JP2000254996A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which shows superb thermal stability and heat-resistant gas barrier properties. SOLUTION: This laminate comprises a heat-curable resin layer 2 consisting of a heat-curable resin, a layer 3 containing an inorganic laminator compound (A) having an inorganic laminator compound (A) and a layer 4 containing an inorganic compound (B) having an inorganic compound (B) containing at least one kind of element selected from the group of an alkaline metal, an alkaline earth metal, a transition element and the Group 3B, Group 4B and Group 5B elements of the periodic table, all being laminated in that order.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a layer comprising a thermosetting resin, a layer having an inorganic layered compound (A), an alkali metal, an alkaline earth metal, a transition element,
And a layer having an inorganic compound (B) containing at least one element selected from the group consisting of a group B element, a group 4B element, and a group 5B element. The present invention relates to a laminated body having excellent characteristics.

[0002]

2. Description of the Related Art In recent years, attempts have been made to obtain a laminate excellent in high hardness, chemical resistance, gas barrier properties and the like by forming a thin film made of an inorganic compound. For example, JP-A-10-44299 discloses that a layer composed of an inorganic layered compound and a polymer and an inorganic layer composed of a metal and / or a metal oxide are laminated on a substrate composed of a thermoplastic polymer, and a gas barrier property is obtained. There is disclosed a technique for increasing the pressure.

[0003]

However, when a substrate made of a thermoplastic polymer is used, the outermost inorganic layer is easily broken due to plasticization or thermal expansion due to high temperature, and the performance of the inorganic layer is high. In particular, there is a problem that the gas barrier property is easily deteriorated. For this reason, there is a demand for a laminate that has improved thermal stability and does not cause a decrease in the gas barrier properties of the inorganic layer due to heating, that is, a laminate that has excellent heat-resistant gas barrier properties.

[0004] The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a laminate having good thermal stability and excellent heat-resistant gas barrier properties.

[0005]

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, the present inventors have found that a layer made of a thermosetting resin, a layer having an inorganic layered compound (A), an alkali metal Earth metals, transition elements, and periodic table 3B
A layer having an inorganic compound (B) containing at least one element selected from the group consisting of a group IV element, a group 4B element, and a group 5B element, in this order, has good thermal stability, and has a heat-resistant gas barrier. It has been found that a laminate having excellent properties can be obtained, and the present invention has been completed.

That is, in order to solve the above-mentioned problems, the laminate of the present invention has a first layer, a second layer, and a third layer laminated in this order, and the first layer is made of a thermosetting resin. The second layer is a layer having an inorganic layered compound (A), and the third layer is an alkali metal, an alkaline earth metal, a transition element, and a 3B group element and a 4B group element in the periodic table. ,
It is a layer having an inorganic compound (B) containing at least one element selected from the group consisting of group 5B elements.

According to the above configuration, in the second 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 second layer. By the labyrinth effect of the inorganic layered compound, gas barrier properties can be imparted to the obtained laminate together with the third layer.

In addition, in the above structure, since the first layer is made of a thermosetting resin, the second layer or the third layer is broken due to plasticization or thermal expansion due to high temperature, and in particular, a conventional laminate is used. The destruction of the inorganic layer made of metal or the like (corresponding to the third layer), which is a problem in the above, can be prevented. Therefore, according to the above configuration, the thermal stability is improved, so that the performance of the second and third layers, such as gas barrier properties, can be sufficiently exhibited even by heating. Therefore, according to the above configuration, a laminate having excellent heat-resistant gas barrier properties can be provided.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below with reference to FIGS. As shown in FIG. 1, the laminate according to the present invention includes a thermosetting resin layer 2 (first layer) made of a thermosetting resin and an inorganic layered compound (A) -containing layer having an inorganic layered compound (A). 3
(B) an inorganic compound containing an alkali metal, an alkaline earth metal, a transition element, and at least one element selected from the group consisting of a group 3B element, a group 4B element, and a group 5B element Compound (B) containing layer 4 having
(Third layer) are laminated in this order.
The laminate according to the present invention has excellent thermal stability by having the above-described configuration, and particularly has an oxygen permeability (m
1 / atm · m ² · day) is 10 or less, which is an excellent heat-resistant gas barrier property.

In the laminate, in order to impart sufficient strength, for example, tensile strength, to the laminate, as shown in FIG.
The thermosetting resin layer 2 may be laminated on the surface opposite to the laminating surface of the layer 3 containing the inorganic layered compound (A). According to the present invention, the support layer 1, the inorganic layered compound (A) -containing layer 3, and the inorganic compound (B) -containing layer 4 include the support layer 1, the inorganic layered compound (A) -containing layer 3, Provided with the thermosetting resin layer 2 interposed therebetween, the inorganic layered compound (A) -containing layer 3 and the inorganic compound (B) due to plasticization or thermal expansion of the support layer 1 due to, for example, high temperature. The destruction of the containing layer 4 can be prevented. Therefore, according to the above configuration, even when heated, the inorganic layered compound (A) -containing layer 3 and the inorganic compound (B) -containing layer 4 have various performances, particularly, the inorganic compound (B) -containing layer 4 has It is possible to sufficiently exhibit performance such as gas barrier properties, and it is possible to obtain a laminate having excellent heat-resistant gas barrier properties.

In the present invention, the support layer 1 may be appropriately selected according to the use, and is not particularly limited. For example, the support layer 1 may be used in the below-mentioned applications, particularly in applications requiring a heat-resistant gas barrier property. In order to use for microwave heating cooking or sterilization packaging, retort / boil sterilization packaging, high temperature material / high temperature liquid packaging, etc., it can hold liquid contents such as soup, paste food, etc., and It is preferable that the material has water repellency capable of preventing water penetration and leakage, and solvent resistance to a solvent such as alcohol which dissolves an aromatic substance.

The shape of the support layer 1 is not particularly limited, and may be a desired shape according to, for example, containers (bottles, trays, etc.), films (including sheets), tubes, and other various molded products. And preferably in the form of a film.

As a specific example of the support layer 1, a film-shaped one may be mentioned, for example, metal foil such as stainless steel foil, copper foil, silver foil, gold foil, aluminum foil; kraft paper, woodfree paper, structural paper, Glassine paper, parchment paper, synthetic paper,
Paper such as cardboard; cloth made of natural fiber, cloth made of synthetic fiber, cloth such as nonwoven fabric; sheet glass; ceramic sheet; resin film made of thermoplastic polymer; Among them, the base material used for the support layer 1 is preferably at least one base material selected from the group consisting of metal foil, paper, cloth, and synthetic resin film.

The synthetic resin film may be made of, for example, polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer,
Polyolefin resins such as ethylene-hexene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, and ionomer resin; polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate Polyester resin such as Nylon
6, Nylon-6,6, meth-xylenediamine-adipic acid condensation polymer, amide resin such as polymethylmethacrylimide; acrylic resin such as polymethylmethacrylate; polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile- Styrene-acrylonitrile resins such as butadiene copolymer and polyacrylonitrile; hydrophobicized cellulose resins such as cellulose triacetate and cellulose diacetate; halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and Teflon; polyvinyl Hydrogen bonding resins such as alcohols, ethylene-vinyl alcohol copolymers and cellulose derivatives; polycarbonate resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, polyphenylene Kishido resins, polymethylene oxide resins, engineering plastics resins such as liquid crystal polymer; and the like.

