JPH11314671A - Gas-replacement packaging container and gas-replacement packaging method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas-replacement packaging container excellent in gas barrier properties as to oxygen and water vapor, and a gas-replacement packaging method using it. SOLUTION: The gas-replacement packaging container has, between a base layer 1 of a thermoplastic resin or paper matter and a heat sealable film 5, a resin-composition layer 3 containing an inorganic-layer compound. After air inside the gas-replacement packaging container is replaced with a gas which is different in composition from the air, stuff to be packaged is packaged in the gas-replacement packaging container. Thus, degradation in gas barrier properties during the packaging can be restrained, and also the gas-replacement packaging container which can reduce load on the environment and is low in cost can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas replacement used for a gas replacement package for packaging an article (package) such as food by a container in which the air inside is replaced by a gas having a composition different from air. The present invention relates to a packaging container. More specifically, the present invention relates to a gas replacement packaging container having excellent gas barrier properties against oxygen, water vapor, and the like.

[0002]

2. Description of the Related Art In a gas replacement package, an article (packaged object) such as food is packaged in a container in which the air inside is replaced with a gas having a composition different from that of air. Gas replacement packaging is used to package articles in a state in which active gases that cause the deterioration of the articles such as oxygen and water vapor are almost completely removed from the container, and to suppress deterioration of the contents to be packaged (contents). It has the advantage of being possible. Gas replacement packaging also has the advantage of not impairing the shape of the article to be packaged, unlike vacuum packaging.

Conventionally, as a container used for gas replacement packaging, that is, a gas replacement packaging container, a gas replacement packaging container provided with a gas barrier layer made of polyvinylidene chloride has been mainly used.

[0004]

The gas replacement packaging container is required to have a high gas barrier property so that the gas composition in the container can be maintained for a long period of time. However,
The above-mentioned conventional gas replacement packaging container has problems such as a decrease in gas barrier properties at the time of packaging, a large environmental load due to containing chlorine atoms, and a high cost.

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 low-cost gas replacement packaging container capable of suppressing a decrease in gas barrier properties during packaging and reducing an environmental load. To provide.
Another object of the present invention is to provide a gas replacement packaging method capable of remarkably suppressing deterioration of an article to be packaged (content).

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on a container for gas replacement packaging, and as a result, by providing a resin composition layer containing an inorganic layered compound, the environmental load has been reduced. It has been found that the gas barrier property at the time of packaging can be improved at low cost without using a halogen atom having a large value, and the present invention has been completed.

[0007] That is, the gas replacement packaging container of the present invention is characterized by comprising a resin composition layer made of a resin composition containing an inorganic layered compound in order to solve the above problems.

According to the above structure, in the resin composition layer, the inorganic layered compounds face each other due to the shape of the layer and are oriented so as to be substantially parallel to the surface direction of the resin composition layer. Excellent gas barrier properties can be imparted by the maze effect of the inorganic layered compound. Therefore, a decrease in gas barrier properties during packaging can be suppressed, and the effect of gas replacement can be particularly sustained, so that the contents are excellent in protection after filling. Further, there is no need to use a halogen atom having a large environmental load, and the cost is low.

Therefore, it is possible to provide a low-cost gas replacement packaging container which can be used for any packaging having such a form, can suppress a decrease in gas barrier properties at the time of packaging, and can reduce an environmental load.

Further, by laminating a base layer made of a thermoplastic resin or a paper-like material on the resin composition layer, it is possible to impart sufficient strength, for example, tensile strength, to the container for gas replacement packaging. Becomes

Further, by laminating a heat sealable film on the resin composition layer, it becomes possible to impart heat sealability to the gas replacement packaging container.

In addition, by laminating a stretched film on the resin composition layer and laminating a heat sealable film on the stretched film, it is possible to impart heat sealability and easy tearing property to the gas replacement packaging container. Become.

In order to solve the above problems, the gas replacement packaging method of the present invention replaces the air inside the gas replacement packaging container of the present invention with a gas having a composition different from that of the air, and then replaces the gas with the gas. It is characterized in that an article to be packaged is packed in a packaging container.

According to the above method, for example, by replacing the inside of the gas replacement packaging container with an inert gas, the inside of the gas replacement packaging container can be kept free of an active gas such as oxygen or water vapor. it can. As a result, deterioration of the packaged object (content) can be significantly suppressed.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to FIGS. As shown in FIG. 1, the gas replacement packaging container according to the present embodiment includes a base material layer 1, a resin composition layer 3 made of a resin composition containing an inorganic layered compound, and a heat-sealing film 5 laminated in this order. It is provided with a film laminate obtained. In the film laminate, the substrate layer 1 can impart sufficient strength, for example, tensile strength to the film laminate. The gas replacement packaging container of the present invention only needs to include the resin composition layer 3, and thus one or both of the base material layer 1 and the heat-sealing film 5 may be omitted.

Examples of the material of the base material layer 1 include a paper-like material and a thermoplastic resin described later. Paper-like materials include kraft paper, woodfree paper, imitation paper, glassine paper, parchment paper,
Synthetic paper and various cardboards can be mentioned.

The thermoplastic resin of the base layer 1 is not particularly limited, but may be polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, Polyolefin resins such as ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid copolymer, ionomer resin, polyethylene terephthalate, Polyester resins such as polybutylene terephthalate and polyethylene naphthalate; amide resins such as nylon-6, nylon-6,6, metaxylene diamine-adipic acid condensation polymer, polymethyl methacrylimide; and acrylic resins such as polymethyl methacrylate Resin, polystyrene , Styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-acrylonitrile resin such as polyacrylonitrile, cellulose triacetate, hydrophobized cellulose resin such as cellulose diacetate, polyvinyl chloride, polyvinylidene chloride, Halogen-containing resins such as polyvinylidene fluoride and Teflon, hydrogen bonding resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and cellulose derivatives, polycarbonate resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, and polyphenylene An engineering plastic resin such as an oxide resin, a polymethylene oxide resin, and a liquid crystal resin may be used.

Among them, biaxially stretched polypropylene (OP) has excellent strength such as tensile strength.
P), biaxially-stretched polyethylene terephthalate, biaxially-stretched nylon, biaxially-stretched polypropylene (OPP), biaxially-stretched polyethylene terephthalate (OPET), or biaxially-stretched polyethylene (OPP) deposited with a metal or metal oxide such as aluminum, silica, or alumina Axial stretched nylon (ONy), biaxially stretched polypropylene coated with polyvinylidene chloride (called K coat), biaxially stretched polyethylene terephthalate coated with polyvinylidene chloride, biaxially stretched nylon coated with polyvinylidene chloride, and strongly charged Prevention application At least one selected from the group consisting of biaxially oriented polypropylene (AS-OP) is preferably used.

As a material of the base material layer 1, in consideration of environmental protection at the time of disposal or recycling, a resin composed of only carbon and hydrogen or a resin composed of only carbon, hydrogen and oxygen is used. preferable.

The inorganic layer compound used in the resin composition layer 3 is an inorganic compound having a layer structure in which unit crystal layers are stacked on each other.

Regarding the gas barrier properties of the inorganic layered compound, the aspect ratio of the inorganic layered compound in the cleaved state may be 50 or more and 5000 or less.
More preferably, it is in the range of 000. If the aspect ratio is less than 50, the gas barrier property is not sufficient, and if the aspect ratio is more than 5000, it is technically difficult and economically expensive.

The particle size of the inorganic layered compound in the cleaved state may be 5 μm or less, but if it is 3 μm or less, the transparency becomes better and the particle size is 1 μm or less.
If it is not more than μm, it is more preferable for applications where transparency is important.

