JPH11314318A - Packaging container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce an environmental load with a low cost and excellent gas barrier properties by heat sealing at least three sides of a resin composition layer made of a resin composition prepared by an inorganic laminar compound and a resin. SOLUTION: The packaging container comprises at least one resin composition layer 3 made of a resin composition prepared by a inorganic laminar compound and a resin. The container is manufactured by using a film laminate having the at least one layer 3. As such a container, in the case of obtaining, for example, a three side sealed packaging container, the laminate having the layer 3 is doubled, and the three sides except the doubled side may be heat sealed. The laminar compound is an organic compound having a laminar structure in which unit crystal layers are stacked with each other, and, for example, a graphite, zirconium phosphate, a chalcogenide, a clay mineral or the like can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging container which has excellent gas barrier properties and can be suitably used for applications such as food packaging for processed foods, electronic material packaging, and pharmaceutical packaging.

[0002]

2. Description of the Related Art Conventionally, polypropylene, polyester,
Packaging containers using a film made of a thermoplastic resin such as polyamide have excellent mechanical properties, heat resistance, transparency, etc., and food fields such as confectionery bags, skipjackets, retort pouches, carbon dioxide beverage containers, It is used in many fields such as cosmetics, agricultural chemicals, and medical care. Because such packaging containers can be manufactured at low cost,
So-called three-side seal packaging bags and four-side seal packaging bags are frequently used.

[0003] The functions required of these packaging materials are diverse as described above. Among the functions required of these packaging materials, the barrier properties as the protection of the contents, particularly the gas barrier properties, are different from those of the contents. It is regarded as an important property that affects the storage stability of (packaged).

[0004] However, gas barrier properties are a weak point of general plastic materials. Therefore, in order to improve the functions such as the gas barrier properties of these plastic materials, the gas barrier properties are improved by bonding a gas barrier layer made of a gas barrier material having a gas barrier property to the various films described above.

Conventionally, as a gas barrier material used for a gas barrier layer in a three-side seal packaging bag and a four-side seal packaging bag, polyvinyldene chloride is mainly used.

[0006]

However, when a halogen-containing compound such as polyvinyl chloride is used as the gas barrier material, measures must be taken to prevent corrosion of the production equipment. Discarding a packaging container using a halogen-containing compound such as this causes problems such as environmental destruction.

Therefore, there is a need for a packaging container which does not cause the above-mentioned conventional problems, is low in cost, has excellent gas barrier properties, and can reduce environmental load. The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a packaging container which is low in cost, has excellent gas barrier properties, and can reduce environmental load.

[0008]

Means for Solving the Problems As a result of diligent studies to solve the above-mentioned problems, the present inventor has provided a resin composition layer comprising at least a resin composition prepared from an inorganic layered compound and a resin, and having at least 3 layers. We have found that packaging containers whose sides are heat-sealed are low cost, have excellent gas barrier properties, and can reduce environmental impact.
The present invention has been completed.

That is, in order to solve the above problems, the packaging container of the present invention comprises a resin composition layer comprising at least a resin composition prepared from an inorganic layered compound and a resin,
At least three sides are heat-sealed.

According to the above configuration, the inorganic layered compounds face each other due to their layered shape,
Since the orientation is substantially parallel to the surface direction of the resin composition layer, it becomes possible to impart gas barrier properties to the resin composition layer by the labyrinth effect of the inorganic layered compound.

In addition, since a halogen-containing compound is not used unlike the conventional case, corrosion and environmental destruction of a manufacturing apparatus which are problems in conventional packaging containers such as three-side sealed packaging bags and four-side sealed packaging bags are prevented. And cost reduction and reduction of environmental load can be realized. In addition, the above-mentioned packaging container has a simple configuration by adopting a configuration in which at least three sides are heat-sealed, and can be manufactured at low cost. Examples of the packaging container having at least three sides heat-sealed include a three-side sealed packaging container such as a three-side sealed packaging bag and a four-side sealed packaging container such as a four-side sealed packaging bag.

[0012]

FIG. 1 shows an embodiment of the present invention.
The following is a description based on FIG.
As an example of the packaging container according to the present invention, FIG.
FIG. 1B is an enlarged view of a portion A in FIG. 1A while FIG. 1B is an external perspective view of the packaging bag in which three sides are heat-sealed.

Although the opening of the packaging bag is finally closed by heat sealing, the packaging container according to the present invention depends on the shape of the article to be packaged (contents) and the like.
As shown in (a), when the packaging bag is a four-sided sealing packaging bag, first, three sides (two sides in the case of a three-sided sealing packaging bag).
Is heat-sealed, after that, after putting the article to be packaged into the heat-sealed bag, the remaining opening may be heat-sealed, or heat-sealed on each side simultaneously or sequentially. You may. The production method and packaging method of the packaging container of the present invention are not particularly limited, and can be produced and packaged using, for example, a commercially available bag making machine.

As shown in FIG. 1B, the packaging container according to the present invention has at least one resin composition layer 3 composed of a resin composition prepared from at least an inorganic layered compound and a resin. The packaging container is manufactured using a film laminate having at least one resin composition layer 3.

[0015] As the packaging container according to the present invention, for example, 3
When obtaining the one-sided seal packaging bag (three-sided sealed packaging container), for example, using a film laminate provided with the resin composition layer 3 as a packaging material, the film laminate is folded in two, and the folded side is formed. The other three sides may be heat-sealed.

Further, as the packaging container of the present invention, for example, 4
When obtaining a one-sided seal packaging bag (four-sided seal packaging container), for example, using a film laminate provided with the resin composition layer 3 as a packaging material, the film laminate is folded in two, or What is necessary is just to heat-seal four sides by laminating two said film laminated bodies.

In addition, the packaging container of the present invention is manufactured and packaged by heat-sealing the overlapping portion (at least each side including the opening) of the film laminate according to its shape.

In the present invention, the above-mentioned inorganic layer compound used in the resin composition constituting the resin composition layer 3 has a layer structure in which unit crystal layers 31 shown in FIG. It is an inorganic compound. In the present invention, in the cleaved state, the inorganic layered compound preferably has a particle size of 5 μm or less, and has an aspect ratio in the range of 50 to 5,000 from the viewpoint of gas barrier properties,
More preferably, the aspect ratio is in the range of 200 to 3,000. If the aspect ratio is less than 50, the gas barrier property is not sufficient, and if the aspect ratio is more than 5,000, it is technically difficult and economically expensive. Further, when the particle size is 3 μm or less, transparency becomes better, and when the particle size is 1 μm or less, it is more preferable for applications where transparency is important.

The average particle size of the above-mentioned inorganic layered compound is determined by diffraction /
It can be measured by a method based on a scattering method, a method based on a dynamic light scattering method, a method based on a change in electric resistance, a method based on image processing after photographing in a liquid microscope, and the like.

For example, as a method for measuring the average particle size of the inorganic layered compound in a pure solvent such as water, a dynamic light scattering method is suitably used.

However, the dynamic light scattering method is difficult to evaluate because the apparent liquid viscosity changes with a pure solvent when a resin coexists, and the method based on the change in electric resistance limits the electrolyte concentration of the liquid. In addition, the method of image processing after photographing in a submerged microscope has a problem of resolution and is limited in use.

For this reason, when measuring the average particle size of the inorganic layered compound in the presence of the resin, the solution containing the resin, for example, the aqueous resin solution is transparent and has substantially little scattering, and the scattering originating from the particles of the inorganic layered compound is small. Is dominant, information on only the particle size distribution of the particles of the inorganic layered compound can be obtained regardless of the presence or absence of the resin. Therefore, a method using the diffraction / scattering method is suitably used.

Therefore, the particle size of the inorganic layered compound used in the present invention refers to a particle size obtained by a diffraction / scattering method in a dispersion medium. Although it is extremely difficult to measure the true particle size in the resin composition layer 3, the resin composition layer 3 is sufficiently swelled and cleaved with a dispersion medium of the same type as the dispersion medium used in the diffraction / scattering method. When compounding with the resin 32, the resin composition layer 3 shown in FIG.
In this case, the particle size of the cleaved inorganic layered compound can be considered to correspond to the particle size of the cleaved inorganic layered compound in the dispersion medium.

Hereinafter, a method for measuring the average particle size of the inorganic layered compound by the diffraction / scattering method will be described. The particle size distribution and the average particle size of the inorganic layered compound obtained by the diffraction / scattering method are calculated from the diffraction / scattering pattern obtained when light passes through the dispersion of the inorganic layered compound according to the Mie scattering theory or the like. It can be obtained by calculating the particle size distribution that is most consistent with the scattering pattern.

As a device for measuring the diffraction / scattering pattern used in the diffraction / scattering method, a commercially available device can be used. Specifically, for example, a laser diffraction / light scattering particle size analyzer LS230 and LS20 manufactured by Coulter Inc.
0, the same LS100; laser diffraction particle size distribution analyzer SALD2000, SALD2000A, manufactured by Shimadzu Corporation
SALD3000; Laser diffraction / scattering type particle size distribution analyzer LA910, LA700, LA manufactured by Horiba, Ltd.
500; Nikkiso Microtrack SPA, Microtrack FRA, and the like.

Next, a method for measuring the aspect ratio (aspect ratio (Z)) of the inorganic layered compound will be described.
The aspect ratio (Z) is a ratio obtained from a relationship represented by Z = L / a. Here, L is in the dispersion,
The particle diameter (volume-based median diameter) of the inorganic layered compound determined by the particle diameter measurement method by the above-mentioned diffraction / scattering method is shown.
a is the unit thickness of the cleaved inorganic layered compound shown in FIG. 2,
That is, it indicates the thickness of the unit crystal layer 31 of the inorganic layered compound.