Among these resin films, a stretched film, in particular, a biaxially stretched film is more preferable because of excellent strength such as tensile strength. Biaxially stretched polyamide, biaxially stretched polyethylene terephthalate, biaxially stretched polyethylene A film composed of at least one selected from the group consisting of naphthalate and biaxially oriented polypropylene is more preferred. Among these, a film obtained by biaxially stretching a base resin such as polypropylene, polyethylene terephthalate, polyethylene naphthalate, or nylon, and further coating with polyvinylidene chloride called K coat; these polypropylene, polyethylene terephthalate, and polyethylene Naphthalate,
A film obtained by biaxially stretching a base resin such as nylon and further evaporating aluminum, silica, alumina or the like; OPP (AS-OP) for strong antistatic use; As the stretched film, a film having a higher tensile strength is more preferable, and a film having an elongation at break of 700% or less is preferable, and a film having a tensile elongation of 500% or less is more preferable.
Although a stretched film is suitably used as the resin film, a film made of the unstretched resin may be used.

In the present invention, the thermosetting resin layer 2
The thermosetting resin used for is a synthetic resin that loses thermoplasticity due to the reaction of unreacted groups remaining in the polymer due to heating, the degree of polymerization increases, the crosslinking proceeds, and a network structure is generated. Show.

The thermosetting resin is not particularly limited as long as it can impart thermal stability to the laminate according to the present invention, and is preferably, but not limited to, an epoxy resin, a xylene resin, or an oligo resin. Ester acrylate, guanamine resin, diallyl phthalate resin, resorcinol resin, epoxy acrylate resin, phenol resin,
Unsaturated polyester resins, furan resins, polyimide resins, urethane resins, maleic resins, melamine resins, urea resins, and the like. These thermosetting resins have a plurality of reactive groups for expressing thermosetting properties in one molecule. One of these thermosetting resins may be used alone, or a mixture of them may be used as appropriate. Among these thermosetting resins, urethane resins composed mainly of an isocyanate compound and an active hydrogen compound are more preferably used from the viewpoint of water resistance of the obtained laminate.

Hereinafter, the urethane resin will be described in detail. The isocyanate compound used in the urethane resin,
Tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), 4,4'-methylenebiscyclohexyl isocyanate (H12MDI), isophorone diisocyanate (IPDI) And the like.

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

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

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

The method for laminating the thermosetting resin layer 2 on the support layer 1 is not particularly limited. For example, a coating method using a thermosetting resin solution obtained by dissolving the thermosetting resin in a solvent, A film made of the thermosetting resin,
A method of laminating on the surface of the support layer 1 is preferably used.

The solvent used for coating the thermosetting resin solution is mainly an organic solvent, for example, alcohols, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, esters, Ketones, ethers,
Halogenated hydrocarbons and mixed solvents thereof are exemplified.

Examples of the method used for coating the thermosetting resin solution include a gravure method such as a direct gravure method, a reverse gravure method, and a microgravure method; a two-roll beat coating method;
A roll coating method such as the reverse coating method; a doctor knife method; a die coating method; a dip coating method; a bar coating method; a spray coating method; a spin coating method;

The interface between the support layer 1 and the thermosetting resin layer 2 may be subjected to a treatment such as a corona treatment, a flame plasma treatment, an ozone treatment, an electron beam treatment, and an anchor treatment. Further, these processes may be incorporated in an in-line multilayer forming machine and performed in-line. still,
Performing these treatments in-line means that the apparatus is sequentially installed on the same line along the flow direction during the production of the laminate according to the present invention, and the production process (layer formation process) of the laminate is performed. And the above process are immediately performed in a series of operations.

In the present invention, the inorganic layered compound (A) used in the inorganic layered compound (A) -containing layer 3 is, as shown in FIG. 3, a unitary crystal layer 31. It is not particularly limited as long as it has an inorganic compound.

Specific examples of the inorganic layered compound (A) include, for example, graphite, phosphate derivative type compounds (zirconium phosphate compounds, etc.), chalcogenides,
And clay minerals. The chalcogenide includes a group IV (Ti, Zr, Hf) and a group V (V, Nb,
Ta) and a dichalcogenide of group VI (Mo, W), wherein the chemical formula is MX ₂ (wherein M represents an element of the above group IV and group VI, and X represents a chalcogen (S, Se,
Which represents Te).

The inorganic layered compound (A) may be used singly or in a combination of two or more. Among the inorganic layered compounds (A), those having the property of swelling or cleaving in a solvent are preferable because they easily give a large aspect ratio and can form a smooth and uniform layer. Those having the property of cleavage (swelling in a solvent and cleavage) are more preferable. The swelling property and cleavage property of the inorganic layered compound (A) in a solvent can be evaluated by a swelling property test and a cleavage property test described below.

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

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

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

The swellability of the inorganic layered compound (A) was determined by the swellability measurement test described above.
The volume of the dispersion layer (that is, the volume after swelling of 2 g of the inorganic layered compound (A)) is preferably about 5 ml or more (that is, the swelling value of 5 or more), and about 20 ml or more (that is, the swelling value of 20 g or more).
Is more preferable.

On the other hand, the cleavage property of the inorganic layered compound (A) is as follows.
In the cleavage test described above, the volume of the dispersion layer of the inorganic layered compound (A) (that is, the volume after swelling of the inorganic layered compound (A) (equivalent to about 2 g) contained in 100 ml of the dispersion) is about 5 ml or more. (Ie, a cleavage value of 5 or more), and preferably about 20 ml or more (ie, a cleavage value of 20 or more).
Is more preferable.

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

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

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

As the dispersion medium for swelling or cleaving the inorganic layered compound (A), for example, when the inorganic layered compound (A) is a natural swellable clay mineral, water; methanol, ethanol, propanol, isopropanol ,
Alcohols such as ethylene glycol and diethylene glycol; dimethylformamide; dimethyl sulfoxide; acetone; and the like. Among them, water and alcohols such as methanol are more preferable. When the inorganic layered compound (A) is an organically modified clay mineral, examples of the dispersion medium include aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as ethyl ether and tetrahydrofuran; acetone and methyl ethyl ketone. And ketones such as methyl isobutyl ketone; n-pentane, n
Aliphatic hydrocarbons such as 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; dimethyl sulfoxide; methyl cellosolve; silicone oil;

In the present invention, the above-mentioned inorganic layered compound (A) in the cleaved state has a particle size of preferably 5 μm or less, more preferably 3 μm or less, particularly preferably 1 μm or less, and the aspect ratio is preferably 10
Within the range of 10,000 to 10,000, more preferably 10 to 3,0.
00, more preferably 30 to 2,000, particularly preferably 200 to 1000. In particular, if the aspect ratio is less than 10, the gas barrier properties (including the heat-resistant gas barrier properties) are not sufficient, and 1
Those greater than 000 are technically difficult and economically expensive.

In the present invention, the aspect ratio indicates the ratio of the major axis to the thickness of the inorganic layered compound (A) and is used as a parameter indicating the state of the layer. The average particle size and aspect ratio of the inorganic layered compound (A) are, for example,
It can be measured by the following method.

The average particle size of the inorganic layered compound (A) is as follows:
It can be measured by 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, a method based on image processing after photographing in a submerged microscope, and the like.

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

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

For this reason, when the inorganic layered compound (A) -containing layer 3 contains components other than the inorganic layered compound (A),
For example, when the average particle size of the inorganic layered compound (A) is measured in the presence of a resin, a solution containing the resin, for example, an aqueous resin solution is transparent and substantially less scattered, and is derived from the particles of the inorganic layered compound (A). When the scattering is dominant, information on only the particle size distribution of the particles of the inorganic layered compound (A) can be obtained regardless of the presence or absence of the resin. Therefore, a method based on the diffraction / scattering method is suitably used.