Specific examples of the inorganic layered compound used in the present invention include graphite, phosphate derivative type compounds (zirconium phosphate type compounds, etc.), chalcogenides,
And clay minerals. Here, the “chalcogen compound” includes a group IV (Ti, Zr, Hf) and a group V (V,
Nb, Ta) and group VI (Mo, W) dichalcogenides represented by the formula MX ₂ (M is the above element, X is chalcogen (S, Se, Te)).

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, it is sufficiently swelled and cleaved with a dispersion medium of the same type as the dispersion medium used in the diffraction / scattering method, and is used for the resin composition layer 3. When combined with a resin, the particle size of the cleaved inorganic layered compound unit crystal layer 31 in the resin 32 in the resin composition layer 3 shown in FIG. 3 is determined by the particle size of the cleaved inorganic layered compound in the dispersion medium. Can be considered as equivalent to

(Method for Determining Average Particle Diameter) The method for determining the average particle diameter of particles in a liquid is a method based on a diffraction / scattering method, a method based on a dynamic light scattering method, a method based on a change in electric resistance, and after photographing in a liquid microscope. A method by image processing or the like is possible.

In the dynamic light scattering method, when the resin and the particles coexist, the apparent liquid viscosity is different from that of the pure dispersion medium, so it is difficult to evaluate the method. There is a problem of resolution in the method using image processing after photographing in a submerged microscope, and each method is difficult to use.

According to the diffraction / scattering method, when a resin solution, for example, a resin aqueous solution has substantially little scattering (transparency), and thus scattering derived from particles is dominant, the method is performed regardless of the presence or absence of the resin. This is preferable because information on only the particle size distribution of the particles can be obtained.

(Measurement of Average Particle Size by Diffraction / Scattering Method) Measurement of the particle size distribution and average particle size by the diffraction / scattering method is based on a method in which a swelled / cleaved inorganic layered compound is dispersed in an aqueous dispersion medium and light is applied to the dispersion. The diffraction / scattering pattern obtained when the light is passed through is calculated by calculating the particle size distribution most consistent with the pattern using Mie scattering theory or the like.

As a commercially available device, a particle size measuring device (LS230, LS200, L
S100, manufactured by Coulter Co., Ltd.), laser diffraction particle size distribution analyzer (SALD2000, SALD2000A, S
ALD3000, manufactured by Shimadzu Corporation) Laser diffraction / scattering type particle size distribution analyzer (LA910, LA700, LA5)
00, manufactured by Horiba and Microtrack SP
A, Microtrack FRA, manufactured by Nikkiso Co., Ltd.).

(Method of Measuring Aspect Ratio) The aspect ratio (Z) is a ratio obtained from the relationship of Z = L / a. Here, L is the particle diameter (volume-based median diameter) of the inorganic layered compound in the dispersion obtained by the particle diameter measurement method by the above-mentioned diffraction / scattering method, and a is the cleaved inorganic particle shown in FIG. This is the unit thickness of the unit crystal layer 31 of the layered compound. The “unit thickness a” is a value determined based on the result of independently measuring the thickness of the inorganic layered compound by a powder X-ray analysis method described later or the like.

More specifically, as schematically shown in the graph of FIG. 4 in which 2θ is on the horizontal axis and the intensity of the X-ray diffraction peak is on the vertical axis, the lowest angle side of the observed diffraction peaks is shown. From the angle θ corresponding to the peak, the Bragg equation (nλ = 2Dsi
The interval determined based on nθ, n = 1, 2, 3,... is defined as “unit thickness a” (for details of the powder X-ray analysis method, for example, see “ Guide (a) ", 1985, published by Kagaku Dojin, p. 69).

When the resin composition corresponding to the resin composition layer 3 obtained by removing the dispersion medium from the dispersion liquid is subjected to powder X-ray analysis, usually, each of the inorganic layered compounds dispersed in the resin composition is removed. The surface distance can be obtained as the surface distance d shown in FIG.

More specifically, as shown in the graph of FIG. 5 in which the horizontal axis indicates 2θ and the vertical axis indicates the intensity of the X-ray diffraction peak, the diffraction corresponding to the above “unit thickness a” is shown. Of the diffraction peaks observed at a lower angle (larger interval) than the peak position, the interval corresponding to the peak at the lowest angle is defined as “plane interval d” (a <d).

As schematically shown in the graph of FIG. 6, when it is difficult to detect the peak corresponding to the above-mentioned "surface interval d" because it overlaps with the halo (or background), the lower angle side than 2θd is detected. The area of the portion excluding the baseline is set as the peak corresponding to the “surface distance d”.
Here, “θd” is a diffraction angle corresponding to “(unit thickness a) + (width of single resin chain)”. (For details of the method of calculating the surface distance d, see, for example, Shuichi Iwata et al. Ed., "Encyclopedia of Clay", 1985, Asakura Shoten Co., Ltd., p. 35 or less and p. 271 or less).

Usually, the difference between the above-mentioned surface distance d and "unit thickness a", that is, the value of k = (da) (when converted to "length") constitutes the resin composition. It is equal to or greater than the width of a single resin chain [k = (da) ≧ width of a single resin chain]. Such “the width of a single resin chain” can be obtained by simulation calculation or the like (for example, “Introduction to Polymer Chemistry”, 1981, Kagaku Dojin, 1
(See pages 03-110), and in the case of polyvinyl alcohol, it is 4-5 angstroms (in the case of water molecules, 2-3).
Angstrom).

It is extremely difficult to directly measure the "true aspect ratio" of the inorganic layered compound in the resin composition layer 3. Although the above aspect ratio Z = L / a is not always equal to the “true aspect ratio” of the inorganic layered compound in the resin composition layer 3, the aspect ratio Z is “true” for the following reason. It is appropriate to approximate the “aspect ratio”.

There is a relation of a <d between the spacing d obtained by the powder X-ray analysis of the resin composition and the “unit thickness a” obtained by the powder X-ray analysis of the inorganic layered compound alone. And the value of (da) is the value of resin 1 in the composition.
If the width of the main chain or more, in the resin composition,
The resin is inserted between the layers of each inorganic layered compound. Therefore, the thickness of the unit crystal layer 31 of the inorganic layered compound in the resin composition layer 3 is approximated by the above “unit thickness a”, that is, the “true aspect ratio” of the inorganic layered compound in the resin composition layer 3. Is adequately approximated by the “aspect ratio Z” in the dispersion liquid of the above-mentioned inorganic layered compound.

As described above, it is extremely difficult to measure the true particle size of the inorganic stratiform compound in the resin composition layer 3, but the particle size of the inorganic stratiform compound in the resin 32 of the resin composition layer 3 is very small. In the dispersion (resin / inorganic layered compound / dispersion medium)
Can be considered to correspond to the particle size L of the inorganic layered compound.

However, the particle diameter L 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, so that the true aspect ratio (Lmax / a) is low. The possibility that the ratio is lower than the “aspect ratio Z” used in the present invention (Lmax / a <Z) is theoretically considerably low.

From the above two points, it is considered that the definition Z of the aspect ratio used in the present invention has sufficient validity. In the present specification, “aspect ratio” or “particle size” means “aspect ratio Z” defined above or “particle size L determined by a diffraction / scattering method”.

From the viewpoint of easily giving a large aspect ratio, an inorganic layered compound having a property of swelling or cleaving in a dispersion medium is preferably used, and an inorganic layered compound having a property of swelling and cleaving in a dispersion medium is more preferably used. .

The degree of "swelling / cleaving" of the inorganic layered compound used in the present invention into a dispersion medium can be evaluated by the following "swelling / cleaving" test. The swellability of the inorganic layered compound is preferably about 5 or more (more preferably, about 20 or more) in a swelling test described below. On the other hand, the cleavage property of the inorganic layered compound is preferably about 5 or more (and more preferably about 20 or more) in the cleavage test. In these cases, a liquid having a density smaller than the density of the inorganic layered compound is used as the dispersion medium. When the inorganic layered compound is a natural swellable clay mineral, it is preferable to use water as the dispersion medium.

