JPH11314677A - Film laminated body for retort packaging, and packaging bag provided therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film laminated body for retort packaging which is excellent in stability of gas barrier property for oxygen, steam or the like, easy in treatment and recycling during the disposal, and improved in protection of a food content, and a packaging bag using it. SOLUTION: A laminated body comprises a base material film layer 1, a resin composition layer 3 containing inorganic compounds, an oriented film layer 4, and a heat sealable film layer 5 which are laminated in this order. The laminated body for retort packaging which is formed without using any aluminum foil, consists of a non-halogen resin, is excellent in adaptability for environmental problems and excellent in gas barrier property, and a packaging bag provided therewith 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 film laminate for retort packaging excellent in gas barrier properties against oxygen and the like, which is suitable for preserving food contents (packaged items) such as curry roux and soup, and provided with the laminate. It relates to packaging bags.

[0002]

2. Description of the Related Art In recent years, demand for retort foods has been steadily expanding. However, the characteristics required for packaging bags for retort foods are a recent environmental problem, PL (Products Liablity).
) It is changing significantly due to problems and changes in cooking methods.

[0003] That is, a retort packaging bag having a structure in which aluminum foils having excellent gas barrier properties are laminated to prevent deterioration of food during long-term storage is widely used.

[0004] However, the above-mentioned conventional retort packaging bag has a problem that a large amount of metal residue due to aluminum foil remains at the time of incineration after disposal and takes much time for processing. Increasing use of detectors, and more and more consumer companies wanting to use food packaging that can use microwave ovens, has led to a growing movement to remove aluminum foil from retort packaging bags. .

However, various studies have been made on retort packaging bags from which aluminum foil has been omitted, but none of them have sufficiently satisfactory properties from the viewpoint of sterilization. For example, when using an ethylene-vinyl alcohol copolymer barrier film, after retort treatment,
The problem of the temporary deterioration of the oxygen barrier property and the ethylene-vinyl alcohol copolymer barrier film becomes cloudy,
There is a problem that appearance is deteriorated.

There is also known an example in which a barrier film in which silica or alumina is vapor-deposited on a biaxially stretched polyethylene terephthalate (hereinafter abbreviated as PET) film is used. However, there is a problem that the gas barrier property after the test for the presence or absence of pinhole formation is greatly reduced, and the durability with respect to the gas barrier property is poor.

Further, a polyvinylidene chloride-based film is known as a barrier film. However, since the polyvinylidene chloride-based film contains a halogen, it causes environmental problems such as generation of harmful substances such as dioxin during incineration such as disposal. Recently, the demand for non-halogenation has been increased due to the load on, and there is a problem that the demand cannot be met.

Therefore, in order to avoid the above problems and problems, the present inventors first did not use aluminum foil.
Proposal of packaging bag for retort (Japanese Unexamined Patent Publication No. 7-25187)
No. 4).

[0009]

However, in the above-mentioned conventional packaging bag for retort, for example, when used in a standing pouch method without using a paper carton, the heat seal strength after retorting is reduced, or the waist is insufficient, that is, the packaging for retort is used. There is a problem that the shape maintenance becomes unstable due to the insufficient strength of the bag, and it takes time to re-heat the retort packaging bag storing the packaged items such as foods, or the protective property of the packaged item is poor. There is a problem.

[0010] The present invention provides a retort packaging film laminate which is made of a non-halogen resin and is excellent in compatibility with environmental problems without using an aluminum foil and which is excellent in gas barrier, and a packaging bag provided therewith. It is intended to be.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a base film layer, a resin composition layer as a gas barrier layer containing an inorganic layered compound, a stretched film layer, By arranging the heat-sealing film layer in this order, it was found that the gas barrier property and the protection of the packaged object could be improved, and the present invention was completed.

That is, in order to solve the above problems, the film laminate for retort packaging of the present invention comprises a substrate film layer, a resin composition layer having an inorganic layered compound, a stretched film layer, and a heat-sealing property. The film layers are stacked on each other in this order.

[0013] According to the above configuration, 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. By the maze effect of the inorganic layered compound, it becomes possible to impart gas barrier properties to the resin composition layer.

In addition, in the above-described structure, since the resin composition layer can use a resin containing no chlorine by providing the inorganic layered compound, a conventional polyvinylidene chloride-based film layer containing chlorine is provided. This makes it easier to dispose of and dispose of the waste than in the case where it is used.

Further, in the above-described configuration, by providing a base film layer, a resin composition layer, a stretched film layer, and a heat-sealing film layer in this order,
The waist shortage can be alleviated, and the protection of the food contents to be packaged in the packaging bag using the above configuration can be improved.

