together so that the sealant layers 30 were opposed to each other, and a three-sided bag 100A of Example 1 as shown in FIG. 5 was produced.
After that, the object 110 to be packaged was accommodated in the packaging bag 100A and sealed to manufacture the package 200A of the first embodiment.
A cysteine aqueous solution containing 0.03% by mass of cysteine was used as the object to be packaged 110 .

[Examples 2 to 22]
As shown in [Table 2], in Examples 2 to 22, the laminated film 60 was prepared in the same manner as in Example 1 except that the coating liquid described in each column was used instead of the coating liquid 11Aa , a packaging bag 100A, and a package 200A.
The amount of zinc oxide particles in coating liquid 11Aa is 1.5% by mass, while the amount of zinc oxide particles in coating liquid 11Aa+ is 9.5% by mass. The particle amount of the zinc oxide particles is 0.8% by mass, and the particle amount of the zinc oxide particles in the coating liquid 11Aa++ is 11% by mass.
The amount of zinc oxide particles in the coating liquid 11Ca is 3.0% by mass, while the amount of zinc oxide particles in the coating liquid 11Ca+ is 5.0% by mass.
The amount of zinc oxide particles in the coating liquid 14Ca is 3.0% by mass, while the amount of zinc oxide particles in the coating liquid 14Ca+ is 5.0% by mass.
The amount of zinc oxide particles in the coating liquid 100a is 1.5% by mass, while the amount of zinc oxide particles in the coating liquid 100a+ is 9.5% by mass.

[Example 23]
In Example 23, Toyobo Ester (registered trademark) film E5100 (trade name; manufactured by Toyobo Co., Ltd.), which is a biaxially oriented polyethylene terephthalate film, was used as the resin layer 12 . The E5100 was 12 μm thick, 500 m long and 600 mm wide.
On the resin layer 12, using a dry lamination machine, a two-liquid curing type polyurethane adhesive A525/A52 (trade name; manufactured by Mitsui Chemicals, Inc.) is applied, resulting in a nylon film with a thickness of 15 μm. Emblem (registered trademark) ON (trade name; manufactured by Unitika Ltd.) was laminated as the intermediate layer 18 . Thus, the adhesive layer 16 and the intermediate layer 18 were formed.

Subsequently, the intermediate layer 18 was again coated with the adhesive in the same manner, and an aluminum film foil having a thickness of 7 μm was laminated as the intermediate layer 18B. Thereby, the adhesive layer 16B and the intermediate layer 18B were formed.

Using the particle dispersion liquid 11Aa, a coating liquid for forming the adhesive layer 20 was prepared as follows.
A525 and A52, which are two-component curable polyurethane adhesives, were mixed at a mass ratio of 8:1 and diluted with ethyl acetate to form an adhesive with a solid content concentration of 30% by mass. . After that, the particle dispersion liquid 11Aa is added to the adhesive, and the ratio of the solid content of the zinc oxide particles to the total mass of the solid content of the adhesive and the solid content of the zinc oxide particles is adjusted to 1.5% by mass. bottom.
Hereinafter, for the sake of simplicity, "the ratio of the solid content of the polyvalent metal compound particles to the total mass of the solid content of the adhesive and the solid content of the polyvalent metal compound particles" will be referred to as "the amount of particles in the coating liquid". [Table 2] is described as "amount of particles".
After that, the mixture of the adhesive and the particle dispersion liquid 11Aa was stirred with a stirring blade for 30 minutes. Thereafter, the mixed liquid was filtered through a membrane filter having a pore size of 3 μm to obtain coating liquid 11Aa used in Example 19. In the particle dispersion liquid 11Aa subjected to dispersion treatment, the zinc oxide particles were less likely to agglomerate, so most of the zinc oxide particles in the mixed liquid passed through the membrane filter.

After that, the intermediate layer 18B was coated with the coating liquid 11Aa using a dry lamination machine, and laminated with a polyolefin-based unstretched coextruded film having a thickness of 80 μm as the sealant layer 30 .
Thus, a laminated film 70 having a laminated structure shown in FIG. 3 was obtained. That is, the laminated film 70 includes a sealant layer 30 made of a polyolefin-based unstretched coextruded film, an adhesive layer 20 containing zinc oxide particles, an intermediate layer 18B made of aluminum foil, an adhesive layer 16B not containing zinc oxide particles, and a nylon film. , an adhesive layer 16 containing no zinc oxide particles, and a resin layer 12 in this order.
The particle amount of the zinc oxide particles in the adhesive layer 20 was 1.5% by mass, the same as the particle amount in the coating liquid.