<Swelling test> 100 mL of the dispersion medium was placed in a 100 mL measuring cylinder, and 2 g of the inorganic layered compound was added thereto.
Add slowly. After standing, the volume (mL) of the inorganic layered compound dispersed layer is read as the swelling value from the scale at the interface between the inorganic layered compound dispersed layer and the supernatant after 24 hours at 23 ° C. The larger the value, the higher the swelling property.

<Cleaving test> 30 g of an inorganic layered compound was slowly added to 1500 mL of a dispersion medium, and a dispersing machine [Despa MH-L, manufactured by Asada Tekko Co., Ltd., blade diameter 52 mm, rotation number 3]
100 rpm, container capacity 3 L, distance 28 between bottom and blade
mm] at a peripheral speed of 8.5 m / sec for 90 minutes (23 ° C.), take 100 mL of the dispersion liquid, put it in a graduated cylinder and let stand for 60 minutes, and then, from the interface with the supernatant, the volume of the inorganic layered compound dispersed layer Read (mL) as cleavage value.

As the inorganic layered compound which swells and cleaves in the dispersion medium, a clay mineral which swells and cleaves in the dispersion medium is particularly preferably used. Such clay minerals are generally
A type having a two-layer structure having an octahedral layer having aluminum or magnesium as a central metal on the upper surface of a tetrahedral layer of silica, and an octahedral layer having a tetrahedral layer of silica having aluminum or magnesium as a central metal. Is classified into a type having a three-layer structure in which is narrowed from both sides. The former two-layer structure type includes kaolinite group and antigolite group, and the latter three-layer structure type includes smectite group, vermiculite group and mica group depending on the number of interlayer cations. Can be.

As these clay minerals, more specifically, kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectite Light, tetrasilyl mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite, zansophyllite, chlorite and the like can be mentioned.

A clay mineral treated with an organic substance (hereinafter sometimes referred to as an organically modified clay mineral) can also be used as an inorganic layered compound (the clay mineral treated with an organic substance is described in Asakura Shoten, See Clay Encyclopedia).

Among the above clay minerals, smectites, vermiculites and micas are preferred from the viewpoint of swelling or cleavage, more preferably smectites. Examples of the smectite group include montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, and hectorite.

As a dispersion medium for swelling or cleaving the inorganic layered compound, for example, in the case of a natural swelling clay mineral, water, alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol and diethylene glycol, dimethylformamide, dimethyl sulfoxide, Acetone and the like are mentioned, and alcohols such as water and methanol are more preferable.

In the case of organically modified clay minerals, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, n-pentane, Aliphatic hydrocarbons such as n-hexane and n-octane; halogenated hydrocarbons such as chlorobenzene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane and perchloroethylene; ethyl acetate; methyl methacrylate (MMA ), Dioctyl phthalate (DOP), N, N-dimethylformamide,
Examples include dimethyl sulfoxide, methyl cellosolve, and silicone oil.

The resin composition layer 3 contains a resin for maintaining flexibility. The weight ratio of the inorganic layered compound to the resin (inorganic layered compound / resin) is from 1/100 to 100/1.
Is preferable, and it is more preferable that it is within the range of 1/20 to 10/1.

The resin contained in the resin composition layer 3 is preferably a high hydrogen bonding resin from the viewpoint of gas barrier properties, but may be a resin other than the high hydrogen bonding resin. The high hydrogen bonding resin is a resin having a hydrogen bonding group or an ionic group. The content of the hydrogen-bonding group and the ionic group in the high hydrogen-bonding resin (the content of one of the two when containing one, and the total content of both when both are contained) is usually 20 to 60 mol%. And preferably 30 to 50 mol%. The content of these hydrogen bonding groups and ionic groups can be determined, for example, by the method of nuclear magnetic resonance (NMR) ( ¹ H
-NMR, ¹³ C-NMR, etc.).

The above-mentioned hydrogen bonding group includes a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group,
Examples of the ionic group include a carboxylate group, a sulfonate ion group, a phosphate ion group, an ammonium group, and a phosphonium group. Among the hydrogen bonding groups or ionic groups, more preferred are a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a carboxylate group, a sulfonic acid ionic group, an ammonium group and the like.

Examples of the high hydrogen bonding resin include polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer having a vinyl alcohol fraction of 40 mol% or more, polysaccharides, polyacrylic acid and its esters, and polyacrylic resin. Sodium acid, polybenzenesulfonic acid, sodium polybenzenesulfonate, polyethyleneimine, polyallylamine and quaternary ammonium salts thereof,
Polyvinyl thiol, polyglycerin and the like. Among the above-mentioned resins, those more preferable as the high hydrogen bonding resin are polyvinyl alcohol, polysaccharide,
And ethylene-vinyl alcohol copolymer.

Here, the polyvinyl alcohol is, for example, a polymer obtained by hydrolyzing or transesterifying (saponifying) an acetic ester portion of a vinyl acetate polymer (ie, a copolymer of vinyl alcohol and vinyl acetate). And a polymer obtained by saponifying a vinyl trifluoroacetate polymer, a vinyl formate polymer, a vinyl pivalate polymer, a t-butyl vinyl ether polymer, a trimethylsilyl vinyl ether polymer, etc. (for details of polyvinyl alcohol). See, for example, edited by the Poval Society, “The World of PVA”, 1992, Kobunshi Publishing Co .; Nagano et al., “Povar”, 1981, Kobunshi Publishing Co., Ltd.).

"Saponification" in polyvinyl alcohol
Is preferably 70% or more in terms of molar percentage, more preferably 85% or more, and particularly preferably 98% or more, a so-called fully saponified product. The degree of polymerization of polyvinyl alcohol is preferably from 100 to 5,000, more preferably from 200 to 3,000. Further, the polyvinyl alcohol referred to in the present invention 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, and herein includes those chemically modified based on them. Examples include cellulose and cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose and carboxymethylcellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan and the like.

The ethylene-vinyl alcohol copolymer (hereinafter referred to as EVOH) has a vinyl alcohol content of from 40 mol% to 80 mol%, more preferably from 45 mol% to 75 mol%. It means a certain EVOH. In addition, the melt index of EVOH (temperature 190
The value measured under the conditions of ° C and a load of 2160 g; hereinafter, referred to as MI) is not particularly limited, but is 0.1 to 50 g / 10 minutes. Further, the EVOH referred to in the present invention may be modified with a small amount of a comonomer as long as the object of the present invention is not hindered.

The above-mentioned modified polyvinyl alcohol and ethylene-vinyl alcohol copolymer can be copolymerized with a vinyl ester monomer such as vinyl acetate and an ester monomer in the process of producing polyvinyl alcohol. After copolymerization with another unsaturated monomer, it is obtained by hydrolyzing or transesterifying (saponifying) the ester portion of the obtained copolymer. Other unsaturated monomers copolymerizable with the ester monomer include, for example,
Olefins such as ethylene, propylene, α-hexene and α-octene, unsaturated acids such as (meth) acrylic acid, crotonic acid, (anhydride) maleic acid, fumaric acid, and itaconic acid, and alkyl esters and alkali salts thereof Sulfonic acid-containing monomers such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid and alkali salts thereof, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and trimethyl- 2-(-1-
(Meth) acrylamide-1,1-dimethylethyl) ammonium chloride, trimethyl-3- (1- (meth)
Acrylamidopropyl) ammonium chloride, 1-
Vinyl-2-ethylimidazole and other quaternizable cationic monomers, styrene, alkyl vinyl ether,
(Meth) acrylamide and others.