Thus, the particle size of the inorganic layered compound (A) used in the present invention refers to a particle size obtained by a diffraction / scattering method in a dispersion medium. Layer 3 containing inorganic laminar compound (A)
When the composition further contains a resin in addition to the inorganic layered compound (A), the inorganic layered compound (A) -containing layer 3 (that is, a layer composed of a resin composition containing the inorganic layered compound (A) and the resin)
Although it is extremely difficult to measure the true particle size in the solution, the inorganic layered compound (A) is sufficiently swollen and cleaved with a dispersion medium of the same type as the dispersion medium used in the diffraction / scattering method to obtain an inorganic layered compound (A). A) In the case of compounding with the resin 32 in the containing layer 3, the particle size of the cleaved inorganic layered compound (A) in the inorganic layered compound (A) containing layer 3 shown in FIG. It can be considered that it corresponds to the particle size of the inorganic layered compound (A).

Hereinafter, a method for measuring the average particle size of the inorganic layered compound (A) by the diffraction / scattering method will be described. The particle size distribution and the average particle size of the inorganic layered compound (A) obtained by the above-mentioned diffraction / scattering method can be calculated from the diffraction / scattering pattern obtained when light is passed through a dispersion of the inorganic layered compound (A). Thus, the particle size distribution can be obtained by calculating the particle size distribution that is most consistent with the diffraction / scattering pattern.

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

Next, as a method for measuring the aspect ratio of the inorganic layered compound (A), a method for measuring the aspect ratio (aspect ratio (Z)) of the inorganic layered compound (A) having swelling and cleavage properties will be described. I do.

The above aspect ratio (Z) is defined as Z = L / a
Is the ratio determined from the relationship shown by Where L
Represents the particle size (volume-based median diameter) of the inorganic layered compound (A) obtained by the particle size measurement method by the above-mentioned diffraction / scattering method in the dispersion liquid, and a represents the cleaved inorganic layered compound shown in FIG. The unit thickness of the compound (A), that is, the thickness of the unit crystal layer 31 of the inorganic layered compound (A) is shown.

The "unit thickness a" of the inorganic layered compound (A) is determined by the powder X-ray diffraction method described later ("Guide for Instrumental Analysis (a)" (1985, published by Kagaku Dojinsha, supervised by Jiro Shiokawa). (See page 69), etc., based on the measurement of the inorganic layered compound (A) alone. More specifically, as schematically shown in the graph of FIG. 4, the Bragg equation (nλ = 2Ds) is obtained from the angle θ corresponding to the lowest angle peak among the diffraction peaks observed by X-ray diffraction.
inθ, n = 1, 2, 3,...) is defined as “unit thickness a”.

In addition, the inorganic layered compound (A) -containing layer 3
Are components other than the inorganic layered compound (A) (for example, resin 3
2), the layer containing the inorganic layered compound (A) 3
Can be used by powder X-ray diffraction of the composition (resin composition) forming the above and the inorganic layered compound (A) alone.

When the inorganic layered compound (A) -containing layer 3 contains the resin 32 in addition to the inorganic layered compound (A), it corresponds to the inorganic layered compound (A) -containing layer 3 obtained by removing the solvent from the dispersion. When powder X-ray diffraction of the resin composition,
Usually, the plane distance of the inorganic layered compound (A) in the resin composition can be determined as “plane distance d” shown in FIG.

More specifically, as schematically shown in the graph of FIG. 5, the diffraction observed at a lower angle (larger interval) than the diffraction peak position corresponding to the above “unit thickness a”. Among the peaks, the interval corresponding to the peak at the lowest angle side is “surface interval d” (where a <d).

As a result of the powder X-ray diffraction, as schematically shown in the graph of FIG. 6, it is difficult to detect the peak corresponding to the “plane spacing d” by overlapping the halo (or background). In such a case, the area of the portion excluding the base line on the lower angle side than 2θd is set as the peak corresponding to “surface interval d”. Here, “θd” is a diffraction angle corresponding to “(unit thickness a) + (width of single resin chain)”. For details of the method of determining the "surface distance d", see, for example, pages 35 and below and page 271 and below of "Encyclopedia of Clay" (ed., 1985, Asakura Shoten Publishing Co., Ltd., edited by Shuichi Iwao). Will be more apparent in

As described above, the integrated intensity of the diffraction peak observed in the powder X-ray diffraction of the resin composition containing the inorganic layered compound (A) is the diffraction intensity corresponding to the reference diffraction peak (that is, the diffraction corresponding to the “plane spacing d”). The relative ratio of the peak to the integrated intensity is preferably 2 or more, more preferably 10 or more.

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

When the inorganic layered compound (A) -containing layer 3 contains the resin 32, it is possible to directly measure the “true aspect ratio” of the inorganic layered compound (A) in the inorganic layered compound (A) -containing layer 3. Extremely difficult. Therefore, when the inorganic layered compound (A) -containing layer 3 contains the resin 32, the above-mentioned “aspect ratio (Z)” is not necessarily the same as that of the inorganic layered compound (A) in the inorganic layered compound (A) -containing layer 3. Although not necessarily equal to the “true aspect ratio”, it is appropriate to approximate the “true aspect ratio” with the “aspect ratio (Z)” for the following reasons.

That is, the "plane spacing 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 (A) alone.
And there is a relationship of a <d, and when the value of k ((da) value) is equal to or greater than the width of the single resin chain in the resin composition, In this case, the resin 32 is inserted between the layers of the inorganic layered compound (A). Accordingly, the thickness of the inorganic layered compound (A) in the inorganic layered compound (A) -containing layer 3 is approximated by the above “unit thickness a”, that is, the resin 3 of the inorganic layered compound (A) -containing layer 3
"True aspect ratio" of the inorganic layered compound (A) in No. 2
There is sufficient validity that the above is approximated by the “aspect ratio (Z)” in the dispersion liquid of the inorganic layered compound (A).

As described above, it is extremely difficult to measure the true particle size of the inorganic layered compound (A) in the resin 32 of the layer 3 containing the inorganic layered compound (A). Layered Compound (A) in Resin 32
Can be considered to correspond to the particle size L of the inorganic layered compound (A) in the dispersion.

However, it is considered that the possibility that the particle size L of the inorganic layered compound (A) in the dispersion obtained by the diffraction / scattering method exceeds the major axis (Lmax) of the inorganic layered compound (A) is very low. The true aspect ratio (Lmax
/ A) "is lower than the" aspect ratio (Z) "used in the present invention (Lmax / a <Z).

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

In the present invention, the components other than the inorganic layered compound (A) which can be used in the inorganic layered compound (A) -containing layer 3 are not particularly limited. Polymer, surfactant,
And organic metal complexes. These components may be used alone or in combination as appropriate.

As the inorganic polymer, specifically, for example, polyphosphazene, polythiazyl, polysilane,
Polymerized sulfur, polysilazane, polysilicon sulfide, etc. (198
9 years, edited by The Society of Polymer Science, published by Maruzen Co., Ltd.)
Is mentioned.

Examples of the organic polymer include polyolefin resins, polyester resins, amide resins, acrylic resins, styrene resins, and the like.
Acrylonitrile resins, cellulose resins, halogen-containing resins, hydrogen bonding resins, liquid crystal resins, polyphenylene oxide resins, polymethylene oxide resins, polycarbonate resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, and the like. .

Further, as an example of a preferable resin, a high hydrogen bonding resin having a hydrogen bonding group or an ionic group described later as a crosslinkable functional group can be given. When the inorganic layered compound (A) -containing layer 3 contains a high hydrogen bonding resin, the strength of the inorganic layered compound (A) -containing layer 3 itself and the gas barrier property at the time of bending can be improved.