The packaging bag of the present invention is provided with the above-mentioned laminated film for retort packaging, for example, in the form of a bag so that the heat-sealing film layer is the innermost layer.

According to the present invention, the food contents which are provided with gas barrier properties and strength, are excellent in the preservability and protection of the package, are easy to process and recycle at the time of disposal, and are packaged. A film laminate for retort packaging with improved product protection and a packaging bag provided with the same are obtained.

[0018]

FIG. 1 shows an embodiment of the present invention.
The following is a description based on FIG. 8.
As shown in FIG. 1, the film laminate for retort packaging of the present invention includes a base film layer 1, a resin composition layer 3 having an inorganic layered compound, and a stretched film layer for imparting strength, for example, tensile strength. 4 and a heat-sealing film layer 5 are laminated on each other in this order. The heat-sealing film layer 5 is set to be the innermost layer on the side that comes into contact with the food to be packaged in the retort packaging film laminate when the retort packaging film laminate is formed in a bag shape. ing.

The film laminate for retort packaging has a resin composition layer 3 provided with an inorganic layered compound, and has an oxygen permeability (mL / atm · m ²⁾ according to a method for measuring oxygen permeability described later. Day) is 1 or less, more preferably 0.1 or less, and even more preferably 0.05 or less.

The base film layer 1 of the present invention can retain liquid contents such as soups, pasty foods, etc., and can prevent water penetration and leakage and dissolve water and aromatic substances. There is no particular limitation as long as it has solvent resistance to solvents such as alcohol, but kraft paper,
Examples include high-quality paper, imitation paper, glassine paper, parchment paper, synthetic paper, various cardboards, and thermoplastic resins. Further, as the base film layer 1, aluminum deposition,
Biaxially-stretched polypropylene (OPP), biaxially-stretched polyethylene terephthalate (OPET), and biaxially-stretched nylon (ONy) on which a metal or metal oxide such as silica evaporation or alumina evaporation has been evaporated can also be suitably used.

Examples of the thermoplastic resin of the base film layer 1 and the material of the heat-sealing film layer 5 include polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, Ethylene-hexene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, polyolefin resins such as ionomer resins, polyethylene terephthalate,
Polyamide resins such as polybutylene terephthalate and polyethylene naphthalate, amide resins such as nylon-6, nylon-6,6, methaxylenediamine-adipic acid condensation polymer, polymethyl methacrylimide,
Acrylic resin such as polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-acrylonitrile resin such as polyacrylonitrile, hydrophobic cellulose-based resin such as cellulose triacetate, cellulose diacetate Resins, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, halogen-containing resins such as Teflon, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, high hydrogen bonding resins such as cellulose derivatives, polycarbonate resins, polysulfone resins, polyethers Engineering plastic resins such as sulfone resins, polyether ether ketone resins, polyphenylene oxide resins, polymethylene oxide resins, and liquid crystal resins. That.

Among them, biaxially stretched polypropylene, polyethylene terephthalate, biaxially stretched polypropylene coated with nylon or polyvinylidene chloride called K coat, polyethylene terephthalate,
Nylon, silica, alumina, aluminum-deposited polyethylene terephthalate, polypropylene, nylon, and OPP (AS-OP) for strong antistatic use are preferably used.

Further, among them, in consideration of environmental protection at the time of disposal or recycling, a resin consisting of only carbon and hydrogen, a resin consisting of only carbon, hydrogen and oxygen,
For example, a polyolefin resin such as polyethylene is preferable.

In the heat-sealable film layer 5, a sealant having a high impact strength is preferable, especially when the sealing property of the contents is required, and polypropylene and propylene are mainly used because of the need to withstand high temperatures during retort. Preferred are polyolefin resins such as copolymers with ethylene or α-olefins, and polyester resins such as polyethylene terephthalate. Further, as the heat-sealing film layer 5, polyethylene, ethylene-synthesized using a metallocene catalyst or a late transition metal complex catalyst.
Polyolefin resins such as α-olefin copolymers and polypropylene are also used.

The method for laminating the heat-sealable film layer 5 as a sealant layer is not particularly limited. For example, a resin used for the heat-sealable film layer 5 is dissolved in a solvent, and Preferable examples include a method of coating the heat-sealable film layer 5 on the stretched film layer 4 and a method of extruding and laminating the heat-sealable film layer 5 on the stretched film layer 4. The interface between the heat-sealable film layer 5 and the stretched film layer 4 may be subjected to a corona treatment, an ozone treatment, an electron beam treatment, or a treatment such as an anchor coating agent.