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

Among these copolymers, a block copolymer obtained by copolymerizing a polycarboxylic acid component with a polyvinyl alcohol component is particularly preferably used, and when the polycarboxylic acid component is polymethacrylic acid, Particularly preferred. Further, the block copolymer is particularly preferably an AB block copolymer in which a polyacrylic acid chain is extended at one end of a polyvinyl alcohol chain, and the polyvinyl alcohol block component (a) Weight ratio of acrylic acid block component (b) (a) /
(B) is preferably 50/50 to 95/5,
In the case of 60/40 to 90/10, particularly preferable gas barrier properties are completed, and the bonding characteristics with the base material layer are remarkably completed. Further, among other modified forms, one particularly preferred form is a silyl group-modified polyvinyl alcohol resin composed of a saponified vinyl ester polymer modified with at least one compound having a silyl group in the molecule. is there.

The method for obtaining the modified polymer having such a composition is not particularly limited, but a silyl group is added to a vinyl alcohol polymer such as polyvinyl alcohol or modified polyvinyl acetate obtained by a conventional method. Reacting a compound having a silyl group into the polymer, or activating the terminal of polyvinyl alcohol or a modified product thereof, and introducing an unsaturated monomer having a silyl group in the molecule to the terminal of the polymer. Various modification methods such as graft copolymerization of the unsaturated monomer to a vinyl alcohol polymer molecular chain, a copolymer comprising a vinyl ester monomer and an unsaturated monomer having a silyl group in the molecule. And saponifying it, or polymerizing a vinyl ester in the presence of a silyl group-containing mercaptan or the like and saponifying it. Introducing silyl groups into Runado end,
Various methods such as are effectively used.

As the modified polyvinyl alcohol-based resin obtained by such various methods, any resin may be used as long as it has a silyl group in the molecule, but the silyl group contained in the molecule may be an alkoxyl group or a silyl group. Those having a reactive substituent such as an acyloxyl group and a hydrolyzate of a silanol group or a salt thereof are preferable, and among them, a silanol group is particularly preferable.

Compounds having a silyl group in the molecule used for obtaining these modified polyvinyl alcohol resins include trimethylchlorosilane, dimethylchlorosilane, methyltrichlorosilane, vinyltrichlorosilane, diphenyldichlorosilane, triethylfluorosilane. Organohalosilanes such as silane, organosilicon esters such as trimethylacetoxysilane and dimethyldiacetoxysilane, organoalkoxysilanes such as trimethylmethoxysilane and dimethyldimethoxysilane,
Examples include organosilanols such as trimethylsilanol and diethylsilanediol, aminoalkylsilanes such as N-amiethyltrimethoxysilane, and organosilicon isocyanates such as trimethylsiliconisocyanate. 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-based compounds such as vinylalkoxysilane and vinylmethyldimethoxysilane represented by vinyltriethoxysilane, and alkyl- or allyl-substituted vinylalkoxysilane represented by vinyltriisopropoxysilane; 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, 3- (meth) acrylamino-propyltrimethoxysilane, 3
(Meth) acrylamide-alkylsilane represented by-(meth) acrylamide-propyltriethoxysilane and the like can also be preferably used.

On the other hand, a method for polymerizing a vinyl ester in the presence of a mercaptan having a silyl group or the like and then saponifying the silyl group to introduce a silyl group into the terminal includes an alkoxysilylalkyl such as 3- (trimethoxysilyl) -propylmercaptan. Mercaptan is preferably used.

The suitable range varies depending on the degree of modification of the modified polyvinyl alcohol-based resin of the present invention, that is, the content of the silyl group, the degree of saponification, etc., but it is important for the gas barrier property which is the object of the present invention. It becomes a factor. The content of the silyl group is usually 30 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, as a monomer containing a silyl group, based on the vinyl alcohol unit in the polymer. 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 indicates the ratio of the introduced silyl group after the silylation to the amount of the hydroxyl group contained in the polyvinyl alcohol resin before the silylation.

The modified polyvinyl alcohol-based resin into which the silyl group has been introduced is alcohol or alcohol /
By heating and dissolving with a mixed solvent of water, the compound is dissolved in an alcohol solvent due to the presence of the introduced silyl group.
The modified polyvinyl alcohol-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 / water.

These polyvinyl alcohol 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 with other monomers. It can be used in combination with other possible 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 method for forming the resin composition layer 3 is as follows.
The method is not particularly limited, and includes a method of coating a coating liquid in which the inorganic layered compound and the resin are dispersed or dissolved in a dispersion medium, a method of extruding the inorganic layered compound and the resin, and the like. When a high hydrogen bonding resin is used, a method of coating a coating liquid is preferred. As the dispersion medium, a liquid that swells or cleaves the above-described inorganic layered compound is preferable from the viewpoint of gas barrier properties of the obtained film laminate.

The composition ratio of the inorganic layer compound and the resin in the coating liquid is not particularly limited, but generally, the weight ratio of the inorganic layer compound and the resin (inorganic layer compound / resin)
Is preferably in the range of 1/100 to 100/1, and more preferably in the range of 1/20 to 10/1.
The higher the weight ratio of the inorganic layered compound is, the more excellent the gas barrier property is, but in consideration of the bending resistance, the range of 1/20 to 2/1 is more preferable. In addition, the concentration of the inorganic layered compound and the resin in the coating solution is usually 0.1 to 70% by weight in total, but from the viewpoint of productivity, it is more preferably 1 to 15% by weight. It is more preferably 4 to 10% by weight.

The resin used in the resin composition layer 3 of the present invention is
In the case of a high hydrogen bonding resin, a crosslinking agent for a hydrogen bonding group can be used for the purpose of improving the water resistance of the resin composition layer 3.

Preferable examples of the crosslinking agent include coupling agents such as a titanium-based coupling agent, a silane-based coupling agent, a melamine-based coupling agent, an epoxy-based coupling agent, and an isocyanate-based coupling agent; Epoxy compounds, copper compounds, zirconium compounds, organometallic compounds and the like can be mentioned. From the viewpoint of improving water resistance, organometallic compounds, zirconium compounds, water-soluble epoxy compounds, silane coupling agents are more preferably used,
More preferably, it is an organic metal compound such as an organic titanium compound.

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

Specific examples of the water-soluble epoxy compound include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, glycidyl ether epoxy resin, heterocyclic epoxy resin, glycidylamine epoxy resin, and aliphatic epoxy resin. I can give it.

Examples of the silane coupling agent include amino silane coupling agents, vinyl or methacryloxy silane coupling agents, epoxy silane coupling agents, methyl silane coupling agents,
Chloro silane coupling agents and mercapto silane coupling agent systems are exemplified.

Preferred examples of the cross-linking agent for a hydrogen-bonding group include a reaction for forming a cross-linked structure by reacting with a plurality of functional groups of a high hydrogen-bonding resin, that is, an organometallic compound capable of a cross-linking reaction. For example, the above-mentioned organometallic compounds which react with a plurality of hydroxyl groups of polyvinyl alcohol and form a cross-linking by a coordination bond or an ionic bond between a metal atom of the organometallic compound and an oxygen atom of the hydroxyl group are preferable.

The above-mentioned organometallic compounds capable of undergoing a crosslinking reaction are:
Higher crosslinking reactivity and higher crosslinking efficiency than inorganic metal salts. However, if the cross-linking reactivity is too high, the cross-linking reaction proceeds in the coating solution and coating (coating) becomes impossible, but the cross-linking reactivity of the organometallic compound can be changed by appropriately changing the ligand. Easy to control. The organic metal compound is also superior to the inorganic metal salt in that it has the advantage that the reactivity is easily controlled. Among the organometallic compounds, an organometallic compound having a chelating ligand such as acetylacetonate has an appropriate crosslinking reactivity and is preferable as a crosslinking agent for a hydrogen bonding group.

Preferred examples of such organometallic compounds include organic titanium compounds, organic zirconium compounds, organic aluminum compounds, and organic silicon compounds.