The “unit thickness a” of the inorganic layered compound is as follows:
Powder X-ray diffraction method described later (“Guidance for instrumental analysis (a)”
(1985, published by Kagaku Dojinsha, supervised by Jiro Shiokawa), p. 69), and the like, based on the measurement of the inorganic layered compound alone. More specifically, as schematically shown in the graph of FIG. 3, the angle θ corresponding to the lowest angle peak among the diffraction peaks observed by X-ray diffraction.
From the Bragg equation (nλ = 2D sin θ, n = 1,
2, 3,...) Is defined as “unit thickness a”.

Further, the solvent is removed from the dispersion,
When the resin composition corresponding to the resin composition layer 3 is subjected to powder X-ray diffraction, the plane spacing of the inorganic layered compound in the resin composition is usually determined as “plane spacing d” shown in FIG. It is possible.

More specifically, as schematically shown in the graph of FIG. 4, the diffraction observed at a lower angle (larger interval) than the diffraction peak position corresponding to the above “unit thickness a”. Among the peaks, the interval corresponding to the peak at the lowest angle side is “surface interval d” (where a <d).

As a result of the powder X-ray diffraction, as shown schematically in the graph of FIG. 5, a peak corresponding to the “plane spacing d” may be detected as overlapping with a halo (or background). If it is difficult, the area of the portion excluding the base line on the lower angle side than 2θd is set as the peak corresponding to “surface interval d”. Here, “θd” is a diffraction angle corresponding to “(unit thickness a) + (width of single resin chain)”. For details of the method of determining the "surface distance d", see, for example, pages 35 and below and page 271 and below of "Encyclopedia of Clay" (ed., 1985, Asakura Shoten Publishing Co., Ltd., edited by Shuichi Iwao). Will be more apparent in

As described above, the integrated intensity of the diffraction peak observed in the powder X-ray diffraction of the resin composition is the diffraction peak serving as a reference (that is, the diffraction peak corresponding to “plane spacing d”).
Is preferably 2 or more, more preferably 10 or more in relative ratio to the integrated intensity.

Normally, the difference k (k = (da)) between the above-mentioned “surface distance d” and “unit thickness a” is, when converted into a length, the resin 1 constituting the resin composition. Equal to or greater than the width of the main chain (k = (da) ≧ width of single resin chain).
Such “the width of a single resin chain” can be determined by a simulation calculation (for example, see pages 103 to 110 of “Introduction to Polymer Chemistry” (Chemical Doujinshi, 1981)). 4-5 for alcohol
（(2Å to 3Å for water molecules).

It is extremely difficult to directly measure the “true aspect ratio” of the inorganic layered compound in the resin 32 of the resin composition layer 3. Therefore, the above-mentioned “aspect ratio (Z)” is not always equal to the “true aspect ratio” of the inorganic layered compound in the resin 32 of the resin composition layer 3, but for the following reason, It is appropriate to approximate “true aspect ratio” with “aspect ratio (Z)”.

That is, the distance between "plane spacing d" determined by the powder X-ray diffraction method of the resin composition and "unit thickness a" determined by the powder X-ray diffraction measurement of the inorganic layered compound alone is <D, and the value of k (((d−
When a) is greater than or equal to the width of a single resin chain in the resin composition, the resin is inserted between layers of the inorganic layered compound in the resin composition. Therefore, the thickness of the inorganic layered compound in the resin 32 of the resin composition layer 3 is approximated by the above “unit thickness a”, that is, the resin composition layer 3
There is sufficient validity in approximating the “true aspect ratio” of the inorganic layered compound therein with the “aspect ratio (Z)” in the dispersion of the inorganic layered compound described above.

As described above, the resin 3 of the resin composition layer 3
Although it is extremely difficult to measure the true particle size of the inorganic layered compound in the resin composition layer 2, the particle size of the inorganic layered compound in the resin 32 of the resin composition layer 3 is determined by the particle size L of the inorganic layered compound in the dispersion. Can be considered as equivalent to

However, the particle diameter L of the inorganic layered compound in the dispersion obtained by the diffraction / scattering method is considered to be very unlikely to exceed the major axis (Lmax) of the inorganic layered compound. Aspect ratio (Lmax / a)
Below the aspect ratio (Z) used in the present invention (Lm
ax / a <Z) The probability is theoretically quite low.

Therefore, for the above two reasons, the definition of "aspect ratio (Z)" used in the present invention is considered to have sufficient validity. In the present embodiment,
The “aspect ratio” indicates the “aspect ratio (Z)” defined above, and the “particle size” indicates “the particle size L obtained by the diffraction / scattering method”.

Specific examples of the inorganic layered compound include graphite, phosphate derivative-type compounds (such as zirconium phosphate compounds), chalcogenides, and clay minerals. The chalcogenide is
Group IV (Ti, Zr, Hf), Group V (V, Nb, Ta)
And a dichalcogenide of Group VI (Mo, W), having the chemical formula MX ₂ (where M represents the above-mentioned Group IV and Group VI element, and X represents chalcogen (S, Se, T)
e)).

The above-mentioned inorganic layered compound may be used alone or in combination of two or more. Among the above-mentioned inorganic layered compounds, those having a property of swelling or cleaving in a solvent are preferable in terms of easily giving a large aspect ratio, and those having a property of cleaving in a solvent (swelling and cleaving in a solvent) are more preferable. . The swelling property and cleavage property of the inorganic layered compound in a solvent can be evaluated by a swelling property test and a cleavage property test described later.

[Swelling Test] 100 ml of a solvent is placed in a 100 ml measuring cylinder, and 2 g of the inorganic layer compound is slowly added thereto. After standing at 23 ° C. for 24 hours, the volume (ml) of the inorganic layered compound dispersed layer is determined from the scale of the interface between the inorganic layered compound dispersed layer and the supernatant in the measuring cylinder.
Is read as the swelling value. The larger the value, the higher the swelling property.

[Cleavability test] 30 g of an inorganic layered compound was slowly added to 1,500 ml of a solvent, and a dispersion machine (manufactured by Asada Iron Works Co., Ltd., Despa MH-L, blade diameter 52 mm, rotation speed 3,100 rpm, container capacity 3 L, bottom surface) After dispersing at 23 ° C. for 90 minutes at a peripheral speed of 8.5 m / min at a distance of 28 mm between the blades, 100 ml of this dispersion was collected in a measuring cylinder. After standing for 60 minutes, the volume (ml) of the inorganic layered compound dispersed layer is read as a cleavage value from the scale at the interface between the inorganic layered compound dispersed layer and the supernatant in the graduated cylinder. The larger the value, the higher the cleavage.

The solvent used in the swelling property measurement test and the cleavage property measurement test is a solvent having a density smaller than the density of the inorganic layered compound. When the inorganic layered compound is a natural swellable clay mineral, it is preferable to use water as the solvent.

The swellability of the above-mentioned inorganic layered compound is such that the volume of the inorganic layered compound dispersed layer (that is, the volume after swelling of 2 g of the inorganic layered compound) is about 5 m in the swellability measurement test described above.
1 or more (ie, a swelling value of 5 or more),
More preferably, it is about 20 ml or more (that is, the swelling value is 20 or more).

On the other hand, the cleavage property of the inorganic layered compound was determined by the above-described cleavage property test after the volume of the inorganic layered compound dispersed layer (ie, the swelling of the inorganic layered compound (equivalent to about 2 g) contained in 100 ml of the dispersion). Is preferably about 5 ml or more (that is, the cleavage value is 5 or more), and about 20 ml or more.
ml or more (ie, a cleavage value of 20 or more).

Among the inorganic layered compounds, as the inorganic layered compound which swells or cleaves in a solvent, a clay mineral having swelling and cleavage properties in a solvent is particularly preferably used. The clay mineral generally has (i) a type having a two-layer structure having an octahedral layer having a central metal such as aluminum or magnesium on the top of a tetrahedral layer of silica; and (ii) a tetrahedral layer of silica. And a type having a three-layer structure in which an octahedral layer having aluminum or magnesium as a central metal is narrowed from both sides. Examples of the former (i) two-layer structure type include clay minerals such as kaolinite and antigolite. Examples of the latter three-layer structure type (ii) include clay minerals such as smectite group, vermiculite group, and mica group depending on the number of interlayer cations.

More specifically, these clay minerals include kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, and stevensite hectorite. , Tetrasilyl mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite, zansophyllite, chlorite and the like. In addition, those obtained by treating these clay minerals with organic substances (see Asakura Shoten, "Encyclopedia of Clays"; hereinafter, sometimes referred to as organically modified clay minerals) can also be used as the inorganic layered compound.

Among the above clay minerals, from the viewpoint of swelling or cleavage, smectites, vermiculites,
And mica clay minerals are preferred, and smectites are more preferred. Specific examples of the smectite group clay mineral include, but are not limited to, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, and hectorite.