After that, the laminate film 70 of Example 1 was pasted together so that the sealant layers 30 were opposed to each other, thereby producing a three-sided bag 100A of Example 1 as shown in FIG.
After that, the object 110 to be packaged was accommodated in the packaging bag 100A and sealed to manufacture the package 200A of the first embodiment.
A cysteine aqueous solution containing 0.03% by mass of cysteine was used as the object to be packaged 110 .

[Examples 24 to 31]
As shown in [Table 2], in Examples 24 to 31, a laminated film 70 was prepared in the same manner as in Example 23, except that the coating liquid described in each column was used instead of the coating liquid 11Aa. , a packaging bag 100A, and a package 200A.

[Comparative Examples 1 to 14]
In Comparative Example 1, the lamination of Comparative Example 1 was performed in the same manner as in Example 1, except that the adhesive layer was formed using only a polyurethane-based adhesive without using the polyvalent metal particles and the polyvalent metal compound particles. A film 60, a packaging bag 100A, and a package 200A were produced.
In Comparative Example 2, the lamination of Comparative Example 2 was performed in the same manner as in Example 9, except that the coating liquid 100bN (the amount of zinc oxide particles was 1.5% by mass) was used instead of the coating liquid 100a. A film 60, a packaging bag 100A, and a package 200A were produced. Coating Liquid 100bN was formed in the same manner as Coating Liquid 100a, except that the adhesive and particle dispersion 100b were stirred for 30 minutes and then filtered through a membrane filter.
In Comparative Examples 3 to 14, the stirring treatment was performed in the same manner as in Comparative Example 2, except that the coating liquids described in the respective columns were used, to produce laminated film 60, packaging bag 100A, and package 200A.
The amount of zinc oxide particles in the coating liquid 100bN is 1.5% by mass, while the amount of zinc oxide particles in the coating liquid 100bP is 3.0% by mass, and the oxidation in the coating liquid 100b+ The particle amount of zinc particles is 9.5% by mass.
The amount of aluminum oxide particles in coating liquid 200b is 1.5% by mass, while the amount of aluminum oxide particles in coating liquid 200b+ is 9.5% by mass.
The amount of magnesium oxide particles in coating liquid 300b is 1.5% by mass, while the amount of magnesium oxide particles in coating liquid 300b+ is 9.5% by mass.

[Comparative Examples 15 to 20]
In Comparative Example 15, the lamination of Comparative Example 16 was carried out in the same manner as in Example 23, except that Coating Liquid 11Ab (the amount of zinc oxide particles was 1.5% by mass) was used instead of Coating Liquid 11Aa. A film 70, a packaging bag 100A, and a package 200A were produced. Coating Liquid 11Ab was formed in the same manner as Coating Liquid 11Aa, except that after stirring the adhesive and particle dispersion liquid 11Ab for 30 minutes, the mixture was not filtered through a membrane filter.
In Comparative Examples 16 to 20, the agitation treatment was performed in the same manner as in Example 23 except that the coating liquids described in the respective columns were used to produce laminated film 70, packaging bag 100A, and package 200A.

[Evaluation method]
In order to evaluate each example and each comparative example, OM image observation results, hydrogen sulfide (H ₂ S) concentration, and laminate strength were measured.

For the OM image observation results, the adhesive layer containing the polyvalent metal compound particles was observed from the resin layer side using an optical microscope.
Aggregates in the range of 500 μm×500 μm were observed under an optical microscope with a magnification of 500×. The number of aggregates of 9 μm or more in the range of 500 μm×500 μm is described in the “Number of Aggregates” column of [Table 2]. The distance between the aggregates was described in the "distance between aggregates" column of [Table 2]. The distance between aggregates is the average value of ten arbitrary aggregate distances.
When aluminum particles are contained in the adhesive layer, the barrier layer, or the like, the cross section of the laminated film may be dissolved and removed with an alkaline solution and then optically observed.