Specific examples of the organic titanium compound include titanium orthoesters such as tetra-n-butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate and tetramethyl titanate; titanium acetylacetonate;
Titanium chelates such as titanium tetraacetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate, titanium triethanolamine, titanium ethyl acetoacetate, and titanium acylates such as polyhydroxytitanium stearate. No.

Specific examples of the organic zirconium compound include zirconium normal propylate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, zirconium acetylacetonate bisethylacetoacetate and the like. No.

Specific examples of the organic aluminum compound include aluminum acetylacetonate, aluminum organic acid chelate and the like. Examples of the organic silicon compound include a silicon compound having a ligand included in the compounds exemplified as the organic titanium compound or the organic zirconium compound.

Of these, chelate compounds are preferred in view of stability in the coating solution. In terms of the stability of the coating solution, the stability is greatly improved by setting the coating solution to be acidic. The above acidic conditions include a pH of 5
Or less, more preferably pH 3 or less. There is no particular lower limit on the pH of the coating solution, but usually the pH is 0.1.
5 or more. As the addition method, it is preferable to dilute with an alcohol and add. 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.

The amount of the crosslinking agent to be added is not particularly limited, but the ratio K (K = CN / HN) of the number of moles of the crosslinking group (CN) of the crosslinking agent to the number of moles of the hydrogen bonding group (HN) of the resin is used. But,
It is preferable to use it in the range of 0.001 or more and 10 or less. More preferably, the molar ratio K is in the range of 0.01 or more and 1 or less.

The method of blending or producing the resin composition comprising the above-mentioned inorganic layered compound and resin is not particularly limited.
From the viewpoint of uniformity or ease of operation during compounding, for example,
A method in which a liquid in which a resin is dissolved in a solvent and a dispersion in which the inorganic layered compound has been swollen and cleaved in advance with a dispersion medium are mixed, and then the solvent and the dispersion medium are removed (method 1). The inorganic layered compound is swollen with the dispersion medium A method of mixing the cleaved dispersion liquid with a resin, dissolving the resin in a dispersion medium, and then removing the dispersion medium (method 2), adding an inorganic layered compound to a liquid in which the resin is dissolved in a solvent. A method of swelling and cleaving the inorganic layered compound using the solvent as a dispersion medium to form a dispersion and removing the solvent (method 3), or a method of hot-kneading the resin and the inorganic layered compound (method 4) can be used. It is. From the point that a large aspect ratio of the inorganic layered compound can be easily obtained,
The former three methods are preferably used. In the former three, it is preferable from the viewpoint of the dispersibility of the inorganic layered compound that the mixed solution of the resin composition containing the inorganic layered compound is subjected to high-pressure dispersion using a high-pressure dispersion apparatus.

In the present invention, the high-pressure dispersion treatment is performed, as shown in FIG. 7, by passing a composition mixture obtained by mixing particles to be dispersed or a dispersion medium and the like through a plurality of narrow tubes 11 to collide with each other. Dispersing under special conditions such as high shear and high pressure.

In such a high-speed dispersion treatment, the composition mixture is preferably passed through a capillary 11 having a diameter of 1 μm to 1000 μm. When the composition mixture passes through the capillary 11, a maximum pressure condition is applied to the composition mixture. Preferably, a pressure of 100 kgf / cm ² or more is applied, and 500 kgf / cm ²
The above is more preferable, and 1000 kgf / cm ² or more is particularly preferable. Further, when the composition mixture passes through the narrow tube 11, the maximum arrival speed of the composition mixture is 100 m /
s or more, and the heat transfer rate is 100 kc
It is preferably at least al / hr.

The principle of high-pressure processing in the high-pressure dispersion processing apparatus used for the high-speed dispersion processing will be described schematically.
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 a high-pressure and high-speed state in the thin tube 11,
Each of the inorganic layered compound particles of the composition mixture collides 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 finely divided and more uniformly dispersed. Then, it is 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 processing sample 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.

Examples of the high-pressure dispersion apparatus used in the high-speed dispersion processing include an ultra-high-pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation and a nanomizer manufactured by Nanomizer. A dispersing device, for example, a homogenizer manufactured by Izumi Food Machinery, and the like can be given.

In the above three methods, after removing the solvent and the dispersion medium from the system and laminating, the resulting film laminate is subjected to heat aging at, for example, 110 ° C. or more and 220 ° C. or less, particularly when the film is used. The water resistance (meaning of gas barrier properties after a water resistance environment test) of the laminate can be improved, which is preferable.

Although the aging time is not limited, it is necessary that the film laminate reaches at least the set temperature. For example, in the case of a method using a heat medium contact such as a hot air dryer, 1
The time is preferably not less than seconds and not more than 100 minutes. There is no particular limitation on the heat source, and various methods such as heat 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 heat-sealable film 5 is not particularly limited as long as it has heat-sealability. However, polyethylene (low density, high density) may be used in consideration of heat seal strength, deodorization of food scent, and resin odor. Density), ethylene, propylene copolymer, ethylene-butene copolymer, 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 resins such as ionomer resins and ethylene-vinyl alcohol copolymers; polyacrylonitrile resins (PAN); and polyester resins are preferably used.

In the case of the heat-sealing film 5, a sealant having a high impact strength is preferable especially when the sealing property of the contents is required. Preferred examples of such a resin include polyolefin resins such as polyethylene, ethylene-α-olefin copolymer, and polypropylene, which are synthesized using a metallocene catalyst or a late transition metal complex catalyst.

The method for laminating the heat-sealable film 5 as the sealant layer is not particularly limited.
For example, a method of dissolving a resin used for the heat-sealing film 5 in a solvent and coating the resin composition layer 3 on the resin composition, a method of extruding and laminating the heat-sealing film 5 on the resin composition layer 3, a method of heat-sealing film A preferred example is a method of dry laminating 5 on the resin composition layer 3. The interface between the heat-sealing film 5 and the resin composition layer 3 is corona-treated,
A treatment such as an ozone treatment, an electron beam treatment, or an anchor coating agent may be performed.

In laminating the resin composition layer 3 of the present invention on the base material layer 1, the base material layer 1 is subjected to a surface treatment, for example, corona treatment, flame plasma treatment, ozone treatment, electron beam irradiation treatment, anchor treatment. May be performed.

When the anchor treatment is performed, that is, when the anchor layer is formed on the base material layer 1, the material of the anchor layer is not particularly limited, for example, polyethyleneimine, alkyl titanate, polybutadiene, urethane, etc. From the viewpoint of properties, an anchor layer composed of a urethane-based compound prepared from an isocyanate compound and an active hydrogen compound is preferable.

The isocyanate compound includes tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), and hexamethylene diisocyanate (HD
I), 4,4'-methylenebiscyclohexyl isocyanate (H12MDI), isophorone diisocyanate (IP
DI).

The active hydrogen compound may be any compound having a functional group capable of binding to an isocyanate compound.
For example, ethylene glycol, diethylene glycol,
Low molecular weight polyols such as dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, polyethylene glycol, polyoxypropylene glycol, ethylene oxide / propylene oxide copolymer, polytetramethylene Examples include polyether polyols such as ether glycol, polyester polyols such as poly-β-methyl-δ-valerolactone, polycaprolactone, polyesters obtained from diols and dibasic acids, and the like.

In the active hydrogen compound, a low molecular weight polyol is particularly preferable, and a diol in the low molecular weight polyol is more preferable. Here, the diol is
Ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and the like. Examples of the dibasic acid include 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, but the amount to be added is determined in consideration of the equivalence relationship between the isocyanate group and the active hydrogen group, for example, —OH, —NH, and —COOH. preferable. For example, the ratio R (R = AN / mol) of the number of moles of isocyanate groups (AN) to the number of moles of active hydrogen groups (BN) of the active hydrogen compound
BN) is preferably used in a range of 0.001 or more and 10 or less. The molar ratio R is equal to 0.1.
It is more preferable that the value be in the range of 01 or more and 1 or less.
When the mole ratio R is less than 0.001, the adhesive strength is inferior.
If it exceeds 0, the tackiness is too high and blocking becomes a problem. Each mole number of the isocyanate group and the active hydrogen group can be quantified by ¹ H-NMR and ¹³ C-NMR.