The high hydrogen bonding resin is a resin having a hydrogen bonding group or an ionic group. The content of the hydrogen-bonding group or the ionic group in the high hydrogen-bonding resin (the total amount of both if both are contained) is usually from 20 mol% to 60 mol%.
Mol%, preferably 30 mol% to 50 mol%. The content of these hydrogen bonding groups and ionic groups can be determined, for example, by nuclear magnetic resonance (for example, 1H-
NMR, 13 C-NMR, etc.).

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

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

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

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

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

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

These resins may be used alone or in a combination of two or more. Among these resins, PVA and its modified products, polysaccharides, ethylene-vinyl alcohol copolymer and its modified products are particularly preferred.

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

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

Among these copolymers, a block copolymer in which a polycarboxylic acid component is copolymerized with a PVA component is particularly preferably used, and particularly when the polycarboxylic acid component is polymethacrylic acid. preferable. Further, the block copolymer is particularly preferably an AB type block copolymer in which a polyacrylic acid chain is extended at one end of a PVA chain, and a PVA block component (a) and a polyacrylic acid are preferably used. It is preferable that the weight ratio (a) / (b) of the block component (b) is 50/50 to 95/5, and particularly preferable when the weight ratio (a) / (b) is 60/40 to 90/10. It is complete, and the bonding property with the substrate is remarkably complete. Further, among other modified forms, one of particularly preferred forms is
There is a silyl group-modified PVA resin composed of a saponified vinyl ester polymer modified with at least one compound having a silyl group in the molecule.

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

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

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

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

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

The suitable range varies depending on the degree of modification of the modified PVA resin of the present invention, that is, the content of the silyl group, the degree of saponification, etc., but it is an important factor for the gas barrier property. 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. , 2 mol%
The following are 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 silylation rate is determined by the PV before silylation.
It shows the ratio of the introduced silyl group after silylation to the amount of hydroxyl group contained in the A-based resin.

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

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

When the resin is a highly hydrogen-bonding resin, a crosslinkable resin capable of undergoing a cross-linking reaction with the high hydrogen-bonding resin may be used as a component other than the inorganic layered compound (A) for the purpose of improving water resistance. Agents can further be used.

As the above-mentioned crosslinking agent, it is possible to impart a high level of water resistance such as boiling property and retort property to the layer 3 containing the inorganic layered compound (A) while maintaining flexibility. Metal organic compounds, especially organometallic complexes, are preferred. The metal organic compound is a compound capable of performing a cross-linking reaction with a high hydrogen bonding resin and a coordination bond, a hydrogen bond, an ionic bond, or the like, and has a high cross-linking reactivity with the high hydrogen bonding resin, for example, an inorganic metal. The crosslinking efficiency can be improved as compared with the salt. When the inorganic layered compound (A) -containing layer 3 is laminated, for example, by coating with a coating liquid containing a composition comprising the above-described components, if the reactivity is too high, a crosslinking reaction proceeds in the coating liquid, and Not suitable for However, the organometallic compound is suitable for coating because its reactivity is easily controlled by changing its ligand.

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

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

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

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

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

The metal organic compounds may be used alone or in a combination of two or more.
Among the above-mentioned metal organic compounds, a chelate compound, for example, a metal organic compound (organometal complex) having a chelating ligand such as acetylacetonate and coordinating with the high hydrogen bonding resin is crosslinked. Titanium chelate compounds are particularly preferred from the viewpoint of appropriate reactivity, and among them, titanium chelate compounds are particularly preferred in terms of stability in a coating solution when the resulting composition is applied. In addition, titanium chelate compound,
Particularly effective in improving water resistance.

The crosslinking agent for the hydrogen-bonding group may be a coupling agent such as a titanium-based coupling agent, a silane-based coupling agent, a melamine-based coupling agent, an epoxy-based coupling agent, or an isocyanate-based coupling agent. Agents; water-soluble epoxy compounds; copper compounds; zirconium compounds; and the like.

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

Specific examples of the zirconium compound include 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; zirconium salts of organic acids such as zirconium formate, zirconium acetate, zirconium propionate, zirconium caprylate, zirconium stearate;
Zirconium complex salts such as ammonium zirconium carbonate, sodium zirconium sulfate, zirconium ammonium acetate, sodium zirconium oxalate, sodium zirconium citrate and zirconium ammonium citrate;

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

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

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

When a urethane resin is used for the thermosetting resin layer 2, the inorganic layered compound (A)
It is preferable that the containing layer 3 further contains a surfactant for improving adhesion and adhesion to the thermosetting resin layer 2. The surfactant is not particularly limited as long as it can improve the adhesiveness and the adhesiveness between the inorganic layered compound (A) and the thermosetting resin layer 2. Examples include anionic, cationic, zwitterionic and nonionic surfactants.

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

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

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 groups and alkylene oxide adducts, and polysiloxane-polyoxyalkylene copolymers. Polymer, ether type such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block polymer, etc., ester ether type such as polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc., aliphatic alkanolamide And fluorinated compounds such as perfluorodecanoic acid-diglycerin ester and perfluoroalkylalkylene oxide compounds.

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

The amount of the surfactant may be such that when the inorganic layered compound (A) -containing layer 3 is formed, for example, when a coating solution is used, the content in the coating solution is 0 from the viewpoint of the effect. .0
It is preferably set to be from 0.01% by weight to 5% by weight, more preferably from 0.003% by weight to 0.5% by weight, and more preferably from 0.005% by weight to 0.1% by weight.
It is particularly preferred to set the weight%.

Further, the inorganic layered compound (A) -containing layer 3
May contain various conventionally known additives such as an ultraviolet absorber, a coloring agent, and an antioxidant, as long as the effects of the present invention are not impaired.

The composition ratio of the inorganic layered compound (A) in the inorganic layered compound (A) -containing layer 3 is not particularly limited.
Inorganic layered compound (A) with respect to all components (composition)
Weight ratio (all components (composition) of the layer 3 containing the inorganic layered compound (A) / inorganic layered compound (A)) is 0.1 to 1
Is more preferable, and it is more preferable that it is in the range of 0.3 to 1.

Further, the inorganic layered compound (A) -containing layer 3
When the component (composition) constituting the above contains a resin, particularly a high hydrogen bonding resin, the weight ratio of the inorganic layered compound (A) to the resin (inorganic layered compound / resin) is 1/9.
９9/1, preferably 3 / 7、３8 /
More preferably, it is within the range of 2. In the case where the inorganic layered compound (A) -containing layer 3 is formed by coating a dispersion, the concentrations of the resin and the inorganic layered compound (A) in the coating liquid used for the coating are not particularly limited. ,
Usually, it is preferable that the total of the two is in the range of 4% by weight to 15% by weight.

When the layer 3 containing the inorganic layered compound (A) contains components other than the inorganic layered compound (A) (hereinafter, referred to as other components), such as the high hydrogen bonding resin,
The method of blending the inorganic layered compound (A) with other components (the method of producing a composition comprising the inorganic layered compound (A) and other components) is not particularly limited, but is not particularly limited. From the viewpoint of sex or ease of operation, for example,
A method of mixing a solution obtained by dissolving other components in a solvent and a dispersion obtained by swelling or cleaving the inorganic layered compound (A) in a dispersion medium in advance, and then removing the solvent and the dispersion medium; the inorganic layered compound (A) A method in which a dispersion obtained by swelling or cleaving the above with a dispersion medium is added to other components, the other components are dissolved in the dispersion, and then the dispersion medium is removed; A method in which the layered compound (A) is added, and the inorganic layered compound (A) is swollen or cleaved with the above solution to form a dispersion, and then the solvent is removed; A method of kneading; and the like can also be adopted.