As a dispersion medium for swelling or cleaving the inorganic layered compound, for example, when the inorganic layered compound is a natural swelling clay mineral, water; methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, etc. Alcohols; dimethylformamide; dimethyl sulfoxide; acetone;
Among them, water and alcohols such as methanol are more preferable. When the inorganic layered compound is an organically modified clay mineral, the dispersion medium may be, for example, aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as ethyl ether and tetrahydrofuran; acetone, methyl ethyl ketone and methyl isobutyl. Ketones such as ketones; aliphatic hydrocarbons such as n-pentane, n-hexane, n-octane; halogenated hydrocarbons such as chlorobenzene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, perchloroethylene Kind;
Ethyl acetate; methyl methacrylate (MMA); dioctyl phthalate (DOP); dimethylformamide; dimethyl sulfoxide; methyl cellosolve;

The resin used in the above resin composition is not particularly limited, but specific examples thereof include a polyolefin resin, a polyester resin, an amide resin, an acrylic resin, and styrene. Resin,
Acrylonitrile resins, cellulose resins, halogen-containing resins, hydrogen bonding resins, liquid crystal resins, polyphenylene oxide resins, polymethylene oxide resins, polycarbonate resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, and the like. .

Further, as an example of a preferable resin, a high hydrogen bonding resin having a hydrogen bonding group or an ionic group described later as a crosslinkable functional group can be given. The content of the hydrogen-bonding group or the ionic group in the high hydrogen-bonding resin (the total amount of both if both are included) is usually 20 mol%.
６０60 mol%, preferably 30 mol%
It is in the range of 50 mol%. The content of these hydrogen bonding groups and ionic groups can be determined, for example, by nuclear magnetic resonance (for example,
1H-NMR, 13C-NMR, etc.).

The hydrogen bonding group contained in the high hydrogen bonding resin is, specifically, a hydroxyl group, an amino group, a thiol group,
Examples thereof include a carboxyl group, a sulfonic group, and a phosphoric group. Further, as the ionic group, a carboxylate group,
Sulfonate ion group, phosphate ion group, ammonium group,
An ionic group such as a phosphonium group is exemplified. Among these hydrogen bonding groups and ionic groups, particularly preferable functional groups include a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a carboxylate group, a sulfonic acid ion group, and an ammonium group.

Specific examples of the high hydrogen bonding resin include:
For example, polyvinyl alcohol, polysaccharides, ethylene-vinyl alcohol copolymer described below, polyacrylic acid and its esters, sodium polyacrylate, polystyrene sulfonic acid, sodium polystyrene sulfonate, polyethylene imine, polyallylamine and quaternary ammonium Salts, polyvinyl thiol, polyglycerin and the like.

The polyvinyl alcohol (PVA) is, for example, a copolymer of vinyl alcohol and vinyl acetate, and is a polymer obtained by hydrolyzing or transesterifying (saponifying) an acetic ester portion of a vinyl acetate polymer. Polymers obtained by saponifying trifluorovinyl acetate polymer, vinyl formate polymer, vinyl pivalate polymer, t-butyl vinyl ether polymer, trimethylsilyl vinyl ether polymer, and the like. The P
For details of VA, see, for example, “PV
The world of A (1992, Kobunshi Publishing Co., Ltd.); "Poval" (1981, Kobunshi Publishing Co., Ltd., written by Nagano et al.); Would.

The saponification rate of the PVA is preferably at least 70 mol%, more preferably at least 85 mol%, particularly preferably at least 98 mol%, and most preferably a completely saponified product. preferable. Further, the degree of polymerization of the PVA is preferably in the range of 100 to 5,000, and more preferably in the range of 200 to 3,000. Further, the above PVA may be modified with a small amount of a copolymer monomer as long as the object of the present invention is not hindered.

The polysaccharide is a biopolymer synthesized in a biological system by polycondensation of various monosaccharides.
Also included are those obtained by chemically modifying the biopolymer. Specific examples of the polysaccharide include cellulose; cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose; amylose; amylopectin; pullulan; curdlan; xanthan; chitin;

The ethylene-vinyl alcohol copolymer (EVOH) has a vinyl alcohol content of 4
The EVOH is in the range of 0 mol% to 80 mol%, preferably the EVOH having a vinyl alcohol fraction in the range of 45 mol% to 75 mol%. The melt index (MI) of the EVOH is not particularly limited, but at a temperature of 190 ° C. and a load of 2,160 g,
It is preferably 0.1 g / 10 min to 50 g / 10 min. The above EVOH may be modified with a small amount of a comonomer as long as the object of the present invention is not hindered.

One of these resins may be used alone, or two or more of them may be used as a mixture. Among these resins, PVA and its modified products, polysaccharides,
Ethylene-vinyl alcohol copolymers and modified products thereof are particularly preferred.

The above-mentioned modified form of PVA and ethylene-vinyl alcohol copolymer refers to another unsaturated monomer copolymerizable with a vinyl acetate monomer in a vinyl ester resin during the production process of PVA, for example, ethylene. , Propylene, α-hexene, olefins such as α-octene and
Unsaturated acids such as (meth) acrylic acid, crotonic acid, (anhydride) maleic acid, fumaric acid, itaconic acid, and their alkyl esters and alkali salts, vinylsulfonic acid, styrenesulfonic acid, 2-acrylamide-2-methylpropane Sulfonic acid-containing monomers such as sulfonic acid and alkali salts thereof, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
Trimethyl-2- (1- (meth) acrylamide-1,
1-dimethylethyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamidopropyl) ammonium chloride, 1-vinyl-2-ethylimidazole, other quaternizable cationic monomers, styrene,
Examples include alkyl vinyl ether, (meth) acrylamide, and others.

The ratio of these copolymer components is not particularly limited, but may be 5 to vinyl alcohol units.
It is preferably about 0 mol% or less, preferably about 30 mol% or less, and the form of the copolymer may be various forms obtained by any method such as random copolymerization, block copolymerization, and graft copolymerization. Can be

Among these copolymers, a block copolymer obtained by copolymerizing a polycarboxylic acid component with a PVA component is particularly preferably used, and particularly when the polycarboxylic acid component is polymethacrylic acid. preferable. Further, the block copolymer is particularly preferably an AB type block copolymer in which a polyacrylic acid chain is extended at one end of a PVA chain, and a PVA block component (a) and a polyacrylic acid are preferably used. It is preferable that the weight ratio (a) / (b) of the block component (b) is 50/50 to 95/5, and when the weight ratio (a) / (b) is 60/40 to 90/10, the gas barrier property is completed. The coupling characteristics with the chromium are remarkably complete. Further, among other modified products, a particularly preferable embodiment is a silyl group-modified PVA resin composed of a saponified vinyl ester polymer modified with at least one compound having a silyl group in the molecule. .

The method for obtaining the modified polymer having such a composition is not particularly limited.
A compound having a silyl group in the molecule is reacted with a vinyl alcohol-based polymer such as VA or modified polyvinyl acetate to introduce the silyl group into the polymer, or to activate the terminal of PVA or a modified product thereof, thereby obtaining A method by various modifications such as introducing an unsaturated monomer having a silyl group into the polymer terminal, and further graft-copolymerizing the unsaturated monomer to a vinyl alcohol-based polymer molecular chain; A method of obtaining a copolymer from a monomer and an unsaturated monomer having a silyl group in the molecule, and saponifying the copolymer,
Alternatively, various methods such as polymerization of a vinyl ester in the presence of a mercaptan having a silyl group and saponification of the vinyl ester, and introduction of a silyl group at a terminal can be effectively used.

The modified PV obtained by such various methods
The A-based resin may be a resin having a silyl group in the molecule as a result, but the silyl group contained in the molecule is an alkoxyl group or an acyloxyl group and a silanol group which is a hydrolyzate thereof or a silanol group thereof. Those having a reactive substituent such as a salt are preferable, and among them, a silanol group is particularly preferable.

Compounds having a silyl group in the molecule used for obtaining these modified PVA resins include trimethylchlorosilane, dimethylchlorosilane, methyltrichlorosilane, vinyltrichlorosilane, diphenyldichlorosilane and triethylfluorosilane. Such as organohalosilanes, trimethylacetoxysilane, dimethyldiacetoxysilane, etc.
Organoalkoxysilanes such as trimethylmethoxysilane and dimethyldimethoxysilane, organosilanols such as trimethylsilanol and diethylsilanediol,
Examples include aminoalkylsilanes such as N-amiethyltrimethoxysilane, organosilicon isocyanates such as trimethylsiliconisocyanate, and others. The degree of modification by these silylating agents can be arbitrarily adjusted depending on the type, amount and reaction conditions of the silylating agent used.

The unsaturated monomer used in the method for saponifying a copolymer of a vinyl ester monomer and an unsaturated monomer having a silyl group in the molecule is vinyltrimethoxysilane. Many vinylsilane compounds such as vinylalkoxysilane and vinylmethyldimethoxysilane represented by vinyltriethoxysilane and the like, and alkyl or allyl-substituted products of vinylalkoxysilane represented by vinyltriisopropoxysilane and the like, Further, polyalkylene glycol-modified vinyl silanes in which a part or all of these alkoxy groups are substituted with a polyalkylene glycol such as polyethylene glycol can be given. Furthermore, (meth) acrylamido-alkylsilane represented by 3- (meth) acrylamino-propyltrimethoxysilane, 3- (meth) acrylamido-propyltriethoxysilane and the like can also be preferably used.

On the other hand, a method of polymerizing a vinyl ester in the presence of a mercaptan having a silyl group or the like, saponifying the vinyl ester and introducing a silyl group to a terminal includes alkoxysilyl such as 3- (trimethoxysilyl) -propylmercaptan. Alkyl mercaptans are preferably used.