[0026] In the film laminate for retort packaging of the present invention, a barrier layer of a metal or metal oxide such as silica, alumina or aluminum is further provided between any of the layers of the film laminate, for example, a resin composition layer. 3 and the base film layer 1, a film thickness of 1 to 1000 nm, preferably 10
It may be provided by laminating with a thickness of 200 nm to 200 nm. With such a barrier layer, gas barrier properties can be further ensured, and light-shielding properties can be imparted. The method for forming the barrier layer is not particularly limited, but includes 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. It took time.

However, in the present invention, by providing the barrier layer with a thickness of 1000 nm or less, the gas barrier properties can be further ensured, and the light shielding properties can be imparted.
And, since the above film thickness can be set thinner than before,
Disposal processing and recycling can also be facilitated.

The resin composition layer 3 of the present invention is formed by applying (coating) a coating liquid in which a resin composition containing a cleaved inorganic layered compound is dispersed in a dispersion medium, for example, on the base film layer 1. To form a coating film, and a dispersion medium from the coating film,
For example, it is made of the above resin composition removed by drying. When coating, the resin contained in the coating liquid is, as the resin in the resin composition, the resin used for the base film layer 1 described above, an ethylene-vinyl acetate copolymer emulsion, an acrylic resin emulsion, and a urethane resin. System emulsion, acrylic-urethane copolymer system emulsion can be suitably used,
From the viewpoint of the dispersibility of the inorganic layered compound, a high hydrogen bonding resin is preferable.

The above-mentioned inorganic layered compound is an inorganic compound having a layered structure in which unit crystal layers are stacked on each other, and has a particle size of 5 μm or less and an aspect ratio of 50 to 5000 in terms of gas barrier property when cleaved. Hereinafter, there is no particular limitation as long as the aspect ratio is more preferably in the range of 200 to 3000.

When the aspect ratio is less than 50, the gas barrier property is not sufficient, and when the aspect ratio is more than 5000, it is technically difficult and economically expensive. Further, when the particle size is 3 μm or less, the transparency becomes better, and when the particle size is 1 μm or less, it is more preferable for applications in which transparency is important.

Specific examples of the inorganic stratiform compound used in the present invention include graphite, phosphate derivative-type compounds (zirconium phosphate 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 means 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 compounded with a resin, the particle size of the unit crystal layer 31 which is a cleaved inorganic layered compound in the resin 32 in the resin composition layer 3 shown in FIG. 2 is a cleaved inorganic layered compound in a dispersion medium. This can be considered to correspond to the grain size of the unit crystal layer.

(Method of Determining Average Particle Diameter) The method of determining the average particle diameter of particles in a liquid includes 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.

In the method based on the diffraction / scattering method, when a resin solution, for example, an aqueous resin solution has substantially no scattering (transparency), and therefore scattering derived from particles is dominant, whether or not the resin is present, 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) The particle size distribution and average particle size measurement by the diffraction / scattering method are based on a method in which a dispersion obtained by dispersing a swollen and cleaved inorganic layered compound in an aqueous dispersion medium is subjected to light irradiation. The diffraction / scattering pattern obtained when the light is allowed to pass through is calculated by using the Mie scattering theory or the like to calculate the most consistent particle size distribution of the pattern.

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 size (volume-based median diameter) of the inorganic layered compound in the dispersion obtained by the particle size measurement method by the above-mentioned diffraction / scattering method, and a is the cleaved unit shown in FIG. This is the unit thickness of the crystal layer 31. The “unit thickness a” is a value determined based on a result of independently measuring the thickness of the unit crystal layer in 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. 3 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) ”, page 69 (1985) published by Kagaku Dojinsha).

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 interval can be obtained as the surface interval d shown in FIG.

More specifically, as shown schematically in the graph of FIG. 4 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. 5, when it is difficult to detect the peak corresponding to the above-mentioned "surface distance d" because it overlaps the halo (or background), the lower angle side than 2θd 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", p. 35 and below and p. 271 and below, 1985,
(See Asakura Shoten Co., Ltd.)

Normally, the difference between the above-mentioned spacing d and the “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”, pp. 103-110, 198).
One year, see Doujin Kagaku) and polyvinyl alcohol (hereinafter abbreviated as PVA) in the case of 4 to 5 angstroms (2 to 3 angstroms of water molecules).

The "true aspect ratio" of the unit crystal layer 31 in the resin composition layer 3 is very difficult to directly measure. Although the above aspect ratio Z = L / a is not always equal to the “true aspect ratio” of the unit crystal layer 31 in the resin composition layer 3, the aspect ratio Z is “ It is valid to approximate the "true aspect ratio".

