JPH11314320A - Tubular container, packaging material for food and packaging material for pharmaceutical preparations - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a material being thinner than a tubular laminate material and having gas barrier properties to be replaced with a laminate having an aluminum foil by using a laminate having 2 gas barrier layer made of a resin composition having an inorganic laminar compound. SOLUTION: The tubular container is formed by laminating a gas barrier layer 3 made of a resin composition containing an inorganic laminar compound on a base material 1 to form a laminate and molding the laminate in a desired shape. The laminar compound contained in the layer 3 has a laminar structure in which unit crystal layers are stacked with each other, and a graphite, a zirconium phosphate, chalcogenide, a clay mineral or the like having a particle size of 5 μm or less and an aspect ratio of 50 to 5,000 with respect to gas barrier properties in a cleaved state can be used. In this case, if an anchor layer 2 is incorporated, more excellent adhesive properties than that of the laminate obtained by laminating the layer 3 on the material l 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 tubular container which is excellent in gas barrier properties and contains creams and pastes therein and is squeezed out at the time of use, a food packaging material provided with the tubular container, and It relates to pharmaceutical packaging materials.

[0002]

2. Description of the Related Art Conventionally, for example, application type pharmaceuticals,
Tubular containers for storing and packaging quasi-drugs such as toothpaste, or foods such as mustard paste and wasabi, usually have a tubular body with a closed lower end and an upper end of the body. The shoulder portion includes a shoulder portion, a mouth and neck portion that is continuous with the shoulder portion, and a cap that is detachably engaged with the mouth and neck portion.

[0003] The contents to be stored and packaged in the above-mentioned tubular container include, as described above, drugs, quasi-drugs,
Foods and the like. Since the quality of these contents significantly deteriorates when they come into contact with the outside air or when volatile components and the like contained in the contents evaporate and diffuse, the gas-barrier property should be imparted to the tubular body. Is particularly preferred.

[0004] Examples of the material used for the tubular container having the body portion provided with a gas barrier property include a laminate in which aluminum foil is laminated. The film thickness of the aluminum foil is usually in the range of about 7 μm to 20 μm, and a laminate including this aluminum foil can realize excellent gas barrier properties, and thus has been widely used.

Another material is disclosed in Japanese Patent Laid-Open No.
No. 3156 discloses a laminated material for tubes. This laminated material for a tube sandwiches a resin inner layer having heat sealing performance between the resin outer layer and an intermediate layer formed between the inner layer and the outer layer. The composite film layer includes a plastic layer of a resin contained therein and a thin film layer of an inorganic oxide formed on the plastic layer.

[0006] The tubular container manufactured by using the above-mentioned laminated material for a tube has transparency such that the sealed state of the filling material (content) can be visually observed from the outside, and further has a gas barrier property. Having the composite film layer.
Therefore, even when squeezing out and using the contents,
Pinholes and the like do not occur in the composite film layer, and the filling does not come into contact with the outside air, and volatile components do not evaporate or diffuse. As a result, the tubular container can improve the preservability of the contents.

[0007]

However, when a tubular container formed by using the above-mentioned laminate of aluminum foils is used and then discarded and incinerated, residual (ingot) remains in the incinerated ash. More. In addition, the resin layer of the container body and the aluminum foil are difficult to separate from each other, so that recycling is also difficult. Therefore, the tubular container having the laminate in which the aluminum foils are laminated has a problem that the load on the environment is very large.

On the other hand, in the tubular container having a laminated material for a tube disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 4-223156, since the aluminum foil is not used, the load on the environment described above is extremely reduced. Can be. However, in order to exhibit a gas barrier property in place of the aluminum foil, in addition to the above-mentioned intermediate layer having a thin film of an inorganic oxide and a plastic layer, at least an outer layer formed on the front and back sides of the tube laminate is required. An inner layer sandwiched between them is required. Therefore, there is a problem that the thickness of the tube laminate increases. Further, the gas barrier properties of the tube laminate are not sufficient.

Therefore, there has been a demand for a tubular container which is thinner than the above-mentioned tubular laminated material and which is formed of a material having gas barrier properties which can replace the laminated body having the above-mentioned aluminum foil.

[0010]

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 tubular container obtained by using a laminate having a gas barrier layer made of a resin composition having an inorganic layered compound. However, it has been found that, despite its very thin thickness, it exhibits excellent gas barrier properties, furthermore, has a small load on the environment, and can exhibit excellent gas barrier properties that can be substituted for a laminate having an aluminum foil.

That is, in order to solve the above-mentioned problems, the tubular container of the present invention is characterized by comprising a laminate having a gas barrier layer made of a resin composition having an inorganic layered compound. .

According to the above configuration, as the gas barrier layer,
Since it has a layer made of a resin composition having an inorganic layered compound, it can exhibit extremely excellent gas barrier properties. Further, since this gas barrier layer has excellent durability, pinholes and the like are not formed even by physical force applied when squeezing the contents from the tubular container.

Therefore, without using aluminum foil for imparting gas barrier properties, the load on the environment can be extremely reduced, and storage stability that can be substituted for a laminate having aluminum foil can be obtained. Furthermore, since the very excellent gas barrier properties can be exhibited only by the inorganic layered compound, the body of the tubular container according to the present invention is to be formed of a thinner laminate than before, and the tubular container It can be more compact.

In the tubular container according to the present invention, it is preferable that the laminate further has at least one metal or metal oxide layer. The formation of the metal or metal oxide layer is not particularly limited, but is preferably formed by an evaporation method. By forming the metal or metal oxide layer, the gas barrier properties of the contents can be improved and the contents can be shielded from light, so that the deterioration of the contents can be further suppressed.

Further, the tubular container according to the present invention preferably has at least one polyolefin resin layer, and more preferably at least one biaxially stretched film layer. By forming these layers, the gas barrier properties of the container can be further improved.

The oxygen permeability of the tubular container according to the present invention is preferably 1 mL / m ² · day · atm or less, more preferably 0.1 mL / m ² · day · atm or less. Preferably, 0.05 mL / m ² day
More preferably, it is atm or less. When the oxygen permeability is within this range, the stored contents can be prevented from deteriorating and can be maintained for a longer period.

In the tubular container according to the present invention, the inorganic layered compound is preferably swelled and cleaved in a dispersion medium, and the gas barrier layer is obtained by subjecting a mixed solution of a resin composition having an inorganic layered compound to high pressure dispersion treatment. It is preferably obtained by the above method. The pressure conditions for the high-pressure dispersion treatment are as follows:
It is preferably at least 100 kgf / cm ² ,
0 kgf / cm ² or more, more preferably 1 kgf / cm ² or more.
It is particularly preferred that it is not less than 000 kgf / cm ² .