The suitability range of the modified PVA resin of the present invention varies depending on the degree of modification, that is, the content of the silyl group, the degree of saponification, etc., but an important factor for the gas barrier property which is the object of the present invention. Becomes The content of the silyl group is usually 30 mol% or less as a monomer containing a silyl group with respect to the vinyl alcohol unit in the polymer,
0 mol% or less is preferable, 5 mol% or less is more preferable, and 2 mol% or less is particularly preferably used.
Although the lower limit is not particularly limited, the effect is particularly remarkably exhibited when it is 0.1 mol% or more.

The silylation rate is determined by the PV before silylation.
It shows the ratio of the introduced silyl group after silylation to the amount of hydroxyl group contained in the A-based resin.

The modified PVA resin into which the silyl group has been introduced is dissolved by heating with an alcohol or a mixed solvent of alcohol / water, so that the resin is dissolved in the alcohol solvent due to the presence of the introduced silyl group. The modified PVA-based resin dissolved in the solvent, on the other hand, partially crosslinks by reacting by a dealcoholization reaction and a dehydration reaction. In the above reaction, the presence of water is essential, and it is preferable to use a mixed solvent of alcohol and water.

These various PVA-based resins may of course be used alone. However, as long as the object of the present invention is not impaired, they may be used as copolymers with other copolymerizable monomers or mixed. It can be used in combination with other resin compounds. Examples of such a resin include polyacrylic acid or esters thereof, polyester resin, polyurethane resin, polyamide resin, epoxy resin, melamine resin, and others.

The mixing ratio of the inorganic layered compound and the resin in the resin composition is not particularly limited, but the weight ratio of the inorganic layered compound to the resin (inorganic layered compound / resin) is 1 /. It is preferably in the range of 100 to 100/1, more preferably in the range of 1/20 to 10/1, and more preferably in the range of 1/20 to 2/1. The higher the weight ratio of the inorganic layered compound is, the more excellent the barrier property is, but in consideration of the bending resistance, the weight ratio is preferably in the range of 1/20 to 2/1.

When the resin is a high hydrogen bonding resin, a crosslinking agent capable of performing a crosslinking reaction with the high hydrogen bonding resin is used in the resin composition for the purpose of improving the water resistance. Can be. That is, it is more preferable that the resin 32 in the resin composition layer 3 has a crosslinked structure from the viewpoint of water resistance.

The above-mentioned crosslinking agent can impart a high level of water resistance such as boiling property and retort property to the resin composition layer 3 while maintaining flexibility. Particularly preferred. The metal organic compound is a compound capable of performing a cross-linking reaction with a high hydrogen bonding resin and a coordination bond, a hydrogen bond, an ionic bond, or the like, and has a high cross-linking reactivity with the high hydrogen bonding resin, for example, an inorganic metal. The crosslinking efficiency can be improved as compared with the salt. For example, when the resin composition layer 3 is laminated by coating with a coating liquid containing the resin composition, if the reactivity is too high, a crosslinking reaction proceeds in the coating liquid, and the resin composition is not suitable for coating. However, the organometallic compound is suitable for coating because its reactivity is easily controlled by changing its ligand.

Preferred examples of the above-mentioned metal organic compound include:
Examples include titanium organic compounds, zirconium organic compounds, aluminum organic compounds, and silicon organic compounds.
These metal organic compounds may be used alone,
As appropriate, two or more kinds may be used as a mixture.

Specific examples of the titanium organic compound include:
For example, titanium orthoesters such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, and tetramethyl titanate; titanium acetylacetonate, titanium tetraacetylacetonate, polytitanium acetylacetonate; Titanium chelates such as titanium octylene glycolate, titanium lactate, titanium triethanol aminate, and titanium ethyl acetoacetate; titanium acylates such as polyhydroxytitanium stearate; and the like.

Specific examples of the zirconium organic compound include, for example, zirconium normal propylate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, zirconium acetylacetonate bisethylacetate Acetate and the like.

Specific examples of the aluminum organic compound include aluminum acetylacetonate, aluminum organic acid chelate and the like.

Specific examples of the above-mentioned organic silicon compounds include, for example, compounds having the ligands exemplified as the above-mentioned organic titanium compounds and organic zirconium compounds.

The above-mentioned metal organic compounds may be used singly or in combination of two or more.
Among the above-mentioned metal organic compounds, a chelate compound, for example, a metal organic compound having a chelating ligand such as acetylacetonate and having a coordination bond with the high hydrogen bonding resin has a moderate crosslinking reactivity. Among them, a titanium chelate compound is particularly preferable in terms of stability in a coating solution when the obtained resin composition is coated. Further, the titanium chelate compound exhibits a particularly excellent effect in improving the water resistance.

In the above resin composition, a titanium-based coupling agent, a silane-based coupling agent, a melamine-based coupling agent, an epoxy-based coupling agent, an isocyanate-based coupling agent is used as a crosslinking agent for the hydrogen-bonding group. A coupling agent such as a ring agent; a water-soluble epoxy compound; a copper compound; a zirconium compound;

From the viewpoint of improving water resistance, among these exemplified compounds, zirconium compounds, water-soluble epoxy compounds, and silane coupling agents are relatively preferably used.

Specific examples of the zirconium compound include halogenated zirconium such as zirconium oxychloride, zirconium hydroxychloride, zirconium tetrachloride and zirconium bromide; and mineral acids such as zirconium sulfate, basic zirconium sulfate and zirconium nitrate. Zirconium salts; zirconium salts of organic acids such as zirconium formate, zirconium acetate, zirconium propionate, zirconium caprylate, zirconium stearate;
Zirconium complex salts such as ammonium zirconium carbonate, sodium zirconium sulfate, zirconium ammonium acetate, sodium zirconium oxalate, sodium zirconium citrate and zirconium ammonium citrate;

Specific examples of the water-soluble epoxy compound include:
Examples thereof include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, glycidyl ether-based epoxy resin, heterocyclic epoxy resin, glycidylamine-based epoxy resin, and aliphatic epoxy resin.

Specific examples of the silane coupling agent include:
Examples include an amino silane coupling agent, a vinyl or methacryloxy silane coupling agent, an epoxy silane coupling agent, a methyl silane coupling agent, a chloro silane coupling agent, and a mercapto silane coupling agent.

The mixing ratio of the crosslinking agent to the high hydrogen bonding resin is not particularly limited, but
The number of moles of the crosslinkable functional group in the high hydrogen bonding resin (that is, the total number of moles of the hydrogen bonding group and the ionic group) is HN, and the crosslink forming group in the crosslinker (the crosslinker is a metal organic compound). In some cases, assuming that the number of moles of the cross-linking group including the ligand) is CN, the ratio of the number of moles of the cross-linking group of the cross-linking agent to the number of moles of the cross-linking functional group of the high hydrogen bonding resin K (K = CN / HN) is 0.0
It is preferably used so as to be in the range of 01 to 10, more preferably in the range of 0.01 to 1.

The resin composition may contain various conventionally known additives such as an ultraviolet absorber, a coloring agent, an antioxidant and the like within a range not to impair the effects of the present invention.

The resin composition layer 3 according to the present invention comprises a coating liquid (composition mixture) containing at least the above resin composition prepared from an inorganic layer compound and a resin and a liquid.
A coating film is formed by coating (coating) on a layer to be a lower layer of the resin composition layer 3 (for example, a substrate 1, an anchor layer, or a barrier layer 2 described later), for example, the above-mentioned coating film Can be easily formed by drying and heat-treating to remove the liquid from the coating film. The resin composition layer 3 can also be formed by a method of laminating a film made of the resin composition on a layer to be a lower layer of the resin composition layer 3 made of the film. Among the above methods, the former is particularly preferred.

The coating liquid used in the present invention is more specifically a liquid obtained by dispersing or dissolving the resin composition in a liquid such as a solvent or a dispersion medium. From the viewpoint of the gas barrier properties of the obtained film laminate, the liquid is preferably a dispersion medium that swells or cleaves the above-mentioned inorganic layered compound. When the liquid is a dispersion medium, the inorganic layered compound,
It is dispersed in the liquid in a swollen or cleaved state.

The concentration of the resin and the inorganic stratiform compound in the coating solution is generally in the range of 0.1% by weight to 70% by weight, and in the range of 1% by weight to 15% by weight. Is preferably in the range of 4% by weight to 10% by weight from the viewpoint of productivity.

Examples of the method used for coating the above-mentioned coating liquid include gravure methods such as direct gravure method, reverse gravure method and microgravure method;
Roll coating methods such as the present roll beat coating method and bottom feed three-reverse coating method; doctor knife method; die coating method; dip coating method; spray coating method; spin coating method; bar coating method; Conventionally known various methods can be adopted.

The method for preparing the coating liquid and the method for mixing the resin with the inorganic layered compound are not particularly limited. As the compounding method (preparation method of the coating liquid), for example, from the viewpoint of uniformity or ease of operation during compounding, for example,
A method of mixing a solution obtained by dissolving a resin in a solvent and a dispersion obtained by swelling or cleaving an inorganic layered compound in advance;
A method in which a dispersion obtained by swelling or cleaving an inorganic layered compound with a dispersion medium is added to a resin, and the resin is dissolved in the dispersion; an inorganic layered compound is added to a solution obtained by dissolving the resin in a solvent; A method in which a compound is swollen or cleaved with the above solution to form a dispersion.