The method of laminating the anchor layer on the resin composition layer 3 or another layer, for example, the base layer 1 is not particularly limited, but an anchor coating agent containing an isocyanate compound and an active hydrogen compound is dissolved in a solvent. However, a coating method using an anchor coating agent solution is preferred. Specific examples of the coating method include a direct gravure method, a reverse gravure method, a microgravure method, a roll coating method such as a two-roll beat coating method and a bottom feed three-reverse coating method, and a doctor knife method and a die coating method. Examples include a dip coating method, a bar coating method, and a coating method combining these methods.

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

The coating thickness obtained by applying the anchor coating agent solution in a film form is not particularly limited, but the dry thickness is 0.01 μm
It is preferable that the distance is set to be about 5 μm. The larger the coating thickness, the better the heat sealing strength, but the poorer the gelbo flex resistance (prevention of pinhole formation due to twisting of the film laminate). Therefore, the coating thickness is more preferably from 0.03 μm to 2.0 μm,
More preferably, it is 0.05 μm to 1.0 μm.

The thickness of the resin composition layer 3 is 10
μm or less, more preferably 1 μm or less. If the thickness exceeds the above range, the flexibility of the obtained film laminate deteriorates. The lower limit of the thickness is not particularly limited, but is preferably 1 nm or more in order to obtain an effective gas barrier effect.

When an anchor layer, particularly a urethane anchor layer, is used in the above film laminate, the resin composition layer 3 preferably contains a surfactant for improving the adhesion to the anchor layer. .

The surfactant used in the present invention includes:
There is no particular limitation as long as the adhesiveness between the anchor layer and the resin composition layer 3 can be improved. Examples thereof include an anionic surfactant, a cationic surfactant, a zwitterionic surfactant and a nonionic surfactant. Surfactants.

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. Sulfonate type such as sulfonic acid type, alkyl sulfate salt, alkyl sulfate polyoxyethylene salt, etc., phosphate type such as alkyl phosphate salt, borate type such as alkyl borate salt, etc. Surfactants, fluorine-based anionic surfactants such as sodium perfluorodecanoate and sodium perfluorooctylsulfonate, and silicone-based anions having an anionic group such as a polymer having a polydimethylsiloxane group and a metal carboxylate. Surfactants.

Examples of the cationic surfactant include, for example,
Amine salt types such as alkylamine salts, alkyltrimethylammonium salts, dialkyldimethylammonium salts,
A quaternary ammonium salt type such as an alkyldimethylbenzylammonium salt is exemplified.

Examples of zwitterionic surfactants 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, polycondensates 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, aliphatic alkanolamide And fluorine types such as perfluorodecanoic acid-diglycerin ester and perfluoroalkylalkylene oxide compounds.

Among the above surfactants, in particular, those having 6 carbon atoms
An alkali metal salt of a carboxylic acid having an alkyl chain of not more than 24 or less, an ether type nonionic surfactant such as polydimethylsiloxane-polyoxyethylene copolymer (silicone nonionic surfactant), Fluorinated nonionic surfactants such as alkyl ethylene oxide compounds (fluorinated nonionic surfactants)
Is preferred.

When the resin composition layer 3 is formed, for example, when a coating liquid is used when forming the resin composition layer 3, the amount of the surfactant is preferably 0.001 to 5% by weight in the coating liquid from the viewpoint of the effect. ,
0.003 to 0.5% by weight is more preferable, and 0.005 to 0.5% by weight.
-0.1% by weight is particularly preferred.

In the present invention, layers other than those described above can be provided as long as the effect is not impaired. For example, FIG.
As shown in (1), a stretched film 4 may be further provided between the heat sealable film 5 and the resin composition layer 3.
In the above configuration, the tearing property can be imparted to the gas replacement packaging container by the internal stress remaining in the stretched film 4.

The stretched film 4 is not particularly limited, but is preferably a biaxially stretched film, preferably a biaxially stretched polyamide, a biaxially stretched polyethylene terephthalate,
At least one selected from the group consisting of biaxially oriented polypropylene is particularly preferred.

As the stretched film 4, a film having higher tensile strength is more preferable, and the elongation at break is preferably 700% or less, more preferably 500% or less. Examples of the polyamide-based biaxially stretched film include nylon-6, nylon-6,6, metaxylenediamine-adipic acid condensation polymer, and the like.

A barrier layer made of a metal such as aluminum or a metal oxide such as silica or alumina may be provided on any one of the layers of the film laminate constituting the gas replacement packaging container, for example, with the base material layer 1. It may be provided between the resin composition layer 3. Thereby, the content filled in the gas replacement packaging container can be shielded from light, and deterioration of the content can be suppressed.

The barrier layer is formed, for example, by coating a metal or metal oxide on the surface of the base material layer 1 on the side of the resin composition layer 3 with a thickness of usually 1 nm to 1000 nm, more preferably 10 nm to 200 nm. It is formed with a film thickness. Examples of a method for forming such a barrier layer include a vapor deposition method and a sol-gel method. In particular, when a barrier layer is provided on the substrate layer 1 where the vapor deposition method is preferable, the substrate layer 1
Preferably comprises at least one selected from the group consisting of biaxially oriented polypropylene, biaxially oriented polyethylene terephthalate, and biaxially oriented nylon.

Note that a packaging container using an aluminum layer as a gas barrier layer has been conventionally known. However, in the above-mentioned conventional packaging container, it is necessary to increase the thickness of the aluminum layer in order to obtain a sufficient gas barrier property, and an aluminum foil having a thickness of 7 to 20 μm is usually used. For this reason, there is a large problem that residues (ingots) increase during incineration at the time of disposal.

On the other hand, since the above-mentioned barrier layer is thin, for example, the amount of metal or metal oxide used per carton container can be reduced, and the problem of residues during incineration can be solved. . In addition, the gas replacement packaging container of the present invention is provided with the resin composition layer 3 having an inorganic layered compound, and thus has a sufficient gas barrier property even when the metal or metal oxide layer is made as thin as a barrier layer. can get.

Each layer of the film laminate constituting the gas replacement packaging container of the present invention may contain additives such as an ultraviolet absorber, a coloring agent and an antioxidant.

The film thickness of the film laminate constituting the gas replacement packaging container of the present invention is not particularly limited.
From the viewpoint of the protection of the contents to be packaged and the cost,
30 μm to 300 μm is preferred.

The shape of the gas replacement packaging container of the present invention is not particularly limited, but the gas replacement packaging container may be a vertical pillow packaging bag, a vertical pillow packaging bag, a gusset packaging bag, a three-sided seal packaging bag, Sealed packaging bag, selected from the group consisting of a pair of vacuum / pressure molded container and lid, a pair of injection or press molded container and lid, squeeze bottle, standing pouch, bag-in-box, paper carton container, and bottle Preferably, the shape is at least one type.

The method for producing the gas replacement packaging container is not particularly limited, and various commercially available packaging container production machines are used.

The gas replacement packaging container of the present invention includes prepared foods; confectionery and snacks such as western confectionery; miso; pickles; konjac; processed fishery products such as chikuwa and kamaboko; Processed meat products;
Pesticides; Fertilizers; Cosmetics; Aromas; 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. Available for use.

The gas-displacement packaging container of the present invention is particularly suitable for food packaging and pharmaceutical packaging, and particularly for processing prepared foods, processed meat (animal meat), processed marine products, confectionery and snacks, etc. It is suitable for use in packaging food.