The aspect ratio of the inorganic layered compound is as follows:
It is preferably in the range of 50 to 5000, and 200
It is more preferably in the range of -3000.

The resin composition preferably contains a high hydrogen bonding resin. At this time, the weight ratio between the inorganic layered compound and the high hydrogen bonding resin is (1/100) to
(100/1), preferably (1/1).
More preferably, it is in the range of 20) to (10/1). Further, the high hydrogen bonding resin preferably has a molar percentage of hydrogen bonding group or ionic group per unit weight of the resin of 30% or more and 50% or less. It is preferable that the product is a polysaccharide, a polysaccharide, or an ethylene-vinyl alcohol copolymer and a modified product thereof.

The outermost layer and / or the innermost layer of the laminate may be a layer made of a resin selected from any one of a polyolefin resin, an ethylene-vinyl alcohol resin, and a polyacrylonitrile resin. Preferably, the laminate has an ultraviolet blocking layer.

By providing each of these components, the gas barrier properties of the tubular container can be further improved, the deterioration of the contents can be suppressed, and the storage can be performed for a longer period of time.

Further, a food packaging material according to the present invention is provided with the above-mentioned tubular container.
As a result, it is possible to satisfactorily preserve foods that are difficult to preserve in general, such as mustard mustard and paste wasabi, which contain fragrance components that are easily volatilized and diffused.

Further, the pharmaceutical packaging material according to the present invention comprises:
It is characterized by using a tubular container having the above-described configuration. Therefore, quasi-drugs such as pharmaceuticals for application and toothpastes can be well preserved.

[0024]

FIG. 1 shows an embodiment of the present invention.
The following is a description based on FIG.
The tubular container according to the present invention is formed by laminating a gas barrier layer made of a resin composition having at least an inorganic layered compound on a substrate to form a laminate, and molding the laminate into a desired shape. It has a configuration.

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 when cleaved, has a particle size of 5 μm or less, an aspect ratio of 50 or more with respect to gas barrier properties. 5000
The aspect ratio is more preferably 200 to 3000 or less.
There is no particular limitation as long as it is within the range.

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. 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 above-mentioned inorganic layered compound include graphite, phosphate derivative-type compounds (zirconium phosphate compounds, etc.), chalcogenides, clay minerals and the like. Here, the “chalcogen compound” includes a group IV (Ti, Zr, Hf) and a group V (V, Nb, T).
a) and dichalcogenides of group VI (Mo, W), wherein the compound is of the formula MX ₂ (M is the above element, X is the chalcogen (S,
Se, Te). ).

The particle size of the above-mentioned inorganic layered compound means a particle size obtained by a diffraction / scattering method in a dispersion medium. It is extremely difficult to measure the true particle size in the gas barrier layer.
In the case where the dispersion medium of the same kind as the dispersion medium used in the scattering method is sufficiently swollen and cleaved to be combined with the resin used for the gas barrier layer, the cleaved unit crystal layer in the resin 32 of the gas barrier layer 3 shown in FIG. The particle size of 31 can be considered to correspond to the particle size of the cleaved inorganic layered compound in the dispersion medium.

[Method for Determining Average Particle Diameter] The method for 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.

According to the diffraction / scattering method, when a resin solution, for example, a resin aqueous solution has substantially little scattering (transparency), and scattering derived from particles is dominant, particles are dispersed regardless of the presence or absence of the resin. It is preferable because information on only the particle size distribution 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 carried out by irradiating a dispersion obtained by dispersing a swollen and cleaved inorganic layered compound in an aqueous dispersion medium. 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.).

[Aspect Ratio Measurement Method] 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 unit shown in FIG. This is the unit thickness of the crystal layer 31. 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 diffraction method described later or the like.

More specifically, as schematically shown in the graph of FIG. 2 in which the horizontal axis represents 2θ and the vertical axis represents the intensity of the X-ray diffraction peak, the lowest diffraction angle 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 diffraction method, for example, see “ Guide (a) ”, page 69 (1985) published by Kagaku Dojinsha).

When the resin composition corresponding to the gas barrier layer 3 obtained by removing the dispersion medium from the dispersion is subjected to powder X-ray diffraction, usually the plane spacing of each of the dispersed inorganic layered compounds in the resin composition is obtained. Can be obtained as the surface distance d shown in FIG.

More specifically, as shown in the graph of FIG. 3 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. 4, when it is difficult to detect a peak corresponding to the above-mentioned "surface distance d" by overlapping with a 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 Iwami et al. Ed., "Encyclopedia of Clay", p. 35 or less and p. 271 or less, 1985
Year, see Asakura Shoten Co., Ltd.).

Normally, the difference between the above-mentioned surface distance d and “unit thickness a”, that is, the value of k = (da) (when converted into “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 “width of a single resin chain” can be determined by simulation calculation or the like (for example, “Introduction to Polymer Chemistry”, pp. 103-110,
1981, see Chemical Doujinshi), and in the case of polyvinyl alcohol, it is 4 to 5 angstroms (2 to 3 angstroms for water molecules).

It is extremely difficult to directly measure the "true aspect ratio" of the unit crystal layer 31 in the gas barrier layer 3. 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 gas barrier layer 3, the aspect ratio Z is “true” for the following reason. It is reasonable to approximate the "aspect ratio".

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

As described above, although it is extremely difficult to measure the true grain size of the unit crystal layer 31 in the gas barrier layer 3, the unit crystal layer 31 in the resin 32 of the gas barrier 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 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 and cleaving in a dispersion medium is preferably used.

The swelling of the inorganic layered compound in the dispersion medium
The degree of "cleavage" can be evaluated by the following "swelling / cleavage" test. The swellability of the inorganic layered compound is
In the following swellability test, the swelling value is preferably about 5 or more (more preferably, about 20 or more). 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 disperser [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
On the top of the tetrahedral layer of silica, a two-layer structure with an octahedral layer with aluminum or magnesium as the central metal, and on an octahedral layer with a silica tetrahedral layer with aluminum or magnesium as the 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 a kaolinite group and an antigolite group, and the latter three-layer structure type includes a smectite group and a smectite group depending on the number of interlayer cations.
Vermiculite, mica and the like can be mentioned.

More specifically, these clay minerals include kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectite. Light, tetrasilicyl 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. (Note that clay minerals treated with an organic substance are described in Asakura Shoten, See Clay Encyclopedia).