In this case, the crosslinking agent is preferably added and mixed after the high hydrogen bonding resin and the inorganic layered compound are mixed. However, the crosslinking agent is added simultaneously with the high hydrogen bonding resin or the inorganic layered compound. Alternatively, it may be used by dissolving or dispersing it in the solvent or dispersion medium in advance. When the crosslinking agent contains a metal organic compound, the crosslinking agent is preferably dissolved in an alcohol and added.
Further, from the viewpoint of the stability of the coating liquid containing the metal organic compound, the coating liquid is preferably made acidic, more preferably pH 5 or less, particularly preferably 3 or less. There is no particular lower limit on the pH of the coating solution, but it is usually 0.5 or more.
By including the mixing step of the above resin and a crosslinking agent, the resin composition layer 3 in which the above resin is crosslinked can be obtained.

Further, as a suitable method of mixing the resin and the inorganic layered compound, besides the above-mentioned methods, for example, a method of hot-kneading the resin and the inorganic layered compound may be employed.

Among the above-mentioned methods, the above-mentioned methods are more preferable in that a large aspect ratio of the inorganic layered compound can be easily obtained. When the above methods (1) to (4) are employed, it is preferable to perform treatment using a high-pressure dispersing device from the viewpoint of dispersibility of the inorganic layered compound.

As the high-pressure dispersion device, for example, Microf
There is an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by luidics Corporation or a Nanomizer manufactured by Nanomizer. Other examples include a Menton-Gaulin type high-pressure dispersing apparatus such as a homogenizer manufactured by Izumi Food Machinery. The composition mixture containing the inorganic layered compound and the resin is subjected to a high-pressure dispersion treatment, particularly, 100 kgf /
By performing high-pressure dispersion treatment under a pressure condition of cm ² or more,
A resin composition in which the inorganic layered compound and the resin are uniformly dispersed, and a coating solution containing the resin composition can be obtained.

In the present invention, the high-pressure dispersion treatment is performed, as shown in FIG. 6, by passing a composition mixture obtained by mixing particles to be dispersed or a dispersion medium and the like into a plurality of narrow tubes 11 at high speed to collide with each other. Dispersion treatment under special conditions such as high shear and high pressure.

In such a high-pressure dispersion treatment, the composition mixture is preferably passed through a thin tube 11 having a diameter of 1 μm to 1,000 μm. It is preferable that a pressure of 100 kgf / cm ² or more is applied.
More preferably, a pressure of f / cm ² or more is applied, and particularly preferably, a pressure of 1,000 kgf / cm ² or more is applied. In addition, the composition mixture is a thin tube 11
When passing through the inside, the maximum arrival speed of the composition mixture is 1
00 m / s or more, and the heat transfer rate is 1
It is preferably at least 00 kcal / hr.

The principle of the high-pressure treatment in the high-pressure dispersion treatment apparatus used for the high-pressure dispersion treatment will be schematically described.
The composition mixture is sucked into the feeder tube 13 having a larger diameter than the thin tube 11 by the pump 12 and taken in. Subsequently, a high pressure is applied to the composition mixture in the feeder tube 13 by the pump 12. At this time,
Check valve provided on feeder tube 13 (not shown)
As a result, the composition mixture in the feeder tube 13 is
Extruded toward one. Therefore, the composition mixture is
In the thin tube 11, a high pressure and a high speed state are established, and the respective inorganic layered compound particles of the composition mixture collide with each other and the inner wall of the thin tube 11, and the diameter and thickness, particularly the thickness, of each of the inorganic layered compound particles are reduced. It is subdivided and more uniformly dispersed and taken out of the discharge pipe 14 to the outside.

For example, when the flow velocity at the point where the maximum velocity is instantaneously reached with respect to the composition mixture as the sample to be processed in the thin tube 11 is 300 m / s, the volume is 1 × 10 ^−3.
passes through a cube of m ³ at 1 / (3 × 10 ⁵ ) sec,
When the temperature of the composition mixture increases by 35 ° C., energy is transferred to the composition mixture by pressure loss. The heat transfer rate is such that the specific gravity of the composition mixture is 1 g / cm ^{3 and the} specific heat 1 cal /
At g ° C., it is 3.8 × 10 ⁴ kcal / hr.

When the above methods (1) to (4) are used, a solvent or a dispersion medium is removed from a coating film formed by coating the above-mentioned coating liquid (composition mixture) on the substrate 1 and laminated.
The obtained coated film is, for example,
Heat aging at a temperature of not more than ° C. is particularly preferable because the water resistance of the obtained film laminate, that is, the gas barrier property after the water resistance environment test can be improved. The aging time is not limited, but it is necessary that the coated film reaches at least the set temperature.
00 minutes or less is preferable.

The heat source is not particularly limited, and various methods such as hot roll contact, heat medium contact (air, oil, etc.), infrared heating, microwave heating and the like can be applied. The aging treatment exhibits particularly excellent effects in improving water resistance when the resin contains a high hydrogen bonding resin.

The coating thickness of the above coating solution may be appropriately set according to the type of the lower layer of the resin composition layer 3 to be obtained, the intended barrier performance, the intended use, etc., but is not particularly limited. From the viewpoints of dryness and adhesion, it is preferable to set the dry thickness (that is, the thickness of the resin composition layer 3) to be 10 μm or less, and the transparency of the obtained resin composition layer 3 is extremely high. Therefore, it is preferable to set the thickness to 1 μm or less. The lower limit of the thickness of the resin composition layer 3 is not particularly limited, but is 1 nm or more in order to obtain an effective gas barrier property due to the unit thickness a of the inorganic layered compound. Is preferred.

In the present invention, the resin composition layer 3 is formed as shown in FIG.
As shown in the figure, the inorganic layered compound has a layered shape such that the layers, for example, the unit crystal layers 31 face each other, and are substantially parallel to the surface direction of the resin composition layer 3. Since it is dispersed and oriented in the resin 32 of the layer 3 in a swollen or cleaved state, a maze effect is generated, and excellent gas barrier properties can be obtained.

The packaging container according to the present invention and the above-mentioned film laminate used as a packaging material for the packaging container include:
By providing the resin composition layer 3, the oxygen permeability according to the oxygen permeability measurement method described below is 1 (ml / atm ·
m ² · day) or less, preferably 0.1 (ml / atm · m)
² · day) or less, more preferably 0.05 (ml / atm)
· M ² · day) or less.

In the present invention, the layer structure in the packaging container, that is, the configuration of the film laminate used as a packaging material for the packaging container may be a configuration provided with the resin composition layer 3. The layers other than the resin composition layer 3 are not particularly limited, but preferably further include a thermoplastic resin layer.

As shown in FIG. 1B, when the thermoplastic resin layer is provided, for example, as the sealant layer 5, it is preferable that the thermoplastic resin layer is laminated on the innermost layer of the packaging container. When the thermoplastic resin layer is provided as the base material layer 1, the thermoplastic resin layer is preferably laminated on the outermost layer in the packaging container.

As the thermoplastic resin used for the sealant layer 5, water-repellent or aromatic substances capable of holding liquid contents such as juice, food in paste form, etc., and preventing penetration or leakage of water can be used. Any solvent may be used as long as it has solvent resistance to a solvent such as an alcohol that dissolves the compound. Further, it is preferable that the thermoplastic resin has a heat sealing property in order to improve heat sealing strength when manufacturing a packaging container.

As the thermoplastic resin, for example, polyethylene (low-density, high-density), ethylene-propylene copolymer, ethylene-butene copolymer may be used due to the problem of heat sealing strength, deodorization of food aroma and resin odor. Polymer, ethylene-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene -Methyl acrylate copolymer, ethylene-acrylic acid copolymer, polyolefin resin such as ionomer resin, polyacrylonitrile resin (PAN), polyester resin, and ethylene-vinyl alcohol copolymer are preferably used.

In the sealant layer 5, a sealant having a high impact strength is preferable especially when the sealing property of the contents is required. As a resin satisfying these, polyolefin-based resins such as polyethylene, polypropylene, and ethylene-α-olefin copolymer synthesized using a metallocene-based catalyst or a late transition metal complex catalyst are preferable. Such a sealant has a density of 0.920 g / cm
³ or less is desirable.

The method of laminating the sealant layer 5 on, for example, the resin composition layer 3 is not particularly limited. For example, the resin used for the sealant layer 5 is dissolved in a solvent, and Preferred examples include a method of coating; a method of extruding and laminating the sealant layer 5 on the resin composition layer 3; and a method of dry laminating the sealant layer 5 on the resin composition layer 3. The interface between the sealant layer 5 and the resin composition layer 3 may be subjected to a treatment such as a corona treatment, a flame plasma treatment, an ozone treatment, an electron beam treatment, or the application of an anchor coating agent.

When a thermoplastic resin is used as the base resin of the base 1, the base resin may be polyethylene (low density, high density), ethylene-propylene copolymer,
Polyolefin resins such as ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, and ionomer resin; polyethylene terephthalate; Polyester resins such as polybutylene terephthalate and polyethylene naphthalate; amide resins such as nylon-6, nylon-6,6, metaxylenediamine-adipic acid condensation polymer, polymethyl methacrylimide; and acrylic resins such as polymethyl methacrylate Resin; polystyrene, styrene
Styrene-acrylonitrile resins such as acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer and polyacrylonitrile; hydrophobicized cellulose resins such as cellulose triacetate and cellulose diacetate; polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride , Teflon and other halogen-containing resins; PVA, ethylene-vinyl alcohol copolymer, hydrogen-bonding resins such as cellulose derivatives; polycarbonate resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, polyphenylene oxide resins, and polyphenylene oxide resins. Engineering plastic resins such as methylene oxide resins and liquid crystal resins;

When the above-mentioned thermoplastic resin is used as the base resin of the base material 1, the base material 1 is preferably a biaxially stretched film because of its excellent strength such as tensile strength. It is more preferable that the film is at least one film selected from the group consisting of biaxially stretched polyamide, biaxially stretched polyethylene terephthalate, and biaxially stretched polypropylene. A film obtained by biaxially stretching these base materials such as polypropylene, polyethylene terephthalate, and nylon, and then coating with polyvinylidene chloride called K coat; biaxially stretching these base materials such as polypropylene, polyethylene terephthalate, and nylon Later, further, aluminum, silica,
Film deposited with alumina etc .;
PP (AS-OP); and the like are more preferable.