For the hydrogen sulfide concentration measurement, a package containing the cysteine aqueous solution in each example and each comparative example was used as a test sample.
The package of each test sample was subjected to retort treatment by heating at 120° C. for 60 minutes. After the retort treatment, the package was stored in a refrigerator for one week. After that, the aqueous solution in each package was sampled, and the concentration of hydrogen sulfide was determined by the methylene blue method (wavelength: 668 nm). A calibration curve prepared in advance was used to calculate the hydrogen sulfide concentration. The measurement results of hydrogen sulfide concentration are shown in [Table 2].

As test samples for the measurement of lamination strength, the corresponding packaging bags before retort treatment and the packaging bags after retort treatment in each example and each comparative example were used.
The corresponding packaging bags were aged at 45° C. for 4 days before retorting. After that, the laminate strength between the nylon layer and the sealant layer was measured according to JIS Z 0238:1998. Specifically, the laminate strength of each test sample is measured by the T-type peeling method (crosshead speed: 300 mm / min) using a Tensilon universal material testing machine (trade name; manufactured by A&D Co., Ltd.). bottom. The measurement results are shown in the "laminating strength before treatment" column of [Table 2].
Using the test sample of the packaging bag after retort treatment, the lamination strength (N/15 mm width) was measured in the same manner as the corresponding packaging bag before retort treatment. The measurement results are shown in the "laminating strength after treatment" column of [Table 2]. However, in [Table 2], (N/15 mm width) is simply written as (N).

[Evaluation results]
As shown in [Table 2], in the laminated films of Examples 1 to 31, in the adhesive layer 20, in the range of 500 µm × 500 µm, 9 µm The number of aggregates was 6 or more and 23 or less, and the concentration of hydrogen sulfide was 0.2 mg/L or less. Moreover, the distance between aggregates was 103 μm or more and 200 μm or less.

Further, the laminated films of Examples 1 to 31 had a lamination strength of 6 N/15 mm width or more after retort treatment.

In Examples 1-31, the number of aggregates is 6-23. In Comparative Examples 2-20, the number of aggregates is 80-156. In Comparative Examples 1 to 20, the results were inferior in both the retort smell adsorption effect and the laminate strength after retort treatment. It can be seen that the lamination strength after treatment is good.

Comparing Example 1 and Example 4, the number of aggregates in Example 4 with 40 parts by mass of the dispersant is 8, whereas the number of aggregates in Example 1 with 5 parts by mass of the dispersant is are 14. Comparing Example 5 and Example 6, the number of aggregates in Example 6 with 40 parts by mass of the dispersant is 9, whereas the number of aggregates in Example 5 with 5 parts by mass of the dispersant is is 16. Comparing Example 7 and Example 8, the number of aggregates in Example 8 with 40 parts by mass of the dispersant is 9, whereas the number of aggregates in Example 7 with 5 parts by mass of the dispersant is is 16. Comparing Example 12 and Example 15, the number of aggregates in Example 15 with 40 parts by mass of the dispersant is 6, whereas the number of aggregates in Example 12 with 5 parts by mass of the dispersant is is 13.
That is, the larger the amount of dispersant, the smaller the number of aggregates, and the better the dispersibility of the additive particles (polyvalent metal particles or polyvalent metal compound particles) in the adhesive component. I understand.

In Examples 1-31, the distance between aggregates is 103-200 μm. In Comparative Examples 2-20, the distance between aggregates is 40-56 μm. In Comparative Examples 1 to 20, the results were inferior in both the retort odor adsorption effect and the laminate strength after retort processing. It can be seen that the lamination strength after retort treatment is good.

Comparing Example 1 and Example 4, the distance between the aggregates in Example 4 with 40 parts by mass of the dispersant is 179 µm, whereas the distance between the aggregates in Example 1 with 5 parts by mass of the dispersant is 179 µm. The distance between them is 133 μm. Comparing Example 5 and Example 6, the distance between the aggregates in Example 6 with 40 parts by mass of the dispersant is 163 μm, whereas the distance between the aggregates in Example 5 with 5 parts by mass of the dispersant The distance between them is 126 μm. Comparing Example 7 and Example 8, the distance between aggregates in Example 8 with 40 parts by mass of dispersant is 163 μm, whereas the distance between aggregates in Example 7 with 5 parts by mass of dispersant is 163 μm. The distance between them is 126 μm. Comparing Example 12 and Example 15, the distance between aggregates in Example 15 with 40 parts by mass of dispersant is 200 μm, whereas the distance between aggregates in Example 12 with 5 parts by mass of dispersant is 200 μm. The distance between them is 141 μm.
That is, it can be seen that the greater the amount of the dispersant, the shorter the distance between the aggregates, and the better the dispersibility of the additive particles in the adhesive component.