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

The dispersion medium for swelling or cleaving the inorganic layered compound is, for example, water,
Examples include alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol and diethylene glycol, dimethylformamide, dimethyl sulfoxide, and acetone, and more preferably alcohols such as water and methanol.

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; halogenated hydrocarbons such as chlorobenzene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane and perchloroethylene; ethyl acetate; methyl methacrylate ( MMA), dioctyl phthalate (DOP), dimethylformamide,
Examples include dimethyl sulfoxide, methyl cellosolve, and silicone oil.

The tubular container according to the present invention is not particularly limited as long as the resin composition containing the above-mentioned inorganic layer compound can be formed into a layer to obtain a laminate having the gas barrier layer 3. For example, a method in which the above resin composition is molded into a film shape and bonded to a substrate may be used, or a coating liquid composed of a resin composition containing an inorganic layered compound is prepared, and this coating liquid is used as a base. A method of coating a material may be used.

The resin used in the method for molding the resin composition into a film is not particularly limited, and may be any resin that does not lower the gas barrier properties of the gas barrier layer 3. In addition, as a method of molding the resin composition into a film, extrusion molding, calendering, or the like is preferably used, but is not particularly limited.

The tubular container according to the present invention is
The gas barrier layer 3 can be molded into various shapes depending on the contents to be packaged. In this case, the gas barrier layer 3 is formed by a resin composition rather than a method of forming a film and then laminating a base material. Is preferably used as a coating liquid, and a method of coating this coating liquid is preferably used.

In the method of coating the coating liquid,
Since the gas barrier layer 3 can be laminated after the base material is first formed into a desired shape, the degree of freedom in forming the tubular container according to the present invention can be further improved.

The resin contained in the above-mentioned coating liquid is not particularly limited. For example, polyolefin resin, polyester resin, amide resin, acrylic resin, styrene resin, acrylonitrile resin, cellulose resin,
Examples include a halogen-containing resin, a hydrogen bonding resin, a liquid crystal resin, a polyphenylene oxide resin, a polymethylene oxide resin, a polycarbonate resin, a polysulfone resin, a polyethersulfone resin, and a polyetheretherketone resin.

Preferred examples of the resin include resins containing a high hydrogen bonding resin having a hydrogen bonding group or an ionic group described below. The content of the hydrogen bonding group or the ionic group in the high hydrogen bonding resin (when both are included, the total amount of both) is usually 20 to 60 mol%, preferably 30 to 50 mol%. is there. 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, polyvinyl alcohol, an ethylene-vinyl alcohol copolymer having a vinyl alcohol fraction of 40 mol% or more, polysaccharides, polyacrylic acid and its esters, and polyacrylic acid. Sodium acid, polysulfonic acid, sodium polysulfonate, polyethyleneimine, polyallylamine and its quaternary ammonium salt, polyvinyl thiol, polyglycerin and the like. Among the above-mentioned resins, more preferred are polyvinyl alcohol and polysaccharides.

Here, the polyvinyl alcohol is a polymer obtained by, for example, 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). Is, for example, edited by the Poval Society, “The World of PVA”, 1992,
Nagano et al., “Poval” 1981
Year, see Polymer Publishing Association).

"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. Furthermore, the PVA 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 modified polyvinyl alcohol described above is
In the process of producing a polyvinyl alcohol resin, a vinyl ester, particularly a vinyl acetate monomer, is copolymerized with another unsaturated monomer copolymerizable therewith. Examples of the other unsaturated monomers include olefins such as ethylene, propylene, α-hexene and α-octene, (meth) acrylic acid, crotonic acid, maleic acid (anhydride), fumaric acid, and itaconic acid. Such as unsaturated acids, and alkyl esters and alkali salts thereof, vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-
Sulfonic acid-containing monomers such as 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 and other quaternizable cationic monomers, styrene, alkyl vinyl ether, (meth) Acrylamide and others.

The ratio of these copolymer components is not particularly limited, but may be 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 in which a polycarboxylic acid component is copolymerized 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 may be 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 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 an acyloxyl group. And those having a reactive substituent such as a silanol group or a salt thereof, which is a hydrolyzate of these groups,
Among them, a case of a silanol group is particularly preferred.

Compounds having a silyl group in the molecule used to obtain these modified polyvinyl alcohol resins include trimethylchlorosilane, dimethylchlorosilane, methyltrichlorosilane, vinyltrichlorosilane, diphenyldichlorosilane and triethylfluorosilane. Organosilicon esters such as organohalosilanes, trimethylacetoxysilane and dimethyldiacetoxysilane, organoalkoxysilanes such as trimethylmethoxysilane and dimethyldimethoxysilane, organosilanols such as trimethylsilanol and diethylsilanediol, N-amiethyltrimethoxy Examples include aminoalkylsilanes such as silane, organosilicon isocyanates such as trimethylsilicon isocyanate, and others. It is. 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 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 suitability range of the modified polyvinyl alcohol resin of the present invention varies depending on the degree of modification, that is, the content of the silyl group, the degree of saponification, etc., but an important factor for the gas barrier property which is the object of the present invention. Becomes
The content of the silyl group is usually 30 mol% or less, 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. 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.

These polyvinyl alcohol resins may of course be used alone, but may be used as copolymers with other copolymerizable monomers or as long as they do not inhibit the object of the present invention. It can be used in combination with other resin compounds. Examples of such a resin include polyacrylic acid or esters thereof, polyester resin, polyurethane resin, polyamide resin, epoxy resin, melamine resin, and others.

Polysaccharides are biopolymers synthesized in a biological system by polycondensation of various monosaccharides, and here also include 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 EVOH is a modified one for cross-linking, and preferably a modified one so as to be soluble in alcohol. To impart such properties, a silyl group is introduced into EVOH.

The introduction of the silyl group can be carried out by, for example, 3-isocyanatopropyltriethoxysilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, vinyltrichlorosilane, diphenyldichlorosilane, triethylfluoroorganohalosilane,
It is carried out by reacting a reactive silane compound, such as trimethylacetoxysilane, with a hydroxyl group of EVOH.

The introduction of the silyl group, ie, the silylation, needs to be performed at least so that EVOH becomes soluble in alcohol. Specifically, it is preferable that the silylation rate is 0.2 mol% or more. The upper limit of the silylation ratio is not particularly limited from the viewpoint of alcohol solubility, but is preferably 5 mol% or less, more preferably 2 mol% or less, from the viewpoint of the arrangement of the inorganic layered compound in the present invention. The silylation rate is based on the amount of hydroxyl groups contained in the polyvinyl alcohol resin before silylation.
It shows the ratio of silyl groups introduced after silylation.