As the base material 1, a material other than the base resin described above, for example, a base material made of kraft paper, woodfree paper, imitation paper, glassine paper, parchment paper, synthetic paper, various cardboards, or the like, It is also possible to use a film made of a base resin that has not been stretched.

When the base material 1 is made of a material other than the base resin, for example, a base material made of kraft paper, woodfree paper, imitation paper, glassine paper, parchment paper, synthetic paper, various cardboards, etc. When using a film made of a base resin that has not been stretched, the obtained packaging container is further provided with a strength, for example, a stretched film layer 4 made of a stretched film as described above in order to impart tensile strength. It is preferable to laminate between the resin composition layer 3 and the sealant layer 5. As the above-mentioned stretched film, the one having a higher tensile strength is more preferable, and the one having a breaking elongation of 700% or less is more preferable, and one having a tensile strength of 500% or less is more preferable.

The substrate 1 used in the packaging container of the present invention is not particularly limited as long as it has a strength capable of forming a packaging container. However, in consideration of environmental protection at the time of disposal or recycling, the substrate 1 is preferably made of a resin composed of only carbon and hydrogen, or a resin composed of only carbon, hydrogen and oxygen, for example, a polyolefin resin. It is suitable.

The above-mentioned film laminate used as a packaging material for the packaging container of the present invention further comprises a barrier layer 2 made of a metal such as aluminum or a metal oxide such as silica or alumina. Between any of the layers, for example, between the resin composition layer 3 and the substrate 1, the film thickness is 1 nm to 1000 nm, more preferably 10 nm to 2 nm.
It may be provided by laminating at 00 nm. With such a barrier layer 2, gas barrier properties can be further ensured, and
Light shielding properties and water vapor barrier properties can also be imparted. Examples of a method for preparing the barrier layer 2 include a vapor deposition method and a sol-gel method, and a vapor deposition method is particularly preferable.

By the way, in the conventional gas barrier container,
In order to impart gas barrier properties, a metal layer such as an aluminum foil was required at a film thickness of 7 μm to 20 μm, so when disposing of the gas barrier container, for example, during incineration,
Many residues (ingots) of the metal layer remained, and the disposal process was troublesome.

However, in the present invention, by providing the barrier layer 2 with a film thickness of 1000 nm or less, the gas barrier properties can be further ensured, the light-shielding property can be provided, and the film thickness is set to be thinner than before. Because it is possible, disposal at the time of disposal can be facilitated. As described above, the thickness of the barrier layer 2 can be suppressed to be thin, so that, for example, the amount of metal or metal oxide used per carton container can be suppressed to a low level, and residues during incineration can be reduced. can do. In addition, the packaging container according to the present invention includes the resin composition layer 3 having the above-described configuration, so that the layer made of a metal or a metal oxide has a sufficient gas barrier property and a water vapor barrier even when the layer has a small thickness as described above. The property is obtained.

As shown in FIG. 1 (b), when the barrier layer 2 is directly laminated on the substrate 1,
The film is preferably made of at least one selected from the group consisting of biaxially oriented polyamide, biaxially oriented polyethylene terephthalate, and biaxially oriented polypropylene.

FIG. 1B shows a configuration in which a barrier layer 2, a resin composition layer 3, a stretched film 4, and a sealant layer 5 are laminated on the base material 1 in this order. However, in the packaging container of the present invention, the order of lamination of the above layers is not particularly limited. For example, the order of lamination of the barrier layer 2 and the resin composition layer 3 may be reversed. Other layers may be laminated.

For example, when laminating the resin composition layer 3 of the present invention on a layer to be a lower layer of the resin composition layer 3, for example, on the above-described substrate 1, the resin composition layer 3 and the substrate 1 May be subjected to a treatment such as corona treatment, flame plasma treatment, ozone treatment, electron beam treatment, or formation of an anchor layer. When the anchor layer is formed, the anchor layer can be formed using various compounds (anchor coating agents) such as a polyethyleneimine compound, a titanium compound, a polybutadiene compound, and a urethane compound. However, from the viewpoint of water resistance, a urethane-based anchor layer obtained by reacting an isocyanate compound with an active hydrogen compound is preferable.

As the isocyanate compound used for the anchor layer, specifically, for example, tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate ( HD
I), 4,4'-methylenebiscyclohexyl isocyanate (H12MDI), isophorone diisocyanate (IP
DI) and the like.

As the active hydrogen compound, specifically, for example, ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-
Low molecular weight polyols such as hexanediol, neopentyl glycol and trimethylolpropane; polyether polyols such as polyethylene glycol, polyoxypropylene glycol, ethylene oxide / propylene oxide copolymer and polytetramethylene ether glycol; poly-β-methyl-δ Valerolactone, polycaprolactone, polyester polyols such as polyesters from diols / dibasic acids; and the like.

As the active hydrogen compound, a low molecular weight polyol is particularly preferable, and among them, a diol is more preferable. Here, the diol means ethylene glycol, diethylene glycol, dipropylene glycol,
1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and the like; and dibasic acids such as adipic acid, azelaic acid, sebacic acid, isophthalic acid, and terephthalic acid. Other polyols include castor oil, liquid polybutadiene, epoxy resin, polycarbonate diol, acrylic polyol, and active hydrogen compounds such as neoprene.

The mixing ratio between the isocyanate compound and the active hydrogen compound is not particularly limited.
It is preferable to determine the amount to be added in consideration of the equivalence relationship with active hydrogen groups, for example, -OH group, -NH group, and -COOH group. For example, assuming that the number of moles of the isocyanate group is AN and the number of moles of the active hydrogen group of the active hydrogen compound is BN, the ratio R (R = AN / BN) of the number of moles of the isocyanate group to the number of moles of the active hydrogen group is as follows: 0.00 from the viewpoint of adhesive strength
It is preferably 1 or more, and more preferably 10 or less from the viewpoint of tackiness and blocking. More preferably, the molar ratio R is in the range of 0.01 or more and 1 or less. Each mole number of the isocyanate group and the active hydrogen group can be quantified by 1H-NMR and 13C-NMR.

The method of laminating the anchor layer on the resin composition layer 3 or another layer, for example, the substrate 1, is not particularly limited, but the anchor coating agent described above, for example, the anchor coating containing an isocyanate compound and an active hydrogen compound is used. A coating method using an anchor coat agent solution obtained by dissolving the agent in a solvent is preferred. Examples of the coating method include a gravure method such as a direct gravure method, a reverse gravure method, and a microgravure method; a roll coating method such as a two-roll beat coating method and a bottom feed three-reverse coating method; a doctor knife method; A dip coating method; a bar coating method; a spray coating method; a spin coating method; or a coating method combining these methods;

The solvent component in the above anchor coating agent solution is mainly an organic solvent and includes, for example, alcohols, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, esters, ketones, and ethers. , Halogenated hydrocarbons, and mixed solvents thereof.

Coating (coating) of the above anchor coating agent solution
The thickness is not particularly limited, but is preferably set so that the dry thickness (that is, the thickness of the anchor layer) is in the range of 0.01 μm to 5 μm. The larger the coating thickness, the better the heat sealing strength, but the lower the gelboflex resistance. Therefore, the coating thickness is more preferably in the range of 0.03 μm to 2.0 μm, and particularly preferably in the range of 0.05 μm to 1.0 μm.

In the film laminate used in the packaging container of the present invention, when the resin composition layer 3 is laminated on the anchor layer, or when the anchor layer is laminated on the resin composition layer 3, The resin composition layer 3 preferably contains a surfactant for improving the adhesion to the anchor layer. As the surfactant, any surfactant can be used as long as it can improve the adhesion between the anchor layer and the resin composition layer 3.
Although not particularly limited, examples thereof include an anionic surfactant, a cationic surfactant, a zwitterionic surfactant and a nonionic surfactant.

Examples of the anionic surfactant include a carboxylic acid type such as an aliphatic monocarboxylate, N-acyloylglutamate, an alkylbenzene sulfonate, a naphthalene sulfonate-formaldehyde condensate, and a dialkyl sulfosuccinate. Sulfonic acid type, alkyl sulfate type, sulfate type such as alkyl polyoxyethylene salt, phosphate type such as alkyl phosphate type, borate type such as alkyl borate type, etc. Activator, sodium perfluorodecanoate,
Examples include fluorine-based anionic surfactants such as sodium perfluorooctylsulfonate, and silicone-based anionic surfactants having an anionic group such as a polymer having a polydimethylsiloxane group and a metal carboxylate.

Examples of the cationic surfactant include:
Amine salt types such as alkylamine salts, alkyltrimethylammonium salts, dialkyldimethylammonium salts,
And quaternary ammonium salts such as alkyldimethylbenzylammonium salts.

Examples of the amphoteric surfactant include carboxybetaine type such as N, N-dimethyl-N-alkylaminoacetic acid betaine and glycine such as 1-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine. Type.