There is a relation of a <d between the plane distance d obtained by powder X-ray analysis of the resin composition and the “unit thickness a” obtained by 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 unit crystal layer 31 in the resin composition layer 3
Is approximated by the above “unit thickness a”, that is, the “true aspect ratio” of the unit crystal layer 31 in the resin composition layer 3 is referred to as the “aspect ratio” in the dispersion of the inorganic layered compound. Approximating with "Z" is of sufficient relevance.

As described above, it is extremely difficult to measure the true grain size of the unit crystal layer 31 in the resin composition layer 3, but the unit crystal layer 31 in the resin 32 of the resin composition layer 3 is extremely difficult.
Is the particle size of the dispersion liquid (resin / inorganic layered compound / dispersion medium)
Can be considered to correspond to the particle size L of the unit crystal layer in the inorganic layer compound.

However, since 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, 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 and cleaving in a dispersion medium is preferably used.

The degree of "swelling / cleaving" of the inorganic layered compound used in the present invention to the 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 speed 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, and 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 swellable 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 ethyl 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, chlorobenzene, carbon tetrachloride,
Chloroform, dichloromethane, 1,2-dichloroethane,
Examples include halogenated hydrocarbons such as perchlorethylene, ethyl acetate, methyl methacrylate (MMA), dioctyl phthalate (DOP), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, and silicone oil.

In the resin composition layer 3 of the present invention, the aforementioned high hydrogen bonding resin having a high content of a hydrogen bonding group or an ionic group is desirably used as the resin. The high hydrogen bonding resin is a content of a hydrogen bonding group or an ionic group in the high hydrogen bonding resin (when both are contained,
(Total amount of both) is 20 to 60 mol%, preferably 30 to 50 mol%. The content of these hydrogen bonding groups and ionic groups can be measured, for example, by a nuclear magnetic resonance (NMR) technique (1H-NMR, 13C-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.

Specific examples of the high hydrogen bonding resin include, for example, PVA, ethylene-vinyl alcohol copolymer having a vinyl alcohol content of 40 mol% or more, polysaccharides, polyacrylic acid and its esters, and polyacrylic acid. Sodium, polystyrene sulfonic acid, sodium polystyrene sulfonate, polyethylene imine, polyallylamine and its quaternary ammonium salt, polyvinyl thiol,
And polyglycerin. Among the above-mentioned resins, more preferable ones include PVA, polysaccharide, and ethylene-vinyl alcohol copolymer.

Here, PVA refers to, for example, a polymer obtained by hydrolyzing or transesterifying (saponifying) an acetic ester portion of a vinyl acetate polymer (that is, a polymer that has become a copolymer of vinyl alcohol and vinyl acetate). )
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 (for details of PVA, for example, Povar Association, "PVA World", 1
992, Polymer Publishing Association; Nagano et al., "Poval"
1981, see Polymer Publishing Association).

The degree of “saponification” in PVA is preferably at least 70% by mole percentage, more preferably at least 85%, particularly preferably 98% or more, that is, a completely saponified product. The degree of polymerization in PVA is 100
It is preferably from 5000 to 5,000, more preferably from 200 to 3,000. Further, the PVA 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 here 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 are defined as other unsaturated monomers copolymerizable with a vinyl acetate monomer in a vinyl ester resin in the production process of polyvinyl alcohol, 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 alkalis thereof. Salts, vinyl sulfonic acid, styrene sulfonic acid, 2-
Sulfonic acid-containing monomers such as acrylamide-2-methylpropanesulfonic 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, 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 units of vinyl alcohol.
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. In the case where 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-based 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 having a silyl group in the molecule may be used as a result, 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 to obtain these modified polyvinyl alcohol resins include trimethylchlorosilane, dimethylchlorosilane, methyltrichlorosilane, vinyltrichlorosilane, diphenyldichlorosilane, and 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 of polymerizing a vinyl ester in the presence of a mercaptan having a silyl group 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 above-mentioned silylation ratio 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 various polyvinyl alcohol-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 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 coating liquid used in the present invention is a liquid obtained by dispersing or dissolving the above-mentioned inorganic layer compound and resin in a dispersion medium. From the viewpoint of the gas barrier properties of the obtained film laminate for retort packaging, the dispersion medium is preferably a liquid that swells or cleaves the above-mentioned inorganic layered compound.

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)
But 1/100 to 100/1, and more preferably 1/20 to 10
/ 1 is preferred. 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,
The total of both is 0.1 to 70% by weight, from the viewpoint of productivity 1 to 15% by weight, more preferably 4 to 10% by weight.