Modified EVOH into which the above silyl group has been introduced
Is dissolved in an alcohol-based solvent due to the presence of the introduced silyl group by heating and dissolving with an alcohol or a mixed solvent of alcohol / water. The modified EVOH dissolved in the solvent, on the other hand, cross-links by a part of the introduced silyl group 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.

The coating liquid is a liquid in which the above-mentioned inorganic layered compound and resin are dispersed or dissolved in a dispersion medium. From the viewpoint of the gas barrier properties of the obtained laminate, the dispersion medium is preferably a liquid that swells or cleaves the above-described inorganic layered compound.

The composition ratio of the inorganic layered compound to the resin in the coating liquid is not particularly limited, but generally, the weight ratio of the inorganic layered compound to the resin (inorganic layered compound / resin) is 1/100 to 100%. 100/1, furthermore 1/20 to 10/1
Is preferably within the range. 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.

The concentration of the highly hydrogen-bonding resin and the inorganic layered compound in the coating solution is usually
It is preferably in the range of 0.1% to 70% by weight, more preferably 1% to 15% by weight, and more preferably 4% to 1% by weight.
The range of 0% by weight is more preferable from the viewpoint of productivity.

Gas barrier layer 3 (coating liquid) in the present invention
In the case where the resin used is 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 gas barrier 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, for example, halogenated zirconium such as zirconium oxychloride, zirconium hydroxychloride, zirconium tetrachloride and zirconium bromide; and mineral acids such as zirconium sulfate, basic zirconium sulfate and zirconium nitrate. Zirconium salts 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 organic metal 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 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 organoaluminum 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 step of mixing the resin and the crosslinking agent, the gas barrier layer 3 in which the 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. The molar ratio K is more preferably 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 at the time of blending, for example, after mixing a liquid obtained by dissolving a resin in a solvent and a dispersion obtained by previously swelling and cleaving an inorganic layered compound with a dispersion medium,
A method of removing a solvent and a dispersion medium (method 1), a method in which a dispersion liquid in which an inorganic layered compound is swollen and cleaved by a dispersion medium is mixed with a resin, the resin is dissolved in the dispersion medium, and then the dispersion medium is removed. Method (method 2), a method in which an inorganic layered compound is added to a liquid in which a resin is dissolved in a solvent, and the inorganic layered compound is swelled and cleaved using the solvent as a dispersion medium to form a dispersion, and the solvent is removed (method 3). Alternatively, a method of hot-kneading the resin and the inorganic layered compound (method 4) can be used. The former three methods are preferably used from the viewpoint that a large aspect ratio of the inorganic layered compound can be easily obtained. 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, Microflu
There is an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by idics Corporation or a Nanomizer manufactured by Nanomizer, and a Menton-Gaulin type high-pressure dispersing apparatus such as a homogenizer manufactured by Izumi Food Machinery.

In the above three methods, after removing the solvent or the dispersion medium from the system and laminating, the resulting laminate is heat-aged at, for example, 110 ° C. or more and 220 ° C. or less. Is preferable because it can improve the water resistance (meaning of gas barrier properties after a water resistance environment test).

The aging time is not limited, but it is necessary that the laminated body reaches at least a set temperature. For example, in the case of a method using a hot medium such as a hot air dryer, the time is preferably from 1 second to 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, and microwave heating can be applied.

The above aging treatment exhibits a particularly excellent effect in improving the water resistance when the resin is a high hydrogen bonding resin.

In the present invention, the high-pressure dispersion treatment is, as shown in FIG. 5, by causing a composition mixture obtained by mixing particles to be dispersed or a dispersion medium and the like to pass through a plurality of small tubes 11 at high speed and collide. Dispersing 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. When the composition mixture passes through the small tube 11, the maximum pressure condition is applied to the composition mixture. 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
The above is particularly preferred. In addition, the composition mixture is a thin tube 11
When passing through the inside, the maximum arrival speed of the composition mixture is 1
00 m / s or more, and the heat transfer rate is 1
It is preferably at least 00 kcal / hr.

The principle of the high-pressure treatment in the high-pressure dispersion treatment apparatus used for the high-pressure dispersion treatment will be schematically described.
The composition mixture is sucked into the feeder tube 13 having a larger diameter than the thin tube 11 by the pump 12 and taken in. Subsequently, a high pressure is applied to the composition mixture in the feeder tube 13 by the pump 12. At this time,
Check valve provided on feeder tube 13 (not shown)
As a result, the composition mixture in the feeder tube 13 is
Extruded toward one. Therefore, the composition mixture is in 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, in the case where the flow velocity at the point where the maximum velocity is instantaneously reached with respect to the composition mixture which is the sample to be processed in the portion of the thin tube 11 is 300 m / s, the volume is 1 × 1
When passing through a cube of 0 ^-3 m ³ at 1 / (3 × 10 ⁵ ) sec and the temperature of the composition mixture rises 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 ca.
At 1 / g ° C., it is 3.8 × 10 ⁴ kcal / hr.

In the tubular container according to the present invention, a corona treatment, a flame plasma treatment, an ozone treatment, an electron beam irradiation treatment, and the like are used to improve the adhesion between the gas barrier layer 3 and the container as the base material. An anchoring treatment may be performed between the layers. Although any of these processes is not particularly limited, for example, an anchor process is suitably used.

The anchor treatment is a treatment for forming the anchor layer 2 between the base material 1 and the gas barrier layer 3 as shown in FIG. The material of the anchor layer 2 is not particularly limited, but preferably contains an isocyanate compound and an active hydrogen compound.

As the isocyanate compound contained in the anchor layer 2, tolylene diisocyanate (TD)
I), 4,4'-diphenylmethane diisocyanate (MD
I), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), 4,4'-methylenebiscyclohexyl isocyanate (H12MDI), isophorone diisocyanate (IPDI) and the like.

The active hydrogen compound may be any compound having a functional group capable of binding to an isocyanate compound. Examples thereof include ethylene glycol, diethylene glycol, and the like.
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.

Among the active hydrogen compounds, low molecular weight polyols are particularly preferable, and diols in the low molecular weight polyols are more preferable. Here, diols include ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and the like, and dibasic acids such as adipic acid, azelaic acid, sebacic acid, 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 the amount to be added may be 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 = A) between the number of moles of isocyanate groups (AN) and the number of moles of active hydrogen groups (BN) of the active hydrogen compound
N / BN) is preferably 0.001 or more from the viewpoint of adhesive strength, and is preferably 10 or less from the viewpoint of tackiness and blocking. More preferably, the molar ratio R is in the range of 0.01 or more and 1 or less. The number of moles of the isocyanate group and the active hydrogen group is 1H-NMR, 13C-N
It can be quantified by MR.