Examples of the nonionic surfactant include ester types such as glycerin fatty acid ester, sorbitan fatty acid ester and sucrose fatty acid ester, condensation polymers of polydimethylsiloxane groups and alkylene oxide adducts, and polysiloxane-polyoxyalkylene copolymers. Polymer, ether type such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block polymer, etc., ester ether type such as polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc., aliphatic alkanolamide And fluorinated compounds such as perfluorodecanoic acid-diglycerin ester and perfluoroalkylalkylene oxide compounds.

Among the above surfactants, in particular, those having 6 carbon atoms
As described above, an alkali metal salt of a carboxylic acid having an alkyl chain of 24 or less, an ether type nonionic surfactant such as polydimethylsiloxane-polyoxyethylene copolymer (silicone nonionic surfactant), Fluorine-type nonionic surfactants such as fluoroalkylethylene oxide compounds (fluorine-type nonionic surfactants) are preferred.

When the resin composition layer 3 is formed, for example, when a coating solution is used in forming the resin composition layer 3, the content in the coating solution is 0.001% by weight from the viewpoint of the effect. -5% by weight, preferably 0.003% by weight.
It is more preferably set to be from 0.5% by weight to 0.5% by weight, and particularly preferably set to be from 0.005% by weight to 0.1% by weight.

When the resin composition further contains a surfactant, the affinity of the resin composition layer 3 with the anchor layer, that is, the wettability can be improved. Adhesion between the excellent anchor layer and the resin composition layer 3 can be improved.

In addition, as long as the effects of the present invention are not impaired,
An ultraviolet absorber for at least one of the above-mentioned layers,
Additives of various species such as a coloring agent and an antioxidant may be mixed.

In the present invention, the thickness of the film laminate used for the packaging container is not particularly limited, but is preferably in the range of 30 μm to 300 μm. If the film thickness is less than 30 μm, the content tends to be inferior in protection. On the other hand, if it is thicker than 300 μm, it becomes a factor of increasing the cost.

In the packaging container of the present invention, if necessary,
(1) an oxygen scavenger, a desiccant, a freshness preserving agent, (2) a shielding agent (material) used for shielding light, ultraviolet rays, visible light, etc., (3) an easy peel used for easy opening. You may use an easy break material (especially, when it is a pair of a container and a lid material), and (4) an easily tearable material. The above-mentioned packaging container can be used, for example, for vacuum packaging. For vacuum packaging, “Food Packaging Handbook” (Japan Packaging Technology Association) can be referred to.

As described above, the packaging container of the present invention is excellent in gas barrier properties by being provided with the resin composition layer 3 having the above-described configuration, and does not deteriorate in packaging. In addition, since a halogen-containing compound is not used to impart gas barrier properties as in the conventional case, corrosion and environmental problems of manufacturing equipment, which are problems in conventional packaging containers such as conventional three-side sealed packaging bags and four-side sealed packaging bags, etc. Destruction can be prevented, and cost reduction and reduction of environmental load can be realized. In addition, the above-mentioned packaging container has a simple configuration by adopting a configuration in which at least three sides are heat-sealed, and can be manufactured at low cost.

The packaging container of the present invention includes: prepared food; confectionery and snacks such as Western confectionery; miso; pickles; konjac; Agrochemicals; Fertilizers; Cosmetics; Fragrances; Oxidizing drugs; Applications for packaging various articles such as precision materials, medical packaging such as infusion packs, electronic packaging such as semiconductor packaging, chemical packaging, mechanical packaging, etc. Can be used for applications. Among them, the packaging container of the present invention is particularly suitable for use in packaging processed foods such as prepared foods, processed meat (animal meat), processed marine products, confectionery and snacks.

[0141]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. The methods for measuring various physical properties are described below.

[Thickness Measurement] The thickness of 0.5 μm or more was measured with a commercially available digital thickness gauge (contact type thickness gauge, trade name: Ultra-high precision decimicro head MH-15M, manufactured by Nippon Kogaku Co., Ltd.) On the other hand, when the thickness is less than 0.5 μm, the thickness of the actual coating film is determined by a gravimetric analysis method (the measured weight value of a film having a certain area is divided by the area and further divided by the specific gravity of the resin composition) or the IR method. Create a calibration curve of thickness and IR absorption,
It was determined from a calibration curve. Further, in the case of measuring the thickness of the coating film of the resin composition of the present invention, the elemental analysis method (specific inorganic element analysis value of the film laminate (derived from the resin composition layer) and the specific elemental content of the inorganic layered compound alone) Method for determining the ratio between the resin composition layer of the present invention and the substrate (substrate film) from the ratio of the ratios)
According to

[Measurement of Particle Size] Using a laser diffraction / scattering type particle size distribution analyzer (LA910, manufactured by HORIBA, Ltd.), the volume-based median of particles considered to be inorganic layered compounds present in the resin matrix of the medium. The diameter was measured as a particle diameter L. The undiluted dispersion was measured with a paste cell at an optical path length of 50 μm, and the diluent of the dispersion was measured with a flow cell method at an optical path length of 4 mm.

[Aspect Ratio Calculation] X-ray diffractometer (XD
-5A (manufactured by Shimadzu Corporation), the diffraction measurement of the inorganic layered compound alone and the resin composition by the powder method was performed. Thereby, the unit thickness a of the inorganic layered compound was obtained, and further, from the diffraction measurement of the resin composition, it was confirmed that there was a portion where the interplanar spacing d of the inorganic layered compound was widened. Using the particle diameter L obtained by the above-described method, the aspect ratio (Z) is calculated as Z = L
/ A was calculated.

[Oxygen permeability measurement] JIS K 7126
Based on the oxygen permeability measurement device (OX-TRAN M
L, manufactured by MOCON) under the conditions of 23 ° C. and 50% RH.

The coating liquid (1) for the resin composition layer is as follows:
It was prepared as follows.

[Coating liquid (1)] In a dispersing vessel (trade name: Despa MH-L, manufactured by Asada Tekko Co., Ltd.), 1,860 g of ion-exchanged water (specific electric conductivity 0.7 μs / cm or less) was added. , PVA as high hydrogen bonding resin (PVA117H; Co., Ltd.)
(Manufactured by Kuraray, saponification degree: 99.6%, polymerization degree 1,700)
128, and the mixture was heated to 95 ° C. under low-speed stirring (1,500 rpm, peripheral speed: 4.10 m / min), stirred for 1 hour and dissolved to obtain a solution (A).

On the other hand, after mixing 125 g of 1-butanol and 375 g of isopropyl alcohol, 0.25 g of a nonionic surfactant (trade name: SH3746, manufactured by Dow Corning Toray Co., Ltd.) was added, and the mixture was added. (B)
I got The nonionic surfactant is a polydimethylsiloxane-polyoxyethylene copolymer.

Next, the temperature of the solution (A) in the dispersing vessel was lowered to 60 ° C. while stirring, and the previously prepared mixture (B) was added to the solution (A) and mixed. Liquid (C)
I got

Next, 1,960 g of the mixed liquid (C) was charged into a stirring emulsifying apparatus (trade name: vacuum emulsifying apparatus PVQ-3UN, manufactured by Mizuho Industry Co., Ltd.). 50 g of natural montmorillonite (trade name: Kunipia F; manufactured by Kunimine Industries, Ltd.) as an inorganic layered compound was added as a powder so that the weight ratio with the layered compound was 2: 1. Subsequently, after confirming that the natural montmorillonite (Kunipia F) was substantially precipitated in the solution, the mixture was rapidly stirred at 600 mmHg and 5,000 rpm for 10 minutes to obtain a mixed solution (D).

Next, a high-pressure dispersion apparatus (trade name: ultrahigh-pressure homogenizer M110-E / H, Microfluidics Corporat)
2,000 g of the above mixed solution (D)
By treating once at 1,750 kgf / cm ² , a uniform dispersion (D ′) having good dispersibility was obtained. The solid content of the dispersion (D ′) was 7.5% by weight. Casting a dispersion composed of PVA and montmorillonite into a film,
X-ray analysis was performed to measure the interplanar spacing d of the swollen and cleaved natural montmorillonite (Kunipia F). The natural montmorillonite (Kunipia F) was sufficiently cleaved. At this time, the aspect ratio (Z) of the natural montmorillonite (Kunipia F) was 450 or more.

The dispersion (D ′) was mixed with titanium acetylacetonate (trade name: TC10) as a metal organic compound.
0, manufactured by Matsumoto Pharmaceutical Co., Ltd.) was gradually adjusted with hydrochloric acid so that the pH of the system was 3 or less under low-speed stirring (1,500 rpm, peripheral speed: 4.10 m / min). By adding, a coating liquid (1) containing the resin composition according to the present invention and a solvent was prepared.

Example 1 A biaxially oriented polypropylene (OPP) film having a thickness of 20 μm (trade name: Pyrene P2)
102; manufactured by Toyobo Co., Ltd.) as a base material, and an anchor coat agent (Adcoat AD) on the base material.
335 / CAT10 = 15/1 (weight ratio: manufactured by Toyo Morton Co., Ltd.) using a test coater (manufactured by Yasui Seiki) by a microgravure coating method at a coating speed of 3 m /
Gravure coating at a drying temperature of 80 ° C. The dry thickness of the coating layer (the thickness of the anchor layer) was 0.15 μm.