The resin used for 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 titanium coupling agents, silane coupling agents, melamine coupling agents, epoxy coupling agents, isocyanate coupling agents, and the like. 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; and 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.

Preferable examples of the crosslinking 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 performing 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 include:
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 an organometallic compound include an organic titanium compound, an organic zirconium compound, an organic aluminum compound and an organic silicon compound.

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.

Among these, a chelate compound is preferable in terms of stability in a 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 for 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 cases, it is preferable to perform treatment using a high-pressure dispersion device from the viewpoint of dispersibility of the inorganic layered compound.

As a high-pressure dispersion device, for example, Microfluid
There is an ultrahigh-pressure homogenizer (trade name: Microfluidizer) manufactured by ics Corporation or a Nanomizer manufactured by Nanomizer, and a homogenizer manufactured by Manton-Gaulin, such as a homogenizer manufactured by Izumi Food Machinery.

In the above three methods, after removing the solvent and the dispersion medium from the system and laminating, the obtained retort packaging film laminate is heat-aged at, for example, 110 ° C. or more and 220 ° C. or less. In particular, the water resistance (meaning of gas barrier properties after a water resistance environment test) of the film laminate for retort packaging can be improved, which is preferable.

The aging time is not limited, but it is necessary that the retort packaging film laminate reaches at least a set temperature. For example, in the case of a method using a heat medium such as a hot air drier, the time is from 1 second to 100 minutes. preferable. 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 a particularly excellent effect in improving water resistance when the resin is a high hydrogen bonding resin.

The high-pressure dispersion treatment in the present invention is, as shown in FIG. 6, a high-speed passage of a composition mixture obtained by mixing particles to be dispersed or a dispersion medium through a plurality of narrow tubes 11 to collide with each other. To perform 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 1000 μm. It is preferable that a pressure of 100 kgf / cm ² or more is applied.
/ Cm ² or more, more preferably 1000
kgf / cm ² or more. Further, when the composition mixture passes through the narrow tube 11, it is preferable that the maximum arrival speed of the composition mixture reach 100 m / s or more, and the heat transfer speed is 100 kcal / hr or more.

The principle of the high-pressure treatment in the high-pressure dispersion treatment apparatus used for the high-pressure dispersion treatment 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 processed 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.

The stretched film layer 4 of the present invention is not particularly limited, but is preferably at least one selected from the group consisting of biaxially stretched polyamide and biaxially stretched polyethylene terephthalate. The above-mentioned stretched film layer 4
The higher the tensile strength, the better, and the elongation at break is preferably 700% or less.
0% or less is preferable. Examples of the polyamide-based biaxially stretched film include nylon-6, nylon-6,6, metaxylenediamine-adipic acid condensation polymer, and the like.

In laminating the resin composition layer 3 of the present invention on the substrate film layer 1, the substrate film layer 1 is subjected to a surface treatment, for example, a corona treatment, a flame plasma treatment, an ozone treatment, an electron beam irradiation treatment. An anchor process may be performed.

When the anchor treatment is performed, for example, as shown in FIG. 7, when the anchor layer 2 is formed on the base film layer 1, the material of the anchor layer 2 may be, for example, polyethyleneimine-based, alkyl titanate-based, polybutadiene. Although not particularly limited, the anchor layer 2 made of a urethane-based compound prepared from an isocyanate compound and an active hydrogen compound is preferable from the viewpoint of water resistance.

The isocyanate compounds include 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, poly-β-methyl-δ-valerolactone, polycaprolactone, and polyester polyols such as polyester from diol / dibasic acid.

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, diols are ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc., and the dibasic acids are adipic acid, azelaic acid, sebacic acid, and isophthalic acid. And terephthalic acid. Other polyols include active hydrogen compounds such as castor oil, liquid polybutadiene, epoxy resin, polycarbonate diol, acrylic polyol, and neoprene. The mixing ratio between the isocyanate compound and the active hydrogen compound is not particularly limited, but isocyanate groups and active hydrogen groups, for example, -OH, -NH,
It is preferable to determine the amount of addition in consideration of the equivalence relationship with —COOH. For example, the number of moles of isocyanate groups (A
N) and the number of moles (BN) of active hydrogen groups of the active hydrogen compound, R (R = AN / BN), are 0. 0 from the viewpoint of adhesive strength.
001 or more is preferable, and 10 or less is preferable from a viewpoint of adhesiveness and blocking. The molar ratio R is 0.01
More preferably, it is within the range of 1 or less. Each mole number of the isocyanate group and the active hydrogen group is 1H-N
It can be quantified by MR and 13 C-NMR.