The method for laminating the anchor layer 2 on the substrate 1 is not particularly limited, but a coating method using an anchor coating agent solution obtained by dissolving an anchor coating agent containing an isocyanate compound and an active hydrogen compound in a solvent is preferable. . 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 of the anchor coating agent solution applied to the substrate 1 in the form of a film is not particularly limited, but is preferably set so that the dry thickness is 0.01 μm to 5 μm. The larger the coating thickness, the better the heat sealing strength, but the lower the gelboflex resistance. Therefore,
The coating thickness is more preferably from 0.03 μm to 2.0.
μm, more preferably 0.05 μm to 1.0 μm
m.

With the anchor layer 2, it is possible to obtain better adhesion than simply laminating the gas barrier layer 3 on the substrate 1. In order to further improve the adhesiveness between the layers, the gas barrier layer 3 may contain a surfactant.

The surfactant is not particularly limited as long as it can improve the adhesiveness between the anchor layer 2 and the gas barrier layer 3. Examples of the surfactant include anionic surfactants, cationic surfactants, and the like. Zwitterionic and non-ionic surfactants are included.

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. Hydrocarbon-based anionic interfaces such as sulfonic acid type, alkyl sulfate type, sulfate type such as alkyl sulfate polyoxyethylene salt, phosphate type such as alkyl phosphate salt, borate type such as alkyl borate salt Activators, fluorinated anionic surfactants such as sodium perfluorodecanoate and sodium perfluorooctylsulfonate; silicone-based anionics having anionic groups such as polymers having polydimethylsiloxane groups and metal carboxylate Surfactants.

Examples of the cationic surfactant include an amine salt type such as an alkylamine salt and a quaternary ammonium salt type such as an alkyltrimethylammonium salt, a dialkyldimethylammonium salt and an alkyldimethylbenzylammonium salt.

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

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

Among the above surfactants, in particular, those having 6 carbon atoms
Alkyl metal salts of carboxylic acids having an alkyl chain of 24 or less, ether-type nonionic surfactants such as polydimethylsiloxane-polyoxyethylene copolymer (silicone nonionic surfactant), and perfluoroalkyl Fluorine-type nonionic surfactants such as ethylene oxide compounds (fluorine-type nonionic surfactants) are preferred.

In the case where a coating liquid is used when forming the gas barrier layer 3, for example, 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,
Particularly preferred is 0.5 to 0.1% by weight.

In the tubular container according to the present invention, the outermost layer (that is, the layer on the side in contact with the outside air) and the innermost layer (that is, the layer on the side in contact with the contents) of the laminate forming the tube are formed. Preferably, the base resin is used as the base material 1.

The base resin used as the base 1 is not particularly limited. Specific examples of the base resin include papers such as kraft paper, woodfree paper, imitation paper, glassine paper, parchment paper, synthetic paper and various cardboard, polyethylene (low density, high density), ethylene-propylene. Copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer,
Polyolefin resins such as ethylene-methyl methacrylate copolymer and ionomer resin, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, nylon
6, Nylon-6,6, meth-xylene diamine-adipic acid condensation polymer, amide resin such as polymethyl methacrylimide, acrylic resin such as polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile- Butadiene copolymer, acrylonitrile resin such as polyacrylonitrile, cellulose triacetate, hydrophobic cellulose resin such as cellulose diacetate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, halogen-containing resin such as Teflon, polyvinyl alcohol, High hydrogen bonding resins such as ethylene-vinyl alcohol copolymers and cellulose derivatives, polycarbonate resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, polyphenylene N'okishido resins, polymethylene oxide resins, engineering plastics resins such as liquid crystal resins.

Among the above-mentioned base resins, it is particularly preferable to use any one of a polyolefin resin, an ethylene vinyl alcohol copolymer and a polyacrylonitrile resin. Specifically, biaxially stretched polypropylene (OPP), biaxially stretched polyethylene terephthalate (OPET), biaxially stretched nylon (ON
y) or KPP-coated OPP, OPET, ONy coated with polyvinylidene chloride, and polypropylene or polyethylene terephthalate on which a metal or metal oxide such as aluminum, silica or alumina is deposited.
Nylon and OPP (AS-O
P), and OP on which the above metal or metal oxide is deposited
P, OPET, ONy and the like are particularly preferably used.
In the tubular container according to the present invention, it is preferable that the layer made of any one of these resins is the outermost layer and / or the innermost layer of the laminate.

The method of laminating the gas barrier layer 3 on the substrate 1 on which the anchor layer 2 is laminated is not particularly limited, but a coating solution of a resin composition is applied to the surface of the substrate 1, dried and heat-treated. A method of coating, a method of laminating a resin composition film on the anchor layer 2 later, and the like are preferable, and a method of performing the above-described coating is particularly preferable. In addition, at the time of coating, the resin contained in the coating liquid is preferably the high hydrogen bonding resin from the viewpoint of dispersibility.

Examples of the coating method include a roll coating method such as a direct gravure method, a reverse gravure method, a microgravure method, a two-roll beat coating method, a bottom feed three-reverse coating method, a doctor knife method, a die coating method, and a dip coating method. Methods, bar coating methods, and coating methods combining these methods.

The film thickness of the gas barrier layer 3 is 10
μm or less is preferable, and 1 μm or less is more preferable.
Particularly preferred is a range of 1 to 1 μm. In particular, when transparency of the tubular container is required, the thickness is preferably 1 μm or less. In order to obtain sufficient gas barrier properties, the thickness of the gas barrier layer 3 should be 1 nm.
It is preferable that it is above.

Further, in the tubular container according to the present invention, as shown in FIG.
A sealant layer 4 for improving heat sealability may be laminated. The resin used for the sealant layer 4 is
Although not particularly limited, polyethylene (low-density, high-density), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, due to the problem of desorption such as heat seal strength, food aroma, and resin odor. , Ethylene-4-methyl-1-pentene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene- Polyolefin resins such as acrylic acid copolymers, ionomer resins and ethylene-vinyl alcohol copolymers; polyacrylonitrile resins (PAN); polyester resins; and the like are preferably used.

In the tubular container according to the present invention, it is preferable to use the sealant layer 4 having high impact strength, especially when the sealing property of the contents is required. Examples of such a resin include polyethylene and ethylene-ethylene obtained using a metallocene catalyst or a late transition metal complex catalyst.
Polyolefin resins such as α-olefin copolymers are preferred. Such a sealant layer 4 has a density of 0.92.
It is preferably 0 g / cm ³ or less.