As described above, the gas replacement packaging container of the present invention is provided with the resin composition layer 3 having excellent gas barrier properties, and has a low oxygen permeability. Oxygen permeability of the container for gas substitution ^{packaging, 1mL / atm · m 2 ·} day
And preferably 0.1 mL / atm.m ^2.
day or less, more preferably 0.05 mL / at
More preferably, it is not more than m · m ² · day.

In the gas replacement packaging method of the present invention, the air inside the gas replacement packaging container is replaced with a gas having a composition different from that of air, for example, an inert gas or a mixed gas of oxygen and carbon dioxide. After that, the article to be packaged is packaged by the gas replacement packaging container. Examples of the inert gas include nitrogen, carbon dioxide, a mixed gas of nitrogen and carbon dioxide, and a rare gas such as argon.

According to the above method, the inside of the gas replacement packaging container can be kept free of an active gas such as oxygen or water vapor by replacing the inside of the gas replacement packaging container with the inert gas. In addition, deterioration of the packaged contents (contents) can be significantly suppressed.

Further, according to the above-mentioned method, by replacing the inside of the gas replacement packaging container with a mixed gas of oxygen and carbon dioxide, deterioration of the packaged object, for example, the growth of microorganisms in raw meat can be remarkably suppressed. Further, the coloring of the meat pigment in the raw meat can be maintained.

The composition of a gas having a composition different from that of air (hereinafter, referred to as a replacement gas) used to replace the air inside the gas replacement packaging container may be appropriately selected depending on the application. For example, microbial control and maintenance of meat pigments for raw meat and fish fillets for commercial use, preservation and microbial control of cooked foods such as terrines and meuniere, prevention of bacterial and mold growth of processed fishery products such as crab-footed kamaboko, meat processing For the purposes of preventing the oxidation of fats and meat pigments in food products and controlling microorganisms, preventing the growth of fatty acids and mold in dairy products such as sliced cheese, preventing the growth of mold in confectionery such as castella, and preventing fatty acids in peanuts and almonds, nitrogen A mixed gas of carbon dioxide and carbon dioxide is suitable as the replacement gas. In addition, it prevents the oxidation of meat pigments in processed fishery products such as shaved nodes, prevents the oxidation of dairy products such as dry milk, prevents the aroma of coffee and black tea, prevents the loss of vitamins and aroma in Japanese tea and powdered juice, and prevents oil confectionery. Nitrogen is suitable as a replacement gas for applications such as the prevention of fatty acid oxidation. A mixed gas of oxygen and carbon dioxide is suitable as a replacement gas for the coloring of meat pigments and suppression of microorganisms in raw consumer meat.

As a gas replacement method for replacing the air inside the gas replacement packaging container with a replacement gas, a nozzle type gas replacement method, a chamber type gas replacement method (vacuum gas replacement method), a gas flash replacement method, or the like is used. Can be.

The nozzle type gas filling method is a method in which air in a gas replacement packaging container containing an article to be packaged is degassed by a nozzle, and then the replacement gas is sealed. It has the advantage that it can be completed.

In the chamber type gas replacement method, a gas replacement packaging container containing an object to be packaged is placed in a chamber, the chamber is sealed, and the air inside the gas replacement packaging container is degassed by a vacuum pump and replaced. This is a method in which a gas is sealed in a gas replacement packaging container, and then the mouth of the gas replacement packaging container is sealed with a heater or an impulse sealer, which has an advantage that a high gas replacement rate can be obtained.

In the gas flush replacement method, a film laminate constituting a gas replacement packaging container is wound into a roll,
The packaged object is inserted while the rolled film laminate is formed into a cylindrical shape, and at the same time, the replacement gas is injected (flashed) into the cylindrical film laminate, and the inside of the cylindrical film laminate is replaced with a replacement gas atmosphere. This is a method of sealing the cylindrical film laminate while keeping it. The gas flush replacement method has the advantage that gas replacement packaging can be performed at high speed.

Further, the gas replacement packaging container of the present invention is used, if necessary, for the purpose of a) an oxygen scavenger, a desiccant, a freshness maintaining agent, and a) a light ray, an ultraviolet ray, a visible light ray or the like. Light-shielding agents (materials), c) easy peels and easy breaks (especially in the case of a pair of a container and a lid material) used for the purpose of easy opening, d) easy tearing imparting materials, and the like may be used. For such gas replacement packaging,
"Food Packaging Handbook" (Japan Packaging Technology Association) can be referred to.

[0138]

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] A thickness of 0.5 μm or more is measured using 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.).
Was measured by On the other hand, a thickness of less than 0.5 μm is actually measured by a gravimetric method (the measured weight of a film having a certain area is divided by the area, and further divided by the specific gravity of the composition) or the IR absorption (infrared absorption) method. Of the coating film thickness and IR absorption were prepared and determined from the calibration curve. Further, in the case of measuring the coating thickness of the resin composition of the present invention, for example, the elemental analysis method [the specific inorganic element analysis value of the laminate (derived from the resin composition layer 3) and the specific element fraction of the inorganic layered compound alone] A method of determining the ratio between the resin composition layer 3 of the present invention and the base material layer 1 from the ratio).

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

[Aspect Ratio Calculation] Using an X-ray diffractometer (trade name “XD-5A”, manufactured by Shimadzu Corporation), diffraction measurement of the inorganic layered compound alone and the resin composition by a powder method was performed. Thereby, the unit thickness a of the inorganic layered compound was determined, and further, from the diffraction measurement of the resin composition, it was confirmed that there was a portion where the plane interval of the inorganic layered compound was widened. Using the particle diameter L obtained by the above method, the aspect ratio Z
It was calculated by the equation of Z = L / a.

[Oxygen Permeability Measurement] Based on JIS K7126, an oxygen permeability measurement device (trade name “OX-TRAN”)
ML "(manufactured by MOCON) at 23.7 ° C. (humidity of 60% RH on outer layer A side, 100% RH on inner layer B side).
H).

[Example 1] [Coating liquid for resin composition layer] Dispersion vessel (trade name "DESPA MH")
-L "(manufactured by Asada Tekko Co., Ltd.), 1860 g of ion-exchanged water (specific electric conductivity 0.7 μS / cm or less) was added, and polyvinyl alcohol (trade name“ PVA117 ”) was added.
H ", manufactured by Kuraray Co., Ltd., degree of saponification; 99.6%, degree of polymerization 170
0) was added thereto, the temperature was raised to 95 ° C. under low-speed stirring (1500 rpm, peripheral speed 4.10 m / min), and the mixture was stirred for 1 hour, and polyvinyl alcohol was dissolved in ion-exchanged water to obtain a polyvinyl alcohol aqueous solution.

Next, the temperature was lowered to 60 ° C. while stirring the aqueous polyvinyl alcohol solution, and then a polydimethylsiloxane-polyoxyethylene copolymer (trade name “SH3746”, a silicone-based nonionic surfactant) was used.
0.18 g of Toray Dow Corning KK 125 g of 1-butanol and 375 g of isopropyl alcohol
Was added to the aqueous solution of polyvinyl alcohol to obtain a mixed solution (B).

1960 g of the mixture (B) 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 Co., Ltd.) is added as powder so that the weight ratio of the resin to the inorganic layered compound is 2: 1, and the montmorillonite is substantially precipitated in the liquid. I confirmed that. Then, 600mmHg,
The mixture was rapidly stirred at 5000 rpm for 10 minutes to obtain a resin composition mixture (C). At this time, the particle diameter of the swelled / cleaved montmorillonite was 1.483 μm.

2,000 g of the resin composition mixture (C) was dispersed in a high-pressure dispersion apparatus (trade name “Ultra-high pressure homogenizer M11”).
0-E / H "(manufactured by Microfluidics Corporation) and subjected to high-pressure dispersion once at 1750 kgf / cm ² to obtain a uniform dispersion (D) having good dispersibility. The solid content concentration of the dispersion liquid (D) was 7.5% by weight.