The method for laminating the anchor layer 2 on the resin composition layer 3 or another layer, for example, the base film layer 1 is not particularly limited, but an anchor coat agent containing an isocyanate compound and an active hydrogen compound is dissolved in a solvent. And a coating method using an anchor coating agent solution.

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. Examples of the method include a die coating method, 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 lower the gelboflex resistance. Therefore, the coating thickness is more preferably from 0.03 μm to 2.0 μm, and still more preferably from 0.05 μm to 1.0 μm.

The thickness of the resin composition layer 3 of the present invention is in the range of 1 nm to 10 μm, more preferably 10 nm in dry thickness.
nm to 5 μm, more preferably 0.1 μm
１1 μm. When the thickness exceeds 10 μm, the flexibility of the obtained film laminate for retort packaging deteriorates. If the thickness is less than 1 nm, an effective gas barrier property cannot be obtained.

In the retort packaging film laminate of the present invention, when the anchor layer 2, particularly the urethane-based anchor layer 2, is used, the resin composition layer 3 is used to improve the adhesion to the anchor layer 2. Those containing a surfactant are desirable. The surfactant is not particularly limited as long as it can improve the adhesiveness and adhesiveness between the anchor layer 2 and the resin composition layer 3, and examples thereof include an anionic surfactant and a cationic surfactant. Agents, zwitterionic surfactants and non-ionic surfactants.

Examples of the anionic surfactant include carboxylic acid types such as aliphatic monocarboxylates and N-acyloylglutamate, alkylbenzene sulfonates, naphthalene sulfonate-formaldehyde condensates, and dialkyl sulfosuccinates. 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 the zwitterionic 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, polycondensates of polydimethylsiloxane group and alkylene oxide adduct, and polysiloxane-polyoxyalkylene. Ether type such as copolymer, 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 alkanol Examples thereof include alkanolamide type such as amide and fluorine type such as diglycerin ester of perfluorodecanoic acid and perfluoroalkylalkylene oxide compound.

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 gas barrier layer 3 is formed, for example, when a coating liquid is used, 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 may be provided as long as the effect is not impaired. Each material of the film laminate for retort packaging may include an ultraviolet absorber, a coloring agent, an antioxidant and the like. Additives may be mixed.

In the packaging bag provided with the retort packaging film laminate, the shape of the container body is as follows.
The shape is not particularly limited as long as the food can be packaged as an object to be packaged and is suitable for heating, but a shape having autonomy is desirable.

The self-sustainability may be any shape such that it can be placed in a horizontal position, for example, in a storage place or a heating place without any special assistance, without any assistance. For example, a cube, a rectangular parallelepiped, a columnar shape (drum shape), Truncated cone Shaped into a truncated pyramid shape.

Specific examples of the above shapes include a three-side sealed packaging bag, a four-side sealed packaging bag, a pillow packaging bag, a packaging bag with a gusset, a carton shape, a brick shape, and a standing pouch-shaped container body shown in FIG. The retort packaging film laminate is formed so that the heat-sealable film layer 5 becomes the innermost layer so as to be No. 6.

The thickness of the film laminate for retort packaging in the above-mentioned packaging bag is not particularly limited, but is preferably 30 μm or more from the viewpoint of protecting the contents to be packaged.
Further, the thickness is preferably 300 μm or less from the viewpoint of cost.

Examples of the use of the packaging bag provided with the film laminate for retort packaging of the present invention include confectionery, confectionery, miso, pickles, konjac, chikuwa, kamaboko, other processed marine products, meatballs, hamburgers, ham and sausages, and coffee. , Sake, sauce, seasoning, soup, curry roux,
Food fields such as food packaging applications such as prepared foods such as miso soup are preferred, but furthermore, temperature adjustment such as heating is required, cosmetics, aromatics, medical infusion packs, semiconductor packaging, It is also used in medical, electronic, chemical and mechanical fields, such as packaging of oxidizing chemicals such as developer and sodium hypochlorite, and packaging of precision materials.

[0126]

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, the thickness of less than 0.5 μm is determined by a gravimetric analysis 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 actual coating film thickness by the IR method. A calibration curve with IR absorption was 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 ratio of the specific inorganic element analysis value of the laminate (derived from the resin composition layer) to the specific element fraction of the inorganic layered compound alone] To determine the ratio between the resin composition layer of the present invention and the substrate film layer).

[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 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] 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 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 was calculated by the equation of Z = L / a.