The method for laminating the sealant layer 4 is as follows.
Although not particularly limited, for example, a method in which the resin used for the sealant layer 4 is dissolved in a solvent and coated on the gas barrier layer 3 made of an inorganic layered compound and a resin, and the sealant layer 4 is extruded and laminated on the gas barrier layer 3 Preferred examples include a method and a method of dry laminating the sealant layer 4 on the gas barrier layer 3. Further, the interface between the sealant layer 4 and the gas barrier layer 3 may be subjected to a corona treatment, a flame plasma treatment, an ozone treatment, an electron beam treatment, or a treatment such as an anchor coating agent.

The tubular container according to the present invention comprises:
It is preferable that at least one ultraviolet blocking layer is provided in addition to the above-described layers. This ultraviolet ray blocking layer is not particularly limited as long as it does not block ultraviolet rays emitted from the back and reach the contents.
For example, a layer made of a resin containing an ultraviolet absorber can be used.

Further, as described above, the tubular container according to the present invention may have a layer made of a metal such as aluminum, silica or alumina or a metal oxide. Examples of a method for forming the metal or metal oxide layer include a sol-gel method and a vapor deposition method, and are not particularly limited, but a vapor deposition method is preferable.

The thickness of the metal or metal oxide layer is usually in the range of 1 nm to 1000 nm, preferably in the range of 10 nm to 200 nm. The layer made of the metal or the metal oxide may be provided between any of the layers of the laminate. Thereby, the gas barrier property of the tubular container according to the present invention can be improved, and, for example, the content can be shielded from light, so that the content can be further prevented from being deteriorated.

In the conventional gas barrier layer, one of the structures for improving the gas barrier property is usually 7
Aluminum foil having a film thickness in the range of about 20 μm to 20 μm is often laminated. However, when the container in which such aluminum foil is laminated is incinerated after use, the residue (ingot) increases, and the resin layer of the container and the aluminum foil are hardly separated. As a result, there arises a problem that the recyclability of the container is reduced, and it is difficult to reuse the container.

However, since the tubular container according to the present invention has the gas barrier layer 3 made of a resin composition having an inorganic layered compound, the gas barrier layer 3
It is possible to exhibit a very excellent gas barrier property even by using only this. Therefore, in the above-mentioned tubular container, it is not necessary to adopt the configuration of laminating the above-mentioned aluminum foil in order to further improve the gas barrier property, and it is not necessary to adopt a configuration in which a metal or metal oxide deposition layer having a thinner film thickness is used. Is sufficient.

The thickness of the above-mentioned vapor deposition layer is usually from 1 nm to 100 nm.
The thickness is in the range of 0 nm, and the film thickness is smaller than that of the aluminum foil. Therefore, by using less metal or metal oxide per container, it is possible to obtain excellent effects such as improvement in recyclability and reduction in the amount of residue (ingot) in incineration disposal. .

In addition, as long as the effects of the present invention are not impaired,
Various additives such as an ultraviolet absorber, a cross-linking agent, a coloring agent, and an antioxidant may be mixed with at least one of the base material 1, the anchor layer 2, the gas barrier layer 3, and the sealant layer 4.

The tubular container according to the present invention is formed by molding using the laminate having the above-described structure.
Further, a conventionally used surface treatment may be performed, or a protective layer may be formed. The tubular container according to the present invention has an oxygen permeability of 1 mL / m ² ···
day · atm or less, preferably 0.1 mL /
m ² · day · atm or less, more preferably 0.05 mL /
m ² · day · atm or less.

When the oxygen permeability is set in this manner, even during storage, there is almost no invasion of oxygen from the outside air through the tubular container, and deterioration of the contents is more effectively suppressed. can do. Also, for example, even if the contents contained in the tubular container contain volatile components, they do not diffuse into the outside air during storage, and can be stored for a longer period of time than conventional tubular containers. Becomes

[0142] The gas barrier layer 3
Does not include an aluminum foil used as a gas barrier layer in a conventional tubular container. Therefore, as described above, it is possible to further reduce the load on the environment, and it is possible to realize an excellent tubular container that can replace the conventional one in which a laminate having an aluminum foil is formed. .

The shape of the tubular container according to the present invention is not particularly limited as long as it is tubular. Specifically, the tubular body whose lower end is closed and the tubular body It is preferable to have a configuration that has a shoulder continuous with the upper end, a mouth and neck continuous with the shoulder, and a cap detachably engaged with the mouth and neck.

The contents contained and packaged in the tubular container according to the present invention are not particularly limited, but include paste foods. Examples of the pasty food include seasonings or condiments such as kneaded mustard, kneaded wasabi, ginger, grated garlic, and the like.

The above seasonings or condiments often contain a large amount of aroma components, but the aroma components may be immediately deteriorated by contact with the outside air (particularly oxygen). Furthermore, many of these fragrance components are highly volatile, and if the container lacks gas barrier properties, the fragrance will disappear over time,
The quality as a seasoning or a condiment will be extremely deteriorated.

However, the tube-shaped container according to the present invention not only has excellent gas barrier properties but also has excellent durability, so that the food can be stored for a long time, Pinholes and the like do not occur in the gas barrier layer 3 due to the physical force applied when the food is squeezed from the food. Therefore, the food can be satisfactorily stored.

Further, in the tubular container according to the present invention, the thickness of the laminated body forming the tubular body can be made smaller than that of the conventional tubular container. Therefore, the tubular container storing the food as a content can be made more compact.
That is, the tubular container according to the present invention can be suitably used as a food packaging material.

Further, the contents are not limited to the above-mentioned foods, but may also include quasi-drugs including pharmaceuticals and toiletries. Specific examples include pharmaceuticals for application such as anti-itching agents and ointments, and quasi-drugs such as toothpastes and cosmetics.

In many cases, these drugs (in this embodiment, quasi-drugs are also included in the drug) contain components which are liable to be degraded by contact with the outside air.
Furthermore, if the gas barrier of the tubular container is low because it contains a lot of volatile components, the quality of the contents may be deteriorated and the container may become unusable, but if the tubular container according to the present invention is used, In addition, deterioration and deterioration of the contents (pharmaceuticals) can be suppressed as much as possible and can be stably stored for a longer period. Therefore, the tubular container according to the present invention can be suitably used as a packaging material for pharmaceuticals.

Further, as the contents stored and packaged in the tubular container according to the present invention, in addition to the above-mentioned foods and pharmaceuticals, there may be mentioned electronic materials and the like.