Comparing Example 1, Example 19, and Example 20, the hydrogen sulfide concentration in Example 20, which has a particle amount of 11% by mass, is 0.01 mg/L, and the particle amount is 1.5% by mass. The hydrogen sulfide concentration in Example 1 is 0.03 mg/L, and the hydrogen sulfide concentration in Example 19, which has a particle amount of 0.8% by mass, is 0.2 mg/L. Comparing Example 2 and Example 3, the hydrogen sulfide concentration in Example 3 with a particle amount of 5.0% by mass was 0.01 mg / L, and the concentration of hydrogen sulfide in Example 2 with a particle amount of 3.0% by mass was Hydrogen sulfide concentration is 0.02 mg/L. Comparing Example 9 and Example 11, the hydrogen sulfide concentration in Example 11, which has a particle amount of 9.5% by mass, is 0.01 mg/L, and the concentration of hydrogen sulfide in Example 9, which has a particle amount of 1.5% by mass, is 0.01 mg/L. Hydrogen sulfide concentration is 0.03 mg/L. Comparing Example 13 and Example 14, the hydrogen sulfide concentration in Example 14 with a particle amount of 5.0% by mass was 0.01 mg / L, and the concentration of hydrogen sulfide in Example 13 with a particle amount of 3.0% by mass was 0.01 mg / L. Hydrogen sulfide concentration is 0.02 mg/L.
That is, it can be seen that the greater the amount of additive particles, the higher the retort odor adsorption effect. When the particle amount is 0.5% by mass or more, the retort odor is sufficiently adsorbed, but it is considered that the particle amount is preferably 1.0% by mass or more.

Comparing Example 1 and Example 20, the laminate strength after retort treatment in Example 1 with a particle amount of 1.5% by mass was 8 N / 15 mm width, and in Example 20 with a particle amount of 11% by mass Laminate strength after retort treatment is 6 N/15 mm width.
That is, although the adsorption effect of the retort odor is higher when the amount of the additive particles is large, the laminate strength decreases when the amount of the additive particles exceeds 10% by mass, so the particle amount of the additive particles is 10 mass % or less is considered to be good.

Comparing Example 12 and Example 21, the concentration of hydrogen sulfide in Example 12, in which the average particle diameter of the primary particles of the additive particles was 20 nm, was 0.03 mg/L, whereas the concentration of the primary particles of the additive particles was 0.03 mg/L. The hydrogen sulfide concentration in Example 21, in which the particles have an average particle diameter of 60 nm, is 0.06 mg/L. Comparing Example 15 and Example 22, the concentration of hydrogen sulfide in Example 15 in which the average particle size of the primary particles of the additive particles was 20 nm was 0.03 mg/L, whereas the concentration of the primary particles of the additive particles was 0.03 mg/L. The hydrogen sulfide concentration in Example 22, in which the particles have an average particle diameter of 60 nm, is 0.06 mg/L.
That is, the average particle size of the primary particles of the additive particles may be 60 nm, but if the average particle size is too large, the effect of adsorbing the retort odor is slightly inferior.

Example 1 and Example 23, Example 4 and Example 24, Example 11 and Example 25, Example 10 and Example 26, Example 12 and Example 27, Example 15 and Example 28, Example No. 16 and Example 29, Example 16 and Example 30, and Example 20 and Example 31 do not contain aluminum film foil in the intermediate layer of the former, and contain aluminum film foil in the intermediate layer of the latter. They are different. In both cases, regardless of the presence or absence of the aluminum film foil, similar results were obtained in terms of the adsorption effect of the retort odor and the laminate strength after the retort treatment.

FIG. 7 is an example of an OM image observation image of Comparative Example 3. In FIG. In Comparative Example 3, as shown in FIG. 7, aggregates P are 9.6 μm, 10.3 μm, and 11.3 μm.