[Oxygen Permeability Measurement] Based on JIS K7126, an oxygen permeability measuring device (OX-TRAN ML,
MOCON) at 23.7 ° C (60% R
H).

[Heat Sealing Test] A bar sealer [Fuji Impulse Co., Ltd., seal width 10 mm, heat seal temperature 205 ° C., heat seal time 0.5] Seconds], heat-seal, cut into strips of 15 mm width,
It was set on an autograph (Autograph AGS-100: manufactured by Shimadzu Corporation), and the heat seal strength (T-shaped peeling) was measured from two directions at a tensile speed of 500 mm / min. The above two directions are the machine discharge directions of the resin during the production of the film laminate.
ction (abbreviated as MD in the table) and Traverse Direciton (T in the table)
D).

[Retort Test] A retort sterilization test was performed on a retort packaging bag produced using the film laminate obtained in Example 1 described later. The retort sterilization was performed at 120 ° C., 2 kg / cm ² , for 30 minutes using a time oaker (high-speed hot water storage type sterilizer; manufactured by Sampras).

[Example 1] [Coating liquid for resin composition layer] Dispersion vessel [trade name: Despa MH]
-L, manufactured by Asada Tekko Co., Ltd.], add 1860 g of ion-exchanged water (specific electric conductivity 0.7 μS / cm or less), and further add P
VA [PVA117H; manufactured by Kuraray Co., Ltd., saponification degree: 99.
6%, degree of polymerization 1700] and stirring under low speed (150
The temperature was raised to 95 ° C. at 0 rpm at a peripheral speed of 4.10 m / min), stirred for 1 hour, and dissolved to obtain a solution (A).

Next, the solution (A) was stirred for 60 hours.
After lowering the temperature to 0 ° C., a solution obtained by adding 0.25 g of a nonionic surfactant (trade name: SH3746, manufactured by Dow Corning Toray Co., Ltd.) to a mixed solution of 125 g of 1-butanol and 375 g of isopropyl alcohol was added. The above solution (A)
To obtain a mixture (B). The nonionic surfactant is a polydimethylsiloxane-polyoxyethylene copolymer.

1960 g of the mixture (B) was charged into a stirring emulsifier (trade name: vacuum emulsifier PVQ-3UN, manufactured by Mizuho Industry Co., Ltd.). 50 g of natural montmorillonite (Kunipia F; manufactured by Kunimine Kogyo Co., Ltd.) as powder so that the weight ratio of the resin to the inorganic layered compound is 2: 1.
After confirming that the montmorillonite was substantially precipitated in the solution, the mixture was stirred at 600 mmHg and 5000 rpm for 10 minutes to obtain a resin composition mixture (C).

A mixture of 2000 g of the resin composition mixture (C) was dispersed in a high-pressure dispersing apparatus (trade name: ultra high pressure homogenizer M110-
E / H, manufactured by Microfluidics Corporation), and treated once under a pressure condition of 1750 kgf / cm ² to obtain a uniform dispersion liquid (D) having good dispersibility. The solid content concentration of the dispersion (D) was 7.5% by weight.

The dispersion (D) comprising PVA and montmorillonite was cast into a film and subjected to X-ray analysis.
The interplanar spacing d of the swelled and cleaved montmorillonite (inorganic layered compound) was measured.

As a result of determining the plane distance d from the diffraction peak obtained from the X-ray analysis, the plane distance d was larger than the unit thickness a. Therefore, the montmorillonite was cleaved sufficiently for the reason described above. I found out. At this time, the aspect ratio of the cleaved inorganic layered compound is 20.
It was 0 or more.

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. Titanium acetylacetonate [TC1
5.3, was gradually added to obtain a coating liquid for a resin composition layer.

[Film laminate for retort packaging] Thickness 1
2 μm biaxially stretched polyethylene terephthalate (OPE
T) Film [ESPET T4102, Toyobo Co., Ltd.
The surface corona treatment of
An anchor coat agent (urethane-based) [Adcoat AD335 / CAT10 = 15/1] on the base film layer
(Weight ratio: manufactured by Toyo Morton Co., Ltd.)] (test coater; manufactured by Yasui Seiki: microgravure coating method, coating speed 3 m / min, drying temperature 80 ° C.). The dry thickness of the anchor coat layer was 0.05 μm.

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

Subsequently, an adhesive [Adcoat AD503 / CAT10 =
15/1 (weight ratio: manufactured by Toyo Morton Co., Ltd.) using a 15 μm thick biaxially stretched nylon (biaxially stretched polyamide) film [Unitika, Emblem (ONBC-
15)], and then a 50 μm-thick CPP is further formed on a biaxially stretched nylon film.
Film (Heat sealable film) [Pyrene P11
53, manufactured by Toyobo Co., Ltd.] to obtain a film laminate for retort packaging.