When the other component contains a crosslinking agent for crosslinking the high hydrogen bonding resin, the crosslinking agent is added after mixing the high hydrogen bonding resin and the inorganic layered compound (A). It is preferable to mix them, but they may be added simultaneously with the high hydrogen bonding resin or the inorganic layered compound (A), or may be used by dissolving or dispersing them in the solvent or dispersion medium in advance. When the crosslinking agent contains a metal organic compound, the crosslinking agent is preferably dissolved in an alcohol and added. When the inorganic layered compound (A) -containing layer 3 is formed by coating, the coating liquid is preferably made acidic from the viewpoint of the stability of the coating liquid containing the metal organic compound, and has a pH of 5 or less. Is more preferable, and 3 or less is particularly preferable. Although there is no particular lower limit on the pH of the coating solution,
Usually, it is 0.5 or more.

Among the methods described above, from the viewpoint that a large aspect ratio of the inorganic layered compound (A) can be easily obtained,
The above-mentioned methods are more preferable. Also, the above ~
When the method is adopted, it is preferable to perform the treatment using a high-pressure dispersion device from the viewpoint of the dispersibility of the inorganic layered compound (A).

As the high-pressure dispersion device, for example, Microf
There is an ultrahigh-pressure homogenizer (trade name: Microfluidizer) manufactured by luidics Corporation or a Nanomizer manufactured by Nanomizer, and a homogenizer manufactured by Manton-Gaulin, such as a homogenizer manufactured by Izumi Food Machinery. The inorganic layered compound is obtained by subjecting a composition mixture containing the inorganic layered compound (A) and the other component such as a resin to a high-pressure dispersion treatment, in particular, a high-pressure dispersion treatment under a pressure condition of 100 kgf / cm ² or more. A composition in which (A) and the above-mentioned other components are uniformly dispersed, and a coating liquid containing the composition can be obtained.

The high-pressure dispersion treatment according to the present invention is, as shown in FIG. 7, by causing a composition mixture obtained by mixing particles or a dispersion medium to be dispersed to pass through a plurality of small tubes 11 at a high speed to collide with each other. Dispersion treatment under special conditions such as high shear and high pressure.

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

The principle of the high-pressure treatment in the high-pressure dispersion treatment apparatus used for the high-pressure dispersion treatment will be 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 the thin tube 11, a high pressure and a high speed state are established, and the respective inorganic layered compound (A) particles of the composition mixture collide with each other and the inner wall of the thin tube 11, and the diameter and thickness of the respective inorganic layered compound (A) particles In particular, the thickness is divided into smaller pieces and more uniformly dispersed, and 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 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 inorganic layered compound (A) according to the present invention
The method for laminating the containing layer 3 on the thermosetting resin layer 2 is not particularly limited, but the constituent components (for example, the inorganic stratiform compound (A)) constituting the above-mentioned inorganic layered compound (A) containing layer 3 A coating liquid (composition mixture) containing a liquid alone or a composition comprising the above-described inorganic layered compound (A) and other components) is applied to the surface of the thermosetting resin layer 2 (coating). After forming the coating film, the coating film is dried and heat-treated, for example, to remove the liquid from the coating film (coating method), or to constitute the inorganic layered compound (A) -containing layer 3 A method of laminating a film composed of the components on the surface of the thermosetting resin layer 2 or the like is suitably used.

The coating liquid containing the components constituting the inorganic layered compound (A) -containing layer 3 and the liquid, more specifically, the components constituting the inorganic layered compound (A) -containing layer 3 Is, as described above, a liquid dispersed or dissolved in a liquid such as a solvent or a dispersion medium. From the viewpoint of the gas barrier properties of the obtained laminate, the liquid is preferably a dispersion medium that swells or cleaves the above-mentioned inorganic layered compound (A). When the liquid is a dispersion medium, the inorganic layered compound (A) is dispersed in the liquid in a state of swelling or cleavage.

Examples of the method used for coating the coating liquid include gravure methods such as direct gravure method, reverse gravure method and microgravure method; rolls such as two-roll beat coating method and bottom feed three-reverse coating method. Various known methods such as a coating method; a doctor knife method; a die coating method; a dip coating method; a spray coating method; a spin coating method; a bar coating method;

In the case where the above-mentioned methods (1) to (3) are used as a method for producing the composition, the solvent and the dispersion medium used for forming the layer 3 containing the inorganic layered compound (A) are removed from the system and then obtained. The laminate is heated to, for example, 110 ° C. or higher,
Heat aging at a temperature of 20 ° C. or less is particularly preferable since the water resistance of the finally obtained laminate can be improved, that is, the gas barrier properties after the water resistance environment test. The aging time is not limited, but it is necessary that the inorganic layered compound (A) -containing layer 3 reaches at least the set temperature. For example, in the case of a method using a heat medium such as a hot air drier, 1 second or more and 100 minutes or less Is preferred.

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

In the present invention, as shown in FIG. 3, the inorganic layered compound (A) -containing layer 3 is made of an inorganic layered compound (A).
However, according to the shape of the layered structure, for example, the inorganic layered compound (A) is formed so that the layers, for example, the unit crystal layers 31 face each other and are substantially parallel to the surface direction of the inorganic layered compound (A) -containing layer 3. ) Since it is dispersed and oriented in a state of being swollen or cleaved in the resin 32 of the containing layer 3, a maze effect is generated, and excellent gas barrier properties (including heat-resistant gas barrier properties) can be obtained.

In the present invention, the inorganic compound (B) used in the inorganic compound (B) -containing layer 4 includes an alkali metal, an alkaline earth metal, a transition element, a group 3B element and a group 4B element in the periodic table. , At least one element selected from the group consisting of Group 5B elements,
2A, 3A, 3B, 4A, 4B, 5A, 5
At least one element selected from the group consisting of elements belonging to Group B, Group 6A, Group 7A, and Group 8, preferably an element having an atomic number of 12 or more among the elements selected from the group consisting of the above elements And an inorganic compound.

The inorganic compound (B) -containing layer 4 is used as a barrier layer together with the inorganic layer compound (A) -containing layer 3 while having high hardness and excellent chemical resistance. Gas barrier properties (including heat-resistant gas barrier properties) and, if necessary, light barrier properties (light-shielding properties). Further, the inorganic compound (B) -containing layer 4 has a low water vapor transmission rate, and can impart excellent water vapor barrier properties to the laminate.

The composition of the inorganic compound (B) -containing layer 4 is as follows:
The inorganic compound (B) may be appropriately set depending on the required physical properties, and is not particularly limited. It is preferably at least one selected from the group consisting of metals, metal oxides, nitrides, and hydroxides containing at least one element selected from the group consisting of metals, metal oxides, and nitrides. More preferably, it is at least one selected from the group.

Examples of the inorganic compound (B) include aluminum, silver, gold, platinum, palladium, silicon oxide, aluminum oxide, aluminum hydroxide, titanium oxide, titanium hydroxide, and zirconium. Oxide, zirconium hydroxide, complex of aluminum oxide and silicon oxide, complex of zinc oxide and silicon oxide, complex of calcium oxide and silicon oxide, boron oxide and silicon Examples thereof include a complex with an oxide and a silicon nitride such as polysilazane, but are not particularly limited. One of these inorganic compounds (B) may be used alone, or two or more of them may be used as a mixture.

The method for forming the inorganic compound (B) -containing layer 4 composed of the inorganic compound (B) is not particularly limited, but a vapor deposition method such as physical vapor deposition or chemical vapor deposition; a sol-gel method; Can be

For example, when the inorganic compound (B) -containing layer 4 is
In the case where the layer is made of aluminum, silicon oxide, aluminum oxide, or the like, a vapor deposition method is suitably used for forming the layer containing the inorganic compound (B).

The inorganic compound (B) -containing layer 4 is
From a composite of aluminum oxide and silicon oxide, a composite of zinc oxide and silicon oxide, a composite of calcium oxide and silicon oxide, a composite of boron oxide and silicon oxide, etc. In such a case, binary evaporation using a plurality of evaporation sources can be employed.