As described above, the tubular container according to the present invention is formed using a laminate having a gas barrier layer made of a resin composition having an inorganic layered compound. Therefore, the deterioration and deterioration of the contents during storage can be more effectively suppressed, and even when the contents are squeezed out of a tube, no pinholes are formed in the gas barrier layer, and the The contents can be stored stably over a period of time.

Further, since the above-mentioned tubular container does not use aluminum foil, the influence on the environment can be reduced and the laminated container can be made thinner than before, so that the shape of the tubular container can be reduced. It can be compact.

Further, a food packaging material and a pharmaceutical packaging material according to the present invention include the above-mentioned tubular container. Therefore, foods and pharmaceuticals that deteriorate due to temperature change or contact with air or contain a large amount of volatile components can be stored well for a long period of time. The use of the above-mentioned tubular container is not limited to packaging of foods or pharmaceuticals, but can be used for any packaging in such a form.

[0154]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In addition,
In this example, various physical properties of the laminate used for the tubular container were measured as follows.

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

[Measurement of Particle Size] Using a laser diffraction / scattering type particle size distribution analyzer (LA910, manufactured by HORIBA, Ltd.), the volume-based median of particles considered to be inorganic layered compounds present in the resin matrix of the medium. The diameter was measured as a particle diameter L. The undiluted dispersion was measured at a light wavelength of 50 μm in a paste cell, and the diluent of the dispersion was measured at a light wavelength 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 obtained, and further, from the diffraction measurement of the resin composition, it was confirmed that there was a portion where the interplanar spacing d of the inorganic layered compound was widened. Using the particle diameter L obtained by the above-described method, the aspect ratio Z is calculated as follows: Z = L / a
It calculated by the formula of.

[Oxygen Permeability Measurement] Based on JIS K7126, an oxygen permeability measuring device (OX-TRANML: M
OCON) at 23 ° C. and 50% RH.

[Example] Dispersing pot [Product name: Despa MH-
L, manufactured by Asada Tekko Co., Ltd.], 1410 g of ion-exchanged water (specific electric conductivity 0.7 μS / cm or less) was added, and polyvinyl alcohol [PVA117H; manufactured by Kuraray Co., Ltd.
Saponification degree: 99.6%, polymerization degree: 1700] and 50 g under low-speed stirring (1500 rpm, peripheral speed: 4.10 m / min).
Heat to 5 ° C., stir for 1 hour, and dissolve.

Next, the temperature was lowered to 60 ° C. while stirring, and 15 g of 1-butanol was added dropwise to adjust the final 1-butanol fraction to 1% by weight. Then, 25 g of natural montmorillonite (Kunipia F; manufactured by Kunimine Industry Co., Ltd.) was added as powder, and after confirming that montmorillonite was substantially precipitated in the liquid, high-speed stirring (31)
(00 rpm, peripheral speed: 8.47 m / min) for 90 minutes to obtain a resin composition mixed solution (A) having a total solid content concentration of 5 wt%. (The particle size of the cleaved natural montmorillonite (Kunipia F) is 560 nm, the a value obtained from powder X-ray diffraction is 1.2156 nm, and the aspect ratio (Z) is 200 or more.) Further, 1-butanol 9
A liquid obtained by adding 0.18 g of a nonionic surfactant SH3746 (polyoxyethylene-methylpolysiloxane copolymer, manufactured by Dow Corning Toray Co., Ltd.) to a mixed liquid of 2 g and 277 g of isopropyl alcohol was designated as (B). I do.

The solution (B) was added to the solution (A) under low-speed stirring (15
00 rpm, peripheral speed 4.10 m / min), and further added titanium acetylacetonate [TC1
00, manufactured by Matsumoto Pharmaceutical Co., Ltd.] under low-speed stirring (1500
(3.3 rpm) at a peripheral speed of 4.10 m / min).

A 280 μm thick polyacrylonitrile (PAN) film [Zeklon, Mitsui Toatsu Chemicals, Inc.]
Made by the surface corona treatment of
An anchor coat agent [Adcoat AD
335 / CAT10 = 15/1 (weight ratio): manufactured by Toyo Morton Co., Ltd.] (test coater; manufactured by Yasui Seiki Co., Ltd .: microgravure coating method, coating speed 3 m / min, drying temperature 80 ° C.). . The dry thickness of the anchor coat layer was 0.15 μm.

Further, as TOP coating liquid, coating liquid 1
By gravure coating (test coater; manufactured by Yasui Seiki Co., Ltd .: microgravure coating method, coating speed 3 m / min, drying temperature 100)
° C) to obtain a coating film having a gas barrier layer based on the coating liquid 1 formed on the anchor coat layer. The dry thickness of the gas barrier layer was 0.5 μm.

Next, a 12 μm-thick polyethylene terephthalate (PET) film (Espet T400, manufactured by Toyobo) is further provided on the gas barrier layer of the coating film.
Are laminated, and then a 280-μm-thick polyacrylonitrile (PAN) [Zeklon, Mitsui Toatsu Chemicals, Inc.]
As the outermost layer to obtain a laminate.

This laminate was formed into a tube to obtain a tube-shaped container according to the present invention. When the oxygen permeability was measured to evaluate the gas barrier properties of this tubular container, it was 0.1 mL / m ² · day · atm.
Therefore, it is understood that the tubular container according to the present invention can exhibit excellent preservability while remarkably suppressing deterioration of the contents.

[0166]

As described above, the tubular container according to the first aspect of the present invention has a structure having a laminate having a gas barrier layer made of a resin composition having an inorganic layered compound. .

As described above, the tubular container according to the second aspect of the present invention has, in addition to the configuration according to the first aspect,
The laminate has a structure in which at least one metal or metal oxide layer is further provided.

[0168] In the tubular container according to the third aspect of the present invention, as described above, in addition to the configuration of the first or second aspect, the laminate further has at least one polyolefin resin layer. Configuration.

As described above, in the tubular container according to the fourth aspect of the present invention, in addition to the configuration according to the first, second or third aspect, the laminate further includes at least one biaxially stretched film layer. It is a configuration that it has.

As described above, the tubular container according to the fifth aspect of the present invention has an oxygen permeability of 1 mL / m ² · da in addition to the configuration according to any one of the first to fourth aspects.
y ・ Atm or less.

As described above, in the tubular container according to the sixth aspect of the present invention, in addition to the configuration according to any one of the first to fifth aspects, the inorganic layered compound swells in a dispersion medium.・ Cleaved configuration.

As described above, in the tubular container according to the seventh aspect of the present invention, in addition to the structure according to any one of the first to fifth aspects, the gas barrier layer has an inorganic layered compound. This is a configuration obtained by subjecting a mixed solution of the resin composition to a high-pressure dispersion treatment.