Thereafter, the film laminate for retort packaging was formed into a bag for retort packaging so that the CPP film became the innermost layer, thereby producing a packaging bag of the present invention.

The characteristics (oxygen permeability) of each of the packaging bags were measured according to the above-described measuring methods. The oxygen permeability of the packaging bag was 0.1 (mL / atm · m ² · day), and the bag had low oxygen permeability and excellent gas barrier properties. Further, the appearance of the packaging bag before and after the retort was examined based on the above-described retort test, but no change in the appearance was observed, and the packaging bag was excellent in retort treatment resistance.

[0145]

As described above, the film laminate for retort packaging of the present invention comprises a base film layer, a resin composition layer having an inorganic layered compound, a stretched film layer, and a heat sealable film layer. , In this order.

Therefore, in the above-described structure, since a resin containing no chlorine can be used in the resin composition layer by providing the inorganic layered compound, a conventional polyvinylidene chloride-based film layer containing chlorine is provided. This makes it easier to dispose of and dispose of the waste than in the case where it is used.

Further, in the above configuration, by providing the base film layer, the resin composition layer, the stretched film layer, and the heat-sealing film layer in this order,
The shortage of the waist can be avoided, and the protection of the food contents can be improved.

As a result, the above-described structure is excellent in protection properties such as gas barrier properties against the packaged items such as food contents, and can facilitate disposal and recycling at the time of disposal.
This has the effect of improving the protection of food contents.

As described above, the packaging bag provided with the retort packaging film laminate of the present invention can facilitate disposal and recycling at the time of disposal, and can improve the protection of food contents. By having a body,
Similarly, it has excellent gas barrier properties, facilitates disposal and recycling at the time of disposal, and improves the protection of food contents.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing one example of a film laminate for retort packaging of the present invention.

FIG. 2 is a schematic sectional view showing a resin composition layer in the film laminate for retort packaging.

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 in the production of the resin composition layer.

FIG. 7 is a schematic sectional view showing another example of the film laminate for retort packaging of the present invention.

FIG. 8 is a schematic perspective view showing an example of a packaging bag formed using the above-described film laminate for retort packaging.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base film layer 2 Anchor layer 3 Resin composition layer 4 Stretched film layer 5 Heat sealable film layer 6 Container main body

Claims (11)

[Claims] 1. A retort packaging comprising: a base film layer, a resin composition layer having an inorganic layered compound, a stretched film layer, and a heat-sealing film layer laminated in this order. Film laminate. 2. The stretched film layer comprises a biaxially stretched polyamide,
The film laminate for retort packaging according to claim 1, wherein the laminate comprises at least one selected from the group consisting of biaxially stretched polyethylene terephthalate. 3. The film laminate for retort packaging according to claim 1, wherein the inorganic layered compound has a property of expanding and cleaving in a dispersion medium. 4. The resin composition according to claim 1, wherein the resin composition layer is obtained by subjecting a mixed solution of a resin composition having an inorganic layered compound to high-pressure dispersion treatment. The film laminate for retort packaging according to the above. 5. The film laminate for retort packaging according to claim 4, wherein the high pressure dispersion treatment is carried out under a pressure condition of 100 kgf / cm ² or more. 6. An inorganic layered compound having an aspect ratio of 50 to 50.
The retort packaging film laminate according to any one of claims 1 to 5, wherein the thickness is 5000. 7. An inorganic layered compound having an aspect ratio of 200
The film laminate for retort packaging according to any one of claims 1 to 5, wherein the thickness is from 3,000 to 3,000. 8. The resin composition layer contains a high hydrogen bonding resin, and the weight ratio of the inorganic layered compound to the high hydrogen bonding resin is:
The film laminate for retort packaging according to any one of claims 1 to 7, wherein the thickness is in the range of (1/100) to (100/1). 9. The retort packaging according to claim 8, wherein the high hydrogen bonding resin has a molar percentage of a hydrogen bonding group or an ionic group in the resin of 20% or more and 60% or less. Film laminate. 10. The retort according to claim 8, wherein the high hydrogen bonding resin is polyvinyl alcohol and a modified product thereof, a polysaccharide, or an ethylene-vinyl alcohol copolymer and a modified product thereof. Film laminate for packaging. 11. A packaging bag comprising the film laminate for retort packaging according to any one of claims 1 to 10 such that the heat-sealing film layer is the innermost layer.