Further, as an example of the sol-gel method, a method of converting a metal alkoxide such as tetraethyl orthosilicate or titanium tetraisopropoxide into a metal oxide (hydroxide) by, for example, a dealcoholization reaction can be mentioned. . As the sol-gel method, for example, an inorganic compound (B) -containing layer 4 made of silicon oxide, titanium oxide, or the like is used.
Used to form a layer.

In the present invention, the inorganic compound (B) -containing layer 4 may contain components other than the inorganic compound (B). Components other than the inorganic compound (B) are not particularly limited. For example, the inorganic compound (B) -containing layer 4 may be made of a compound obtained by compounding the inorganic compound (B) with an organic compound by a chemical vapor deposition method, or an active hydrogen compound by a sol-gel method. And an organic compound such as an isocyanate compound.

As a method of laminating the inorganic compound (B) -containing layer 4 on the inorganic layered compound (A) -containing layer 3, the inorganic compound (B) -containing layer 4 is separately formed, and the inorganic layered compound Although there is a method of laminating on the (A) -containing layer 3, it is preferable to vapor-deposit or coat the components constituting the above-mentioned inorganic compound (B) -containing layer 4 on the inorganic layered compound (A) -containing layer 3. is there. As a specific method in the case of coating, a method of coating a coating liquid containing the constituent components constituting the inorganic compound (B) -containing layer 4 onto the inorganic layered compound (A) -containing layer 3 can be used. .

The shape of the thus obtained laminate of the present invention is not particularly limited, and examples thereof include containers (bottles, trays, etc.), films (including sheets),
Tubes and the like. In addition, for example, various shapes can be used according to the shape of the support 1, and among them, a film shape is preferable.

The thickness of each layer of the laminate may be appropriately set according to the required barrier performance, application, etc. other than the heat-resistant gas barrier property, and is not particularly limited. In addition to sufficiently exhibiting the heat-resistant gas barrier property, the thickness of the thermosetting resin layer 2 is in the range of 0.001 μm to 1000 μm from the viewpoints of drying properties and adhesion, and the inorganic layered compound (A) -containing layer 3 Layer thickness of 0.00
Inorganic compound (B) -containing layer 4 in the range of 1 μm to 10 μm
It is preferable that at least one condition is satisfied in the range of 0.001 μm to 2 μm.

When the laminate is a film laminate, the thickness of the thermosetting resin layer 2 is preferably 0.00
Within the range of 1 μm to 200 μm, more preferably 0.001
μm to 20 μm, and the inorganic layered compound (A)
The layer thickness of the containing layer 3 is preferably in the range of 0.001 μm to 2 μm, more preferably in the range of 0.001 μm to 1 μm, and the layer thickness of the inorganic compound (B) -containing layer 4 is preferably Is in the range of 0.001 μm to 0.5 μm, more preferably in the range of 0.001 μm to 0.1 μm.

In the present invention, the inorganic layered compound (A) -containing layer 3 having the above-described structure is provided, and the respective layers are arranged in the order described above. Even with a very thin film thickness, sufficient heat-resistant gas barrier properties can be obtained. For this reason, according to the present invention, the inorganic compound (B) -containing layer 4 can be set thin, so that disposal at the time of disposal can be facilitated.

When the laminate has the support layer 1, the thermosetting resin layer 2 can be made thinner. In this case, the thickness of the thermosetting resin layer 2 is preferably in the range of 0.001 μm to 2 μm, more preferably in the range of 0.001 μm to 0.2 μm, and contains the inorganic compound (B). The layer thickness of the layer 4 is preferably from 0.001 μm to
Within the range of 2 μm, more preferably 0.001 μm to 1 μm
And the layer thickness of the inorganic compound (B) -containing layer 4 is:
It is preferably in the range of 0.001 μm to 0.5 μm, more preferably in the range of 0.001 μm to 0.1 μm.

In this embodiment, as shown in FIG. 1 or FIG. 2, an inorganic layered compound (A) -containing layer 3 and an inorganic compound (B) -containing layer 4 are formed on the thermosetting resin layer 2. In this order, the configuration in which the layers are stacked in contact with each other is shown.
It may have a configuration in which another layer is laminated between the above-described layers. However, when a layer made of a thermoplastic polymer is provided on the laminating surface side of the layer 3 containing the inorganic layered compound (A) and the layer 4 containing the inorganic compound (B) in the thermosetting resin layer 2, the thermoplasticity due to high temperature is high. Due to plasticization and thermal expansion of molecules, the above-mentioned layer 3 containing inorganic compound (A) and layer 4 containing inorganic compound (B) are destroyed, and the layer 3 containing inorganic layer compound (A) and the layer containing inorganic compound (B) are destroyed. There is a possibility that various properties of the polymer 4 may be deteriorated, and it is not suitable for use at a high temperature. For example, when a layer made of a thermoplastic polymer is formed, such as the support layer 1, the thermoplastic polymer is The layer to be formed is laminated on the surface of the thermosetting resin layer 2 opposite to the surface on which the inorganic layered compound (A) -containing layer 3 and the inorganic compound (B) -containing layer 4 are laminated. That is, in the present invention,
Layers other than those described above can be provided as long as the effects of the present invention are not impaired.

When a metal such as the inorganic compound (B) is directly deposited on, for example, biaxially-stretched polypropylene or the like, the adhesion strength is weak and the quality deteriorates with time. However, the inorganic compound (B) -containing layer 4
Is excellent in adhesion to the above-mentioned layer 3 containing an inorganic layered compound (A), and exhibits a synergistic effect when laminated on the layer 3 containing an inorganic layered compound (A). Therefore, when the inorganic compound (B) -containing layer 4 is formed on the surface of the inorganic layered compound (A) -containing layer 3, the inorganic layered compound (A) -containing layer 3 and the inorganic compound (B) -containing layer 4 The layer thickness can be set thin. In addition, the tearability can be improved.

Incidentally, various additives such as an ultraviolet absorber, a coloring agent, an antioxidant and the like may be mixed in each of the above-mentioned layers, if necessary.

As described above, according to the present invention, the thermosetting resin layer 2 (first layer) made of the thermosetting resin, the inorganic layered compound (A) -containing layer 3 having the inorganic layered compound (A), Second layer), alkali metal, alkaline earth metal, transition element,
And an inorganic compound (B) -containing layer 4 having an inorganic compound (B) containing at least one element selected from the group consisting of a group 3B element, a group 4B element, and a group 5B element in the periodic table.
It can be seen that, by laminating the layers in this order, a laminate having good thermal stability and excellent heat-resistant gas barrier properties can be obtained.

The laminate of the present invention can be used for (yo) confectionery, miso, pickles, konjac, bamboo rings, kamaboko, other processed foods, meatballs, hamburgers, ham and sausages, pet foods, etc., as well as agricultural chemicals.・ Suitable for gas barrier packaging materials in many fields such as medical, electronic, chemical, and mechanical fields, such as fertilizers, cosmetics, fragrances, infusion packs, vacuum insulation materials, semiconductor packaging, oxidizing chemical packaging, precision material packaging, etc. Used. The laminate of the present invention is particularly required to have high heat-resistant gas barrier properties, for example, microwave heating cooking or sterilization packaging, retort / boil sterilization packaging, high-temperature material / high-temperature liquid packaging, vacuum insulation material, and the like. Particularly preferably used.

[0143]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. Various physical properties of the laminates (film laminates) obtained in Examples and Comparative Examples were measured as follows.