A dispersion (D) comprising polyvinyl alcohol and montmorillonite was cast into a film,
X-ray analysis was performed to measure the interplanar spacing d of the swollen / cleaved montmorillonite (inorganic layered compound). From the diffraction peak obtained from the X-ray analysis, the plane spacing d is calculated as 4
1.2 angstrom, and the montmorillonite was sufficiently cleaved. At this time, the aspect ratio of the cleaved inorganic layered compound was 461.

The dispersion (D) was adjusted with hydrochloric acid under low-speed stirring (1500 rpm, peripheral speed 4.10 m / min) while adjusting the pH of the dispersion (D) to 3 or less. 5.33 g of titanium acetylacetonate (trade name “TC100”, manufactured by Matsumoto Pharmaceutical Co., Ltd.) was gradually added, and this was used as a coating liquid for a resin composition layer.

[Laminated Film] A biaxially oriented polypropylene (OPP) film having a thickness of 20 μm (trade name “PYREN P2102”, manufactured by Toyobo Co., Ltd.) was subjected to surface corona treatment to form a base material layer 1. An anchor coating agent (Adcoat AD335 / CAT10 = 15/1)
(Weight ratio, manufactured by Toyo Morton Co., Ltd.) was gravure coated by a micro gravure coating method at a coating speed of 3 m / min and a drying temperature of 80 ° C. using a test coater (manufactured by Yasui Seiki). The dry thickness of the anchor coat layer is 0.05μ.
m.

Next, using a test coater (manufactured by Yasui Seiki Co., Ltd.), the coating solution for the resin composition layer was gravure coated by a microgravure coating method at a coating speed of 3 m / min and a drying temperature of 100 ° C. A coating film (film laminate) having the resin composition layer 3 based on the resin composition layer coating liquid formed on the anchor coat layer was obtained. The dry thickness of the resin composition layer 3 was 0.5 μm.

Subsequently, an adhesive (Adcoat AD503 / CAT10) was applied to the resin composition layer 3 of the coating film.
= 15/1 (weight ratio, manufactured by Toyo Morton Co., Ltd.) and a 50 μm thick metallocene LL film (trade name “TUX-FCS”, manufactured by Toyo Sero Co., Ltd.) as a sealant layer (heat-sealable film 5) ) Was dry-laminated to obtain a film laminate.

The oxygen permeability of the film laminate was measured according to the above-mentioned measuring method. As a result, the film laminate had an oxygen permeability (mL / atm · m ² · da
y) was 0.1 or less, indicating excellent oxygen permeability.

[0153] By molding [gas exchange packaging container] The above film laminate with heat seal method to produce a three-way seal type like gas replacement packaging bag (container). After the air inside the obtained bag for gas replacement packaging was replaced with nitrogen by a chamber type gas replacement method, the ham as a packaged object was subjected to the above gas replacement together with “Ageless Eye” (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.). It was packaged by a heat sealing method using a packaging bag. After that, the color change of the “Ageless Eye” was observed. When stored at 23 ° C., no color change was observed even after 30 days, and it was confirmed that the inside of the gas replacement packaging bag was kept oxygen-free. Was done.

Comparative Example 1 First, a film laminate was obtained in the same manner as in Example 1 except that a vinylidene chloride resin layer was formed on the anchor coat layer instead of the resin composition layer 3. Next, using the above-described film laminate, a three-side sealed gas replacement packaging bag was produced in the same manner as in Example 1.

After the air inside the obtained gas replacement packaging bag was replaced with nitrogen in the same manner as in Example 1, the ham as the article to be packaged was replaced with the “Ageless Eye” by the gas replacement packaging bag. Packaging was performed in the same manner as in Example 1. After that, the color change of “Ageless Eye” was observed.
After 7 days, a color change was observed, and it was confirmed that oxygen had flowed into the gas replacement packaging bag.

[0156]

As described above, the gas replacement packaging container of the present invention has a structure provided with a resin composition layer composed of a resin composition containing an inorganic layered compound.

[0157] Therefore, the above configuration has an effect that it is possible to provide a low-cost gas replacement packaging container that can suppress a decrease in gas barrier properties at the time of packaging and can reduce an environmental load.

In the gas replacement packaging method of the present invention, the air inside the gas replacement packaging container is replaced with a gas having a composition different from that of air, and then the object to be packaged is packed with the gas replacement packaging container. Is the way.

[0159] Therefore, the above method has an effect that a gas replacement packaging method capable of remarkably suppressing deterioration of a packaged object (contents) can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic partial cross-sectional view showing an example of the gas replacement packaging container of the present invention.

FIG. 2 is a schematic partial sectional view showing another example of the gas replacement packaging container of the present invention.

FIG. 3 is a schematic partial cross-sectional view showing a resin composition layer (gas barrier layer) of the gas replacement packaging container.

FIG. 4 is an X-ray diffraction graph of the inorganic layered compound for calculating the “unit thickness a” of the inorganic layered compound in the gas replacement packaging container.

FIG. 5 is a graph showing the X of the inorganic layered compound for calculating the “plane spacing d” of the inorganic layered compound in the gas replacement packaging container.
It is a line diffraction graph.

FIG. 6 calculates the “plane spacing d” of the inorganic layered compound when the peak corresponding to the “plane spacing d” in the graph of FIG. 5 overlaps with a halo (or background) and is difficult to detect. It is an X-ray diffraction graph at the time.

FIG. 7 is an explanatory view schematically showing a high-speed dispersion process used in manufacturing the gas replacement packaging container.

[Explanation of symbols]

 Reference Signs List 1 base material layer 3 resin composition layer 5 heat-sealing film

Claims (13)

[Claims] 1. A gas replacement packaging container comprising a resin composition layer comprising a resin composition containing an inorganic layered compound. 2. The gas replacement packaging container according to claim 1, wherein a base material layer is laminated on the resin composition layer. 3. The gas replacement packaging container according to claim 1, wherein a heat sealable film is laminated on the resin composition layer. 4. A stretched film is laminated on the resin composition layer,
3. The gas replacement packaging container according to claim 1, wherein a heat sealable film is laminated on the stretched film. 5. The gas replacement packaging container according to claim 1, wherein the inorganic layered compound has a property of expanding and cleaving in a dispersion medium. 6. The resin composition according to claim 1, wherein the resin composition layer is obtained by subjecting a mixed solution of a resin composition containing an inorganic layered compound to a high-pressure dispersion treatment. The gas replacement packaging container according to the above. 7. The gas replacement packaging container according to claim 6, wherein the high pressure dispersion treatment is carried out under a pressure condition of 100 kgf / cm ² or more. 8. An inorganic layered compound having an aspect ratio of 50 to 50.
The gas replacement packaging container according to any one of claims 1 to 7, wherein the container is 5000. 9. An inorganic layered compound having an aspect ratio of 200
The container for gas replacement packaging according to any one of claims 1 to 8, wherein the number is from 3,000 to 3,000. 10. The resin composition contains a high hydrogen bonding resin, and the weight ratio of the inorganic layered compound to the high hydrogen bonding resin is:
The gas replacement packaging container according to any one of claims 1 to 9, wherein the range is 1/100 to 100/1. 11. The gas replacement packaging container according to claim 10, wherein the content of the hydrogen bonding group and the ionic group in the high hydrogen bonding resin is in the range of 20 to 60 mol%. 12. The high hydrogen bonding resin is at least one selected from the group consisting of polyvinyl alcohol and modified products thereof, polysaccharides, and ethylene-vinyl alcohol copolymers and modified products thereof. The gas replacement packaging container according to claim 10. 13. The gas replacement packaging container according to any one of claims 1 to 12, wherein the air inside the container is replaced with a gas having a composition different from that of the air, and then the container is packed with the gas replacement packaging container. A gas replacement packaging method characterized by packaging an object.