Further, the above coating liquid (1) was used as a TOP coating liquid by a microgravure coating method using a test coater (manufactured by Yasui Seiki) at a coating speed of 3 m / m.
Gravure coating at a drying temperature of 100 ° C. for a coating film (resin composition layer) based on the above-mentioned coating liquid (1) formed on a substrate via an anchor layer (film laminate) ) Got. The thickness of the resin composition layer, that is, the dry thickness of the coating layer formed by applying the coating liquid (1) on the anchor layer was 0.5 μm.

Next, an adhesive (trade name: Adcoat AD503 / CAT1) was formed on the resin composition layer of the coating film.
0 = 15/1 (weight ratio, manufactured by Toyo Morton Co., Ltd.) and dry-laminated a 50 μm-thick metallocene LL film (trade name “TUX-FCS”, manufactured by Tocelo Co., Ltd.) as an outer layer (sealant layer). Thus, a film laminate was obtained. The oxygen permeability of this film laminate was measured according to the above-described measurement method. As a result, the film laminate had an oxygen permeability (mL / atm · m ² · day) of 0.1 or less and was excellent in oxygen permeability.

Using the above-mentioned film laminate, a four-sided seal packaging bag was prepared by a conventional method. At this time, the air inside the four-sided seal packaging bag is replaced with nitrogen, and “Ageless Eye” (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is sealed in the four-sided sealed packaging bag. The gas barrier property was evaluated by observing the color change of "."
As a result, no color change of “ageless eye” was observed even after 60 days at 23 ° C. From this, it is understood that the four-side sealed packaging bag has excellent gas barrier properties even at the time of packaging.

Comparative Example 1 A four-side sealed packaging bag was produced in the same manner as in Example 1 except that polyvinylidene chloride was used instead of the resin composition to form a polyvinylidene chloride layer on the anchor layer. Was prepared, and its gas barrier properties were evaluated in the same manner as in Example 1. As a result,
After 20 days at 23 ° C., a color change of “ageless eye” was observed.

[0158]

As described above, the packaging container according to the first aspect of the present invention includes a resin composition layer composed of a resin composition prepared from at least an inorganic layered compound and a resin, and has at least three sides. The structure is heat-sealed.

The packaging container according to claim 2 of the present invention is
As described above, the packaging container according to the first aspect is configured to be a four-side seal type packaging container.

The packaging container according to the third aspect of the present invention comprises:
As described above, the packaging container according to claim 1 or 2, further includes a barrier layer made of at least one of a metal and a metal oxide.

The packaging container according to the fourth aspect of the present invention comprises:
As described above, the packaging container according to any one of claims 1 to 3, further includes a layer made of a thermoplastic resin.

The packaging container according to the fifth aspect of the present invention comprises:
As described above, in the packaging container according to the fourth aspect, the thermoplastic resin is a polyolefin-based resin.

The packaging container according to the sixth aspect of the present invention comprises:
As described above, the packaging container according to any one of claims 1 to 5, further includes a layer made of a stretched film.

The packaging container according to the seventh aspect of the present invention comprises:
As described above, in the packaging container according to the sixth aspect, the stretched film is formed of at least one selected from the group consisting of biaxially stretched polyamide, biaxially stretched polyethylene terephthalate, and biaxially stretched polypropylene. .

The packaging container according to the eighth aspect of the present invention comprises:
As described above, in the packaging container according to any one of claims 1 to 7, the oxygen permeability is 1 (ml / atm · m ² · da).
y) The configuration is as follows.

The packaging container according to the ninth aspect of the present invention comprises:
As described above, in the packaging container according to any one of claims 1 to 8, the inorganic layered compound is a compound that swells or cleaves in a solvent.

As described above, the packaging container according to the tenth aspect of the present invention is the packaging container according to any one of the first to ninth aspects, wherein the resin composition comprises an inorganic layered compound and a resin. Is obtained by subjecting a mixed solution containing

[0168] As described above, the packaging container according to the eleventh aspect of the present invention is the packaging container according to the tenth aspect, wherein the resin composition comprises a mixed solution containing an inorganic layered compound and a resin in an amount of 100 kgf / cm. ^This is a configuration obtained by high-pressure dispersion treatment under ^two or more pressure conditions.

As described above, the packaging container according to the twelfth aspect of the present invention is the packaging container according to any one of the first to eleventh aspects, wherein the inorganic layered compound has an aspect ratio of 50 to 5. , 000.

As described above, in the packaging container according to the thirteenth aspect of the present invention, in the packaging container according to the twelfth aspect, the aspect ratio of the inorganic layered compound is from 200 to 200.
The configuration is within the range of 3,000.

As described above, the packaging container according to the fourteenth aspect of the present invention is the packaging container according to any one of the first to thirteenth aspects, wherein the weight ratio of the inorganic layered compound to the resin is: The configuration is within a range of 1/20 to 10/1.

As described above, the packaging container according to claim 15 of the present invention is the packaging container according to any one of claims 1 to 14, wherein the resin is a high hydrogen bonding resin, The ratio of the hydrogen bonding group or the ionic group in the high hydrogen bonding resin is in the range of 20 mol% to 60 mol%.

As described above, in the packaging container according to claim 16 of the present invention, in the packaging container according to claim 15, the high hydrogen bonding resin is PVA or a modified product thereof.
The structure is at least one compound selected from polysaccharides, ethylene-vinyl alcohol copolymers and modified products thereof.

According to the above configuration, the inorganic layered compound can provide gas barrier properties, and is excellent in the protection of packaged items such as food contents, and the inorganic layered compound enables the film thickness of the resin composition layer to be improved. Can be made thinner than before, so that disposal and recycling can be facilitated. In addition, since a halogen-containing compound is not used as in the related art to provide gas barrier properties, corrosion of a manufacturing apparatus, which is a problem in conventional packaging containers such as a conventional three-side sealed packaging bag and a four-side sealed packaging bag, is not required. Environmental destruction can be prevented, and cost reduction and environmental load reduction can be realized.

Further, since the above-mentioned packaging container has a configuration in which at least three sides are heat-sealed, the packaging container can have a simple configuration and also has an effect that it can be manufactured at low cost. .

[Brief description of the drawings]

FIG. 1A is an external perspective view of an example of a packaging container according to the present invention, in which a three-sided heat-sealed packaging bag is shown. FIG. 1B is a perspective view of a portion A in FIG. It is an enlarged view.

FIG. 2 is a schematic sectional view showing a resin composition layer of the packaging container.

FIG. 3 is an X-ray diffraction graph of an inorganic layered compound for calculating the “unit thickness a” of the inorganic layered compound in the resin composition layer.

FIG. 4 is an X-ray diffraction graph of the inorganic layered compound for calculating the “plane spacing d” of the inorganic layered compound in the resin composition layer.

FIG. 5 is a graph for calculating the “plane spacing d” of the inorganic layered compound when the peak corresponding to the “plane spacing d” overlaps with a halo (or background) and is difficult to detect. It is an X-ray diffraction graph at the time.

FIG. 6 is an explanatory view schematically showing a high-pressure dispersion treatment used when forming the resin composition layer.

[Description of Signs] 1 Base material (layer made of thermoplastic resin, layer made of stretched film) 2 Barrier layer 3 Resin composition layer 4 Stretched film layer 5 Sealant layer (layer made of thermoplastic resin) 21 Packaging bag (packaging) container)

Claims (16)

[Claims] 1. A packaging container comprising a resin composition layer composed of a resin composition prepared from at least an inorganic layered compound and a resin, wherein at least three sides are heat-sealed. 2. The packaging container according to claim 1, wherein the packaging container is a four-sided seal type packaging container. 3. The packaging container according to claim 1, further comprising a barrier layer comprising at least one of a metal and a metal oxide. 4. The packaging container according to claim 1, further comprising a layer made of a thermoplastic resin. 5. The packaging container according to claim 4, wherein said thermoplastic resin is a polyolefin resin. 6. The packaging container according to claim 1, further comprising a layer made of a stretched film. 7. The packaging container according to claim 6, wherein said stretched film is made of at least one selected from the group consisting of biaxially stretched polyamide, biaxially stretched polyethylene terephthalate, and biaxially stretched polypropylene. . 8. An oxygen permeability of 1 (ml / atm · m ² · day)
The packaging container according to any one of claims 1 to 7, wherein: 9. The packaging container according to claim 1, wherein the inorganic layered compound is a compound which swells or cleaves in a solvent. 10. The method according to claim 1, wherein the resin composition is obtained by subjecting a mixed solution containing an inorganic layered compound and a resin to high-pressure dispersion. Packaging container. 11. The resin composition according to claim 1, which is obtained by subjecting a mixed solution containing an inorganic layered compound and a resin to high-pressure dispersion under a pressure condition of 100 kgf / cm ² or more. 10. The packaging container according to 10. 12. An inorganic layered compound having an aspect ratio of:
The packaging container according to any one of claims 1 to 11, wherein the value is in the range of 50 to 5,000. 13. An inorganic layered compound having an aspect ratio of:
13. The packaging container according to claim 12, which is within a range of 200 to 3,000. 14. The packaging container according to claim 1, wherein the weight ratio of said inorganic layered compound to said resin is in the range of 1/100 to 100/1. 15. The method according to claim 15, wherein the resin is a high hydrogen bonding resin, and the ratio of the hydrogen bonding group or the ionic group in the high hydrogen bonding resin is in the range of 20 mol% to 60 mol%. The packaging container according to any one of claims 1 to 14. 16. The high hydrogen bonding resin is at least one compound selected from polyvinyl alcohol and modified products thereof, polysaccharides, and ethylene-vinyl alcohol copolymer and modified products thereof. 15. The packaging container according to 15.