[Measurement of Thickness] 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, a thickness of less than 0.5 μm is determined by the gravimetric analysis method (the measured value of the weight of a film having a certain area is divided by the area and further divided by the specific gravity of the composition (resin composition)) or the IR method. A calibration curve between the thickness of the coating film and the IR absorption was prepared and determined from the calibration curve. Further, in the case of measuring the thickness of the coating film of the composition (resin composition) containing the inorganic layered compound (A), the elemental analysis method [specific inorganic elemental analysis value of the laminate (inorganic layered compound (A) From the ratio of the specific element fraction of the inorganic layered compound (A) alone and the inorganic layered compound (A) alone, the inorganic layered compound (A) -containing layer and the lower layer of the inorganic layered compound (A) -containing layer such as a thermosetting resin layer Method for Determining the Ratio to the Layer to be Made].

[Oxygen Permeability Measurement] Based on JIS K7126, an oxygen permeability analyzer (OX-TRAN 100)
A, manufactured by MOCON) at a predetermined temperature.

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

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

[Example 1] [Coating liquid for thermosetting resin layer] Polyester polyol (Adcoat AD335AE: manufactured by Toyo Morton Co., Ltd.) in a 1/1 mixed solvent of toluene / methyl ethyl ketone
And toluene diisocyanate in a weight ratio of 15/1, and a total solid content concentration of the polyester polyol and toluene diisocyanate of 20% by weight to obtain a coating liquid for a thermosetting resin layer. .

[Coating Liquid for Layer Containing Inorganic Layered Compound (A)]
Dispersion kettle with a stirrer (trade name: Despa MH-L, manufactured by Asada Iron Works Co., Ltd.) was charged with ion-exchanged water (specific electric conductivity 1 μs / c
m or less) 1000 g and polyvinyl alcohol (PVA117H; manufactured by Kuraray Co., Ltd.) as a high hydrogen bonding resin
100 g of a saponification degree: 99.6%, a polymerization degree of 1,700) were charged, and the mixture was stirred at a low speed (1,500 rpm, a peripheral speed of about 4).
(m / sec) to 95 ° C., and stirred for 1 hour to dissolve, thereby obtaining a solution (1). Subsequently, the solution (1)
After the temperature was lowered to 65 ° C. while stirring, 400 g of ion-exchanged water and 1-butanol 94 were added to the solution (1).
g and an alcohol aqueous solution obtained by pre-mixing g with g was slowly added dropwise. After completion of the dropping, 50 g of high-purity natural montmorillonite (trade name: Kunipia G; manufactured by Kunimine Industries, Ltd.) as an inorganic layered compound (A) was further added at 65 ° C. as a powder, and the stirring conditions were changed to high-speed stirring (3000 rpm). ,
(Circumferential speed: about 8 m / sec), and the mixture was stirred and dispersed for 90 minutes to obtain a resin composition mixed liquid (2).

Next, a high-pressure dispersion device (trade name: ultrahigh-pressure homogenizer M110-E / H, Microfluidics Corporat)
through the above resin composition mixture (2).
By treating once at 1.750 kgf / cm ² , a uniform dispersion (3) having good dispersibility was obtained. The solid content concentration of the dispersion liquid (3) was about 7.6% by weight.

The dispersion (3) comprising PVA and natural montmorillonite (Kunipia G) was dried, solidified, pulverized, and subjected to powder X-ray analysis to determine the plane spacing of the swollen and cleaved natural montmorillonite (Kunipia G). d was measured. As a result, the interplanar spacing d was larger than the unit thickness a, and it was found that the natural montmorillonite (Kunipia G) was sufficiently cleaved for the reason described above. The aspect ratio of the natural montmorillonite (Kunipia G) opened at this time was 200 or more.

A dispersion vessel equipped with a stirrer (trade name: Despa MH-L, manufactured by Asada Tekko Co., Ltd.) was used for 1500 g of the above dispersion (3).
And adjusted with hydrochloric acid (addition of about 6 g) so that the pH of the system (the pH of the dispersion liquid (3)) becomes about 3, and titanium acetylacetonate as a metal organic compound (trade name: TC1)
00, manufactured by Matsumoto Pharmaceutical Co., Ltd.) was slowly added at room temperature under low-speed stirring (1,500 rpm, peripheral speed: 4.10 m / min). Thereafter, 0.15 g of a nonionic surfactant (trade name: SH3746, manufactured by Dow Corning Toray Co., Ltd.) was added while stirring, and this was used as a coating liquid for an inorganic layered compound (A) -containing layer. .

[Production of Laminated Body] A biaxially stretched polyethylene terephthalate (OPET) film (trade name: Espet T4102; manufactured by Toyobo Co., Ltd., with one-sided corona treatment) having a thickness of 12 μm was used as a support layer. The coating liquid for a thermosetting resin layer was gravure-coated on the corona-treated surface of the layer, and then dried to form a urethane resin layer (thermosetting resin layer) of about 0.1 μm.

Next, the above-mentioned inorganic layered compound (A) -containing coating liquid for the layer was gravure-coated on the urethane resin layer, and then dried, whereby the above-mentioned inorganic material was formed on the urethane resin layer. A coating film having an inorganic layered compound (A) -containing layer formed thereon based on the layered compound (A) -containing layer coating solution was obtained. The dry thickness of the layer containing the inorganic layered compound (A) was about 0.4 μm.

Subsequently, aluminum was vapor-deposited on the inorganic layered compound (A) -containing layer of the coating film using a vacuum vapor deposition device to form an inorganic compound (B) -containing layer having a thickness of about 0.04 μm. Thus, a film laminate as a laminate according to the present invention was obtained. 8 of the obtained film laminate
Oxygen permeability at 0 ° C was measured to be 0.2 (ml /
atm ・ m ²・ day) or less.

Comparative Example 1 A comparative film laminate was obtained in the same manner as in Example 1, except that the layer containing the inorganic layered compound (A) was not laminated. When the oxygen permeability at 80 ° C. of the obtained film laminate was measured, it was inferior to 100 (ml / atm · m ² · day) or more.

[Embodiment 2] In the embodiment 1, the OPET
The procedure was carried out except that a biaxially oriented polypropylene (OPP) film having a thickness of 20 μm (trade name: Bayren Film-OT P2102; manufactured by Toyobo Co., Ltd. with one-sided corona treatment) was used as the support layer instead of the film. The same operation as in Example 1 was performed to obtain a film laminate as a laminate according to the present invention. The resulting film laminate had a low oxygen permeability at 80 ° C., and the laminate had excellent heat-resistant gas barrier properties.

[Example 3] In Example 1, silicon oxide was deposited on the inorganic layered compound (A) -containing layer of the coating film by using a vacuum deposition apparatus instead of aluminum deposition. A film laminate as a laminate according to the present invention was obtained by performing the same operation as in Example 1 except that an inorganic compound (B) -containing layer having a thickness of about 0.04 μm was formed. The oxygen permeability at 80 ° C. of the obtained film laminate was small, and the film laminate was excellent in heat-resistant gas barrier properties.

[Fourth Embodiment] In the third embodiment, the OPET
Instead of film, the same OP as used in Example 2
A film laminate as a laminate according to the present invention was obtained by performing the same operation as in Example 3 except that the P film was used as the support layer. The oxygen permeability at 80 ° C. of the obtained film laminate was small, and the film laminate was excellent in heat-resistant gas barrier properties.

[0160]

According to the first aspect of the present invention, there is provided a laminate comprising:
As described above, the first layer, the second layer, and the third layer are stacked in this order, the first layer is a layer made of a thermosetting resin, and the second layer is formed of an inorganic layered compound (A ), Wherein the third layer comprises an alkali metal, an alkaline earth metal, a transition element, a group 3B element and a group 4B element in the periodic table,
The layer is a layer having an inorganic compound (B) containing at least one element selected from the group consisting of group 5B elements.

As described above, in the laminate according to the second aspect of the present invention, the thermosetting resin may be an epoxy resin, a xylene resin, an oligoester acrylate, a guanamine resin, a diallyl phthalate resin, a resorcinol resin,
The configuration is at least one resin selected from the group consisting of an epoxy acrylate resin, a phenol resin, an unsaturated polyester resin, a furan resin, a polyimide resin, a urethane resin, a maleic resin, a melamine resin, and a urea resin.

As described above, the laminate according to the third aspect of the present invention has a structure in which the inorganic layered compound (A) is a compound which swells in a solvent and is cleaved.

As described above, the laminate according to the fourth aspect of the present invention has a structure in which the inorganic layered compound (A) is a clay mineral.

[0164] In the laminate according to the fifth aspect of the present invention, as described above, the inorganic compound (B) may be at least one selected from the group consisting of metals, metal oxides, nitrides, and hydroxides. It is a kind of inorganic compound.

In the laminate according to the sixth aspect of the present invention, as described above, the layer having the inorganic layered compound (A) is
Further, the structure includes at least one selected from the group consisting of an organic polymer, an inorganic polymer, a surfactant, and an organometallic complex.

As described above, in the laminate according to the seventh aspect of the present invention, the layer having the inorganic layered compound (A) is
Further, the structure includes a high hydrogen bonding resin.

The laminate according to the eighth aspect of the present invention has a structure in which a support layer is provided on the surface of the first layer opposite to the surface on which the second layer is laminated.

[0168] In the laminate according to the ninth aspect of the present invention, as described above, the support layer is formed of at least one base material selected from the group consisting of metal foil, paper, cloth, and synthetic resin film. Configuration.

The laminate according to the tenth aspect of the present invention comprises:
As described above, the thickness of the first layer is 0.001 μm to 1 μm.
2,000 μm, and the thickness of the second layer is 0.001 μm.
m to 10 μm, and the thickness of the third layer is 0.001.
The configuration satisfies at least one condition in the range of μm to 2 μm.

The laminate according to the eleventh aspect of the present invention comprises:
As described above, the configuration is a film laminate.

According to the above configuration, in the second 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 second layer. By the labyrinth effect of the inorganic layered compound, gas barrier properties can be imparted to the obtained laminate together with the third layer.

In addition, in the above configuration, since the first layer is made of a thermosetting resin, destruction of the second or third layer due to plasticization or thermal expansion due to high temperature, especially the conventional laminate The destruction of the inorganic layer made of metal or the like (corresponding to the third layer), which is a problem in the above, can be prevented. Therefore, according to the above configuration, the thermal stability is improved, so that the performance of the second and third layers, such as gas barrier properties, can be sufficiently exhibited even by heating. Therefore, according to the above configuration, there is an effect that a laminate having excellent heat-resistant gas barrier properties can be provided.

[0173] The above-mentioned laminate is composed of (yo) confectionery, miso, pickles,
Konjac, bamboo rings, kamaboko, other processed fishery products, meatballs, hamburgers, ham and sausages, pet foods, and other food fields, as well as agricultural chemicals, fertilizers, cosmetics, fragrances, infusion packs, vacuum insulation materials, semiconductor packaging, and oxidation In many fields such as medicine, electronics, chemistry, machinery, etc.
It is preferably used for gas barrier packaging materials. The laminate is particularly required to have high heat-resistant gas barrier properties, for example, microwave cooking or sterilizing packaging, retort / boil sterilizing packaging, high-temperature material / high-temperature liquid packaging,
It is particularly suitably used for applications such as vacuum heat insulating materials.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a laminate of the present invention.

FIG. 2 is a schematic cross-sectional view showing another example of the laminate of the present invention.

FIG. 3 is a schematic sectional view showing an inorganic layered compound (A) -containing layer of the laminate of the present invention.

FIG. 4 is an inorganic layered compound (A) in the laminate of the present invention.
3 is an X-ray diffraction graph of the inorganic layered compound (A) for calculating the “unit thickness a” of FIG.

FIG. 5 is an inorganic layered compound (A) in the laminate of the present invention.
Inorganic layered compound (A) for calculating the “plane spacing d” of
3 is an X-ray diffraction graph.

FIG. 6 is a graph showing the “plane spacing d” of the inorganic layered compound (A) in the case where the peak corresponding to “plane spacing d” overlaps a halo (or background) and is difficult to detect in the graph of FIG. 6 is an X-ray diffraction graph when calculating.

FIG. 7 is an explanatory view schematically showing a high-pressure dispersion treatment used when forming the inorganic layered compound (A) -containing layer.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 support layer 2 thermosetting resin layer (first layer) 3 layer containing inorganic layered compound (A) (second layer) 4 layer containing inorganic compound (B) (third layer) 31 unit crystal layer 32 resin

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3E086 AD03 AD04 AD05 BA04 BA13 BA14 BA15 BA24 BA35 BA40 BB01 BB41 CA03 4F100 AA00B AA01C AA17C AA40B AB01C AB01D AB33D AC03B AK01A AK01A AK11A AK21A AK21A AK21A AK21A AK21A AK80B AT00D BA03 BA04 BA10A BA10C BA10D DE10B DG10D DG11D EJ38D EJ55D GB15 GB23 GB41 GB66 JB10B JB13A JD01 JJ03 YY00A YY00B YY00C

Claims (11)

[Claims] A first layer, a second layer, and a third layer are laminated in this order, the first layer is a layer made of a thermosetting resin, and the second layer is an inorganic layered compound (A Wherein the third layer comprises at least one element selected from the group consisting of an alkali metal, an alkaline earth metal, a transition element, and a group 3B, 4B, or 5B element of the periodic table. A laminate comprising a layer having an inorganic compound (B) containing the same. 2. The thermosetting resin is an epoxy resin, a xylene resin, an oligoester acrylate, a guanamine resin, a diallyl phthalate resin, a resorcinol resin,
Claims: It is at least one resin selected from the group consisting of epoxy acrylate resin, phenol resin, unsaturated polyester resin, furan resin, polyimide resin, urethane resin, maleic resin, melamine resin, and urea resin. Item 7. The laminate according to Item 1. 3. The laminate according to claim 1, wherein the inorganic layered compound (A) is a compound which swells in a solvent and is cleaved. 4. The laminate according to claim 1, wherein the inorganic layered compound (A) is a clay mineral. 5. The method according to claim 1, wherein said inorganic compound (B) is at least one inorganic compound selected from the group consisting of metals, metal oxides, nitrides, and hydroxides. The laminate according to any one of the above. 6. The layer having the above-mentioned inorganic layered compound (A),
The laminate according to any one of claims 1 to 5, further comprising at least one selected from the group consisting of an organic polymer, an inorganic polymer, a surfactant, and an organometallic complex. 7. The layer containing the above-mentioned inorganic layered compound (A),
The laminate according to any one of claims 1 to 6, further comprising a high hydrogen bonding resin. 8. The method according to claim 1, wherein a support layer is provided on a surface of the first layer opposite to a surface on which the second layer is laminated.
8. The laminate according to any one of the above items 7. 9. The laminate according to claim 8, wherein said support layer is made of at least one substrate selected from the group consisting of metal foil, paper, cloth, and synthetic resin film. 10. The layer thickness of the first layer is 0.001 μm to 1 μm.
2,000 μm, and the thickness of the second layer is 0.001 μm.
m to 10 μm, and the thickness of the third layer is 0.001.
The laminate according to any one of claims 1 to 9, wherein at least one condition in a range of μm to 2 μm is satisfied. 11. The laminate according to claim 1, wherein the laminate is a film laminate.