[comprehensive evaluation]
Regarding the retort odor (described as "smell" in [Table 2]), if the hydrogen sulfide concentration is 0.04 mg / L or less, it is good (described as "A" in [Table 2]). If it exceeds 0.04 mg / L and 0.25 mg / L or less, it is slightly good (described as "B" in [Table 2]), and if it exceeds 0.25 mg / L, it is poor ([Table 2] described as "C").
Regarding the lamination strength (described as "strength" in [Table 2]), if the lamination strength after retort treatment is 7 N / 15 mm width or more, it is good (described as "A" in [Table 2]), retort treatment When the lamination strength after retort treatment is 6 N/15 mm width or more and less than 7 N/15 mm width, it is somewhat good (described as "B" in [Table 2]). It was determined to be defective (described as "C" in [Table 2]).
As a comprehensive evaluation, when both the retort odor and the evaluation of the laminate strength are good (described as "A" in [Table 2]), it is determined as good (described as "A" in [Table 2]). bottom. If one of the retort odor and laminate strength evaluation is good (described as "A" in [Table 2]) and the other is somewhat good (described as "B" in [Table 2]), It was judged as somewhat good (described as "B" in [Table 2]). Both the evaluation of retort odor and lamination strength are somewhat good (listed as "B" in [Table 2]), or one of the evaluations of retort odor and lamination strength is poor ("C" in [Table 2]). ), it was determined to be defective (described as "C" in [Table 2]).

As shown in [Table 2], the overall evaluation was A for Examples 1 to 18 and 23 to 29. The overall evaluation was B for Examples 19-22, 30, and 31.
Comparative Example 1 was rated C for odor, and therefore rated C overall.
Comparative Examples 2 to 8 and 12 to 20 were rated B for retort odor and strength, and therefore rated C overall.
Comparative Examples 9 to 11 were rated C in terms of strength, so they were rated C overall.

Although preferred embodiments of the present invention have been described together with examples, the present invention is not limited to each embodiment and each example. Configuration additions, omissions, substitutions, and other changes are possible without departing from the scope of the present invention.
Moreover, the present invention is not limited by the foregoing description, but only by the appended claims.

10, 10A Base film 12 Resin layer 14 Barrier layer 16 Adhesive layer 18 Intermediate layer 20 Adhesive layer 30 Sealant layer 50, 60, 70 Laminate film 100, 100A, 150, 150A Packaging bag 110 Object to be packaged 200, 200A, 210 Packaging body

Claims (12)

a predetermined layer;
an adhesive layer containing an adhesive component and polyvalent metal particles or polyvalent metal compound particles mixed in the adhesive component;
a sealant layer;
are stacked in this order,
In the adhesive layer, in the range of 500 μm × 500 μm, aggregates formed by the polyvalent metal particles or the polyvalent metal compound particles, the number of aggregates of 9 μm or more is 30 or less.
laminated film. The distance between the aggregates is 100 μm or more,
The laminated film according to claim 1. The predetermined layer is a base film having a barrier layer,
The laminated film according to claim 1 or 2. The base film has a nylon layer,
The laminated film according to claim 3. The adhesive layer contains 0.5% by mass or more and 10% by mass or less of the polyvalent metal particles or the polyvalent metal compound particles.
The laminated film according to any one of claims 1 to 4. The average particle size of the polyvalent metal particles or the polyvalent metal compound particles is 10 nm or more and 45 nm or less.
The laminated film according to any one of claims 1 to 5. The laminated film according to any one of claims 1 to 6, wherein the polyvalent metal particles or the polyvalent metal compound particles have a specific surface area of 1 ^m2 /g or more. The adhesive layer further comprises a dispersant for dispersing the polyvalent metal particles or the polyvalent metal compound particles in the adhesive component,
The laminated film according to any one of claims 1 to 7. The laminated film according to any one of claims 1 to 8, wherein the adhesive component is a cured product of a two-component curing adhesive. A packaging bag made by laminating films,
A packaging bag, wherein the film comprises the laminated film according to any one of claims 1 to 9. The packaging bag according to claim 10;
an object to be packaged contained in the packaging bag;
A package comprising a The item to be packaged contains a sulfur compound,
The package according to claim 11.

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