As described above, the tubular container according to the eighth aspect of the present invention has the following features:
The high pressure dispersion treatment is performed under a pressure condition of 100 kgf / cm ² or more.

As described above, the tubular container according to the ninth aspect of the present invention has an aspect ratio of the inorganic layered compound of 50 to 50 in addition to the constitution according to any one of the first to eighth aspects. The configuration is within the range of 5000.

According to the tenth aspect of the present invention, as described above, the tubular container according to any one of the first to ninth aspects is provided.
In addition to the constitution described in the section, the aspect ratio of the inorganic layered compound is in the range of 200 to 3000.

[0176] According to the eleventh aspect of the present invention, as described above, in addition to the configuration according to any one of the first to tenth aspects, the resin composition further comprises a high hydrogen bonding resin. And the weight ratio between the inorganic layered compound and the high hydrogen bonding resin is in the range of (1/100) to (100/1).

As described above, in the tubular container according to the twelfth aspect of the present invention, in addition to the constitution according to the eleventh aspect, the high hydrogen bonding resin may be a hydrogen bonding group or an ionic resin per unit weight of the resin. More than 30%, 50%
The configuration is as follows.

As described above, in the tubular container according to the thirteenth aspect of the present invention, in addition to the constitution according to the eleventh or twelfth aspect, the high hydrogen bonding resin may be a polyvinyl alcohol and a modified or modified polyvinyl alcohol. The composition is a saccharide or an ethylene-vinyl alcohol copolymer and a modified product thereof.

According to the fourteenth aspect of the present invention, as described above, the outermost layer and / or the outermost layer of the laminate is provided in addition to the configuration according to any one of the first to thirteenth aspects. The inner layer is a polyolefin resin, ethylene-
This is a configuration in which the layer is formed of a resin selected from any one of a vinyl alcohol-based resin and a polyacrylonitrile-based resin.

According to a fifteenth aspect of the present invention, as described above, in addition to the configuration of the first aspect, the laminated body has an ultraviolet shielding layer. This is the configuration.

Therefore, in each of the above-described configurations, a load on the environment can be reduced even when disposed after use, and a tube-like container having an excellent gas barrier property that can replace a laminate having an aluminum foil is realized. The effect that it becomes possible is produced.

The food packaging material according to claim 16 of the present invention provides the food packaging material according to any one of claims 1 to 15 as described above.
It is the structure provided with the tubular container as described in the item.

Further, the pharmaceutical packaging material according to the seventeenth aspect of the present invention has a configuration using the tubular container according to any one of the first to fifteenth aspects as described above.

Therefore, with the above-mentioned structure, foods such as wasabi paste, paste mustard, ginger, grated garlic and the like, and pharmaceuticals and quasi-drugs such as toothpaste, cosmetics, ointments and the like can be stored for a good period of time. This has the effect.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a gas barrier layer of a laminate used as a tubular container according to one embodiment of the present invention.

FIG. 2 is an X-ray diffraction graph of the inorganic layered compound for calculating the “unit thickness a” of the inorganic layered compound in the laminate.

FIG. 3 is an X-ray diffraction graph of an inorganic layered compound for calculating “plane spacing d” of the inorganic layered compound in the laminate.

FIG. 4 calculates the “plane spacing d” of the inorganic layered compound when the peak corresponding to the “plane spacing d” overlaps the halo (or background) and is difficult to detect in the graph of FIG. It is an X-ray diffraction graph at the time.

FIG. 5 is an explanatory view schematically showing a high-pressure dispersion process used in the production of the laminate.

FIG. 6 is a schematic sectional view showing an example of a laminate used as a tubular container according to the present invention.

FIG. 7 is a schematic cross-sectional view showing another example of a laminate used as a tubular container according to the present invention.

[Explanation of symbols]

 1 base material (outermost layer and innermost layer) 2 anchor layer 3 gas barrier layer 4 sealant layer

Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 27/00 B32B 27/00 H 27/28 102 27/28 102 27/30 102 27/30 102 B65D 81/24 B65D 81/24 A

Claims (17)

[Claims] 1. A tubular container comprising a laminate having a gas barrier layer made of a resin composition having an inorganic layered compound. 2. The tubular container according to claim 1, wherein said laminate further has at least one metal or metal oxide layer. 3. The laminate according to claim 1, further comprising at least one polyolefin resin layer.
Or the tubular container according to 2. 4. The laminate according to claim 1, further comprising at least one biaxially stretched film layer.
4. The tubular container according to 2 or 3. 5. The tubular container according to claim 1, wherein the oxygen permeability is 1 mL / m ² · day · atm or less. 6. The method according to claim 1, wherein said inorganic layered compound swells and cleaves in a dispersion medium.
Item 14. The tubular container according to Item. 7. The gas barrier layer according to claim 1, wherein the gas barrier layer is obtained by subjecting a mixed solution of a resin composition having an inorganic layered compound to high-pressure dispersion treatment.
Item 14. The tubular container according to Item. 8. The method according to claim 1, wherein the high pressure dispersion treatment is performed at 100 kgf / cm ^2.
The tubular container according to claim 7, which is processed under the above pressure conditions. 9. An inorganic layered compound having an aspect ratio of 50 to 50.
The tubular container according to any one of claims 1 to 8, wherein the range is within a range of 5000. 10. An inorganic layered compound having an aspect ratio of 200.
The tubular container according to any one of claims 1 to 9, wherein the range is in the range of ~ 3000. 11. The method according to claim 1, wherein 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 in the range of (1/100) to (100/1). The tubular container according to any one of claims 1 to 10, characterized in that: 12. The tubular container according to claim 11, wherein the high hydrogen bonding resin has a molar percentage of hydrogen bonding groups or ionic groups per unit weight of the resin of 30% or more and 50% or less. . 13. The tube according to claim 11, wherein the high hydrogen bonding resin is polyvinyl alcohol and a modified product thereof, or a polysaccharide, or an ethylene-vinyl alcohol copolymer and a modified product thereof. Container. 14. An outermost layer and / or an innermost layer of the laminate is a layer made of a resin selected from one of a polyolefin resin, an ethylene-vinyl alcohol resin, and a polyacrylonitrile resin. The tubular container according to any one of claims 1 to 13, wherein: 15. The tubular container according to claim 1, wherein the laminate has an ultraviolet shielding layer. 16. A food packaging comprising the tubular container according to claim 1. Description: 17. A packaging material for a medicine, comprising the tubular container according to claim 1. Description: