JP4205241B2 - Laminated body - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention includes a layer made of a thermosetting resin, a layer having an inorganic layered compound (A), an alkali metal, an alkaline earth metal, a transition element, a periodic table group 3B element, a group 4B element, and a group 5B element. The present invention relates to a laminate including an inorganic compound (B) containing at least one element selected from the group, and more particularly to a laminate excellent in heat-resistant gas barrier properties.
[0002]
[Prior 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, in Japanese Patent Application Laid-Open No. 10-44299, a gas barrier property is obtained by laminating a layer made of an inorganic layered compound and a polymer, an inorganic layer made of a metal and / or a metal oxide on a substrate made of a thermoplastic polymer. A technique for enhancing the above is disclosed.
[0003]
[Problems to be solved by the invention]
However, when a substrate made of a thermoplastic polymer is used, the outermost inorganic layer is easily destroyed by plasticization or thermal expansion due to high temperature, and the performance of the inorganic layer, particularly the gas barrier property, is easily deteriorated. There's a problem. For this reason, there is a demand for a laminate that improves thermal stability and does not cause a decrease in gas barrier properties of the inorganic layer due to heating, that is, a laminate excellent in heat-resistant gas barrier properties.
[0004]
The present invention has been made in view of the above-described conventional problems, and an object thereof is to provide a laminate having good thermal stability and excellent heat-resistant gas barrier properties.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the inventors of the present application, as a result, a layer made of a thermosetting resin, a layer having an inorganic layered compound (A), an alkali metal, an alkaline earth metal, a transition element, and a period By arranging the layer having the inorganic compound (B) containing at least one element selected from the group consisting of Table 3B group element, 4B group element, and 5B group element in this order, the thermal stability is good, The inventors have found that a laminate having excellent heat-resistant gas barrier properties can be obtained, and have completed the present invention.
[0006]
That is, in the laminate of the present invention, in order to solve the above problems, the first layer, the second layer, and the third layer are laminated in this order, and the first layer is a layer 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, alkaline earth metal, transition element, and periodic table group 3B element, group 4B element, group 5B It is a layer having an inorganic compound (B) containing at least one element selected from the group consisting of elements.
[0007]
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. Due to the labyrinth effect of the layered compound, gas barrier properties can be imparted to the obtained laminate together with the third layer.
[0008]
In addition, in the above configuration, the first layer is made of a thermosetting resin, so that the second layer or the third layer is destroyed due to plasticization or thermal expansion due to high temperature, particularly in the conventional laminate. The destruction of the inorganic layer made of metal or the like (corresponding to the third layer) can be prevented. Therefore, according to said structure, performance, such as gas barrier property which the said 2nd layer and 3rd layer have, can fully be exhibited by heating by improving thermal stability. Therefore, according to said structure, the laminated body excellent in heat-resistant gas barrier property can be provided.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
One embodiment of the present invention will be described with reference to FIGS. 1 to 7 as follows.
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 (second layer) and an inorganic compound (B) containing at least one element selected from the group consisting of alkali metals, alkaline earth metals, transition elements, and periodic table 3B group elements, 4B group elements, and 5B group elements ) -Containing inorganic compound (B) containing layer 4 (third layer) is laminated in this order. The laminate according to the present invention has excellent thermal stability by having the above-described configuration, and in particular, oxygen permeability at 80 ° C. (ml / atm · m ² -Day) has an excellent heat-resistant gas barrier property of 10 or less.
[0010]
In the laminate, in order to impart sufficient strength, for example, tensile strength, to the laminate, as shown in FIG. 2, the support layer 1 is used as the fourth layer as the thermosetting resin layer. The inorganic layered compound (A) -containing layer 3 in 2 may be laminated on the surface opposite to the laminated surface. 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 and the inorganic layered compound (A) -containing layer 3. Between 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 said structure, the said inorganic layered compound (A) containing layer 3 and the various performance which the inorganic compound (B) containing layer 4 have, especially the said inorganic compound (B) containing layer 4 have also by heating. Performances such as gas barrier properties can be sufficiently exhibited, and a laminate having excellent heat-resistant gas barrier properties can be obtained.
[0011]
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 is a use that will be described later, in particular, a use that requires heat-resistant gas barrier properties. Can be used for wave cooking or sterilization packaging, retort / boil sterilization packaging, high temperature / high temperature liquid packaging, etc., can hold liquid contents such as soup, pasty food, etc. Those having water repellency capable of preventing permeation and leakage and those having solvent resistance to a solvent such as alcohol that dissolves aromatics are preferred.
[0012]
The shape of the support layer 1 is not particularly limited, and can be a desired shape according to, for example, a container (bottle, tray shape, etc.), a film (including a sheet), a tube, and other various molded products. The film shape is preferable.
[0013]
Specific examples of the support layer 1 include, for example, film-shaped ones such as metal foils such as stainless steel foil, copper foil, silver foil, gold foil, and aluminum foil; craft paper, fine paper, structured paper, glassine paper, Examples thereof include paper such as parchment paper, synthetic paper and cardboard; cloth made of natural fiber, cloth made of synthetic fiber, cloth such as nonwoven fabric; plate glass; ceramic sheet; resin film made of thermoplastic polymer and the like. Among them, the substrate used for the support layer 1 is preferably at least one substrate selected from the group consisting of metal foil, paper, cloth, and synthetic resin film.
[0014]
Examples of the material of the synthetic resin film include polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, Polyolefin resins such as polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; Nylon-6, Nylon-6 6, amide resins such as metaxylenediamine-adipic acid condensation polymer, polymethylmethacrylamide; acrylic resins such as polymethylmethacrylate; polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile- Styrene-acrylonitrile resins such as tadiene copolymer and polyacrylonitrile; Hydrophobized 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 alcohol, ethylene-vinyl alcohol copolymer, cellulose derivatives; polycarbonate resins, polysulfone resins, polyether sulfone resins, polyether ether ketone resins, polyphenylene oxide resins, polymethylene oxide resins, liquid crystal resins, etc. Engineering plastic resins; and the like.
[0015]
Among these resin films, a stretched film, in particular, a biaxially stretched film is more preferable because it is excellent in strength such as tensile strength, biaxially stretched polyamide, biaxially stretched polyethylene terephthalate, biaxially stretched polyethylene naphthalate, And a film made of at least one selected from the group consisting of biaxially oriented polypropylene. Among these, a film formed by biaxially stretching a base resin such as polypropylene, polyethylene terephthalate, polyethylene naphthalate, or nylon, and further coated with polyvinylidene chloride called K coat; these polypropylene, polyethylene terephthalate, polyethylene A film obtained by biaxially stretching a base resin such as naphthalate or nylon and further vapor-depositing aluminum, silica, alumina or the like; a strong antistatic use OPP (AS-OP); The stretched film preferably has a higher tensile strength, and preferably has a breaking elongation of 700% or less and more preferably 500% or less. In addition, as said resin film, although a stretched film is used suitably, it is also possible to use the film which consists of said resin which is not extended | stretched.
[0016]
In the present invention, the thermosetting resin used for the thermosetting resin layer 2 is a network structure in which the unreacted groups remaining in the polymer react with heating to increase the degree of polymerization, and the crosslinking proceeds. This indicates a synthetic resin that loses its thermoplasticity.
[0017]
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 an epoxy resin, a xylene resin, an oligoester acrylate, Examples thereof include guanamine resin, diallyl phthalate resin, resorcinol resin, epoxy acrylate resin, phenol resin, unsaturated polyester resin, furan resin, polyimide resin, urethane resin, maleic acid resin, melamine resin, and urea resin. These thermosetting resins have a plurality of reactive groups in one molecule for expressing thermosetting properties. These thermosetting resins may be used alone or as a mixture as appropriate. Among these thermosetting resins, a urethane resin composed mainly of an isocyanate compound and an active hydrogen compound is more preferably used from the viewpoint of water resistance of the resulting laminate.
[0018]
Hereinafter, the urethane resin will be described in detail. The isocyanate compound used in the urethane resin is tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), 4,4'-methylenebis. Examples include cyclohexyl isocyanate (H12MDI) and isophorone diisocyanate (IPDI).
[0019]
Specific examples of the active hydrogen compound include low molecular weight polyols such as ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and trimethylolpropane; polyethylene Polyether polyol such as glycol, polyoxypropylene glycol, ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol; poly-β-methyl-δ-valerolactone, polycaprolactone, polyester from diol / dibasic acid, etc. Polyester polyols; and the like.
[0020]
As the active hydrogen compound, a low molecular weight polyol is particularly preferable, and a diol is more preferable. Here, the diol is 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, terephthalic acid and the like. Other polyols include active hydrogen compounds such as castor oil, liquid polybutadiene, epoxy resin, polycarbonate diol, acrylic polyol, and neoprene.
[0021]
The mixing ratio of the isocyanate compound and the active hydrogen compound is not particularly limited, but the addition amount should be determined in consideration of the equivalent relationship between the isocyanate group and the active hydrogen group, for example, —OH group, —NH group, and —COOH group. Is preferred. For example, assuming that the number of moles of isocyanate groups is AN and the number of moles of active hydrogen groups in the active hydrogen compound is BN, the ratio R (R = AN / BN) of the number of moles of isocyanate groups to the number of moles of active hydrogen groups is From the viewpoint of adhesive strength, it is preferably 0.001 or more, and from the viewpoint of tackiness and blocking, it is preferably 10 or less. The mole ratio R is more preferably in the range of 0.01 or more and 1 or less. The number of moles of isocyanate group and active hydrogen group can be determined by 1H-NMR and 13C-NMR.
[0022]
The lamination method of 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 method of laminating a film made of a curable resin on the surface of the support layer 1 is preferably used.
[0023]
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, Examples include ethers, halogenated hydrocarbons, and mixed solvents thereof.
[0024]
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 micro gravure method; a roll such as a two-roll beat coat method and a bottom feed three-pin reverse coat method. A 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;
[0025]
Further, the interface between the support layer 1 and the thermosetting resin layer 2 may be subjected to treatments such as corona treatment, flame plasma treatment, ozone treatment, electron beam treatment, and anchor treatment. Further, these processes may be incorporated in an inline multilayer forming machine and performed inline. In addition, performing these processes in-line means using the apparatus sequentially installed on the same line along the flow direction at the time of manufacture of the laminated body concerning the present invention, and the manufacturing process (layer forming process) of the laminated body And these processes are promptly performed in a series of operations.
[0026]
Further, in the present invention, the inorganic layered compound (A) used for the inorganic layered compound (A) -containing layer 3 has a layered structure in which unit crystal layers 31 are stacked on each other as shown in FIG. The inorganic compound is not particularly limited as long as it is an inorganic compound.
[0027]
Specific examples of the inorganic layered compound (A) include graphite, phosphate derivative compounds (such as zirconium phosphate compounds), chalcogenides, and clay minerals. The chalcogenide is a dichalcogenide of group IV (Ti, Zr, Hf), group V (V, Nb, Ta) and group VI (Mo, W), which has the chemical formula MX ₂ (Wherein, M represents the group IV and VI elements and X represents chalcogen (S, Se, Te)).
[0028]
As the inorganic layered compound (A), only one type may be used, or two or more types may be appropriately mixed and used. Among the inorganic layered compounds (A), those having a property of swelling or cleaving in a solvent are preferable because a large aspect ratio can be easily given and a smooth and uniform layer can be formed. Those having the property of cleaving (swelling in a solvent and cleaving) are more preferable. The swelling property and cleavage property of the inorganic layered compound (A) in a solvent can be evaluated by the following swelling property test and cleavage property test.
[0029]
(Swellability test)
100 ml of solvent is put into a 100 ml graduated cylinder, and 2 g of the inorganic layered compound (A) is slowly added thereto. After standing at 23 ° C. for 24 hours, the volume (ml) of the inorganic layered compound (A) dispersed layer is read as a swelling value from the scale of the interface between the inorganic layered compound (A) dispersed layer and the supernatant in the graduated cylinder. It shows that swelling property is so high that this figure is large.
[0030]
[Cleavage test]
Slowly add 30 g of inorganic layered compound (A) to 1,500 ml of solvent, and disperser (Asada Tekko Co., Ltd., Despa MH-L, blade diameter 52 mm, rotation speed 3,100 rpm, container volume 3 L, distance between bottom surface and blades 28 mm) at a peripheral speed of 8.5 m / min and a dispersion at 23 ° C. for 90 minutes, 100 ml of this dispersion was collected in a graduated cylinder. After standing for 60 minutes, the volume (ml) of the inorganic layered compound (A) dispersed layer is read as a cleavage value from the scale of the interface between the inorganic layered compound (A) dispersed layer and the supernatant in the graduated cylinder. The larger this value, the higher the cleaving property.
[0031]
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.
[0032]
The swelling property of the inorganic layered compound (A) is such that the volume of the inorganic layered compound (A) dispersion layer (that is, the volume after swelling of 2 g of the inorganic layered compound (A)) is about 5 ml or more in the aforementioned swellability measurement test. (That is, a swelling value of 5 or more) is preferable, and about 20 ml or more (that is, a swelling value of 20 or more) is more preferable.
[0033]
On the other hand, the cleavage property of the inorganic layered compound (A) is determined by the volume of the inorganic layered compound (A) dispersion layer (that is, the inorganic layered compound (A) contained in 100 ml of the dispersion (about 2 g) in the above-described cleavage property test. The volume after swelling) is preferably about 5 ml or more (that is, cleavage value of 5 or more), more preferably about 20 ml or more (that is, cleavage value of 20 or more).
[0034]
Among the inorganic layered compounds (A), as the inorganic layered compound (A) that swells or cleaves in a solvent, a clay mineral having swelling property and cleaving property in a solvent is particularly preferably used. The clay mineral is generally composed of (i) a type having a two-layer structure having an octahedral layer mainly composed of aluminum, magnesium, or the like on an upper part of a tetrahedral layer of silica, and (ii) a tetrahedral layer of silica. In addition, it is classified into a type having a three-layer structure in which an octahedral layer having aluminum or magnesium as a central metal is narrowed from both sides. The former (i) two-layer structure type includes clay minerals such as kaolinite group and antigolite group. The latter (ii) three-layer structure type includes clay minerals such as smectite group, vermiculite group, and mica group depending on the number of interlayer cations.
[0035]
More specifically, these clay minerals include kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite hectorite, tetracite. Examples include lyric mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite. In addition, those obtained by treating these clay minerals with an organic substance (see Asakura Shoten, “Encyclopedia of Clay”; hereinafter sometimes referred to as “organic modified clay mineral”) can also be used as the inorganic layered compound (A).
[0036]
Among the clay minerals, smectite group, vermiculite group, and mica group clay minerals are preferable and smectite group is more preferable from the viewpoint of swelling or cleavage. Specific examples of the smectite clay mineral include montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, and hectorite, but are not particularly limited.
[0037]
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, ethylene glycol And alcohols such as diethylene glycol; dimethylformamide; dimethyl sulfoxide; acetone; and the like. Among them, alcohols such as water and 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. Ketones such as methyl isobutyl ketone; aliphatic hydrocarbons such as n-pentane, n-hexane, and n-octane; halogens such as chlorobenzene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, and perchloroethylene Hydrocarbons; ethyl acetate; methyl methacrylate (MMA); dioctyl phthalate (DOP); dimethylformamide; dimethyl sulfoxide; methyl cellosolve;
[0038]
In the present invention, in the cleaved state, the inorganic layered compound (A) has a particle size of preferably 5 μm or less, more preferably 3 μm or less, particularly preferably 1 μm or less, and an aspect ratio of preferably 10 to 10 Within the range of 1,000, more preferably within the range of 10-3,000, even more preferably within the range of 30-2,000, and particularly preferably within the range of 200-1000. In particular, if the aspect ratio is less than 10, gas barrier properties (including heat-resistant gas barrier properties) are not sufficient, and those exceeding 10,000 are technically difficult and economically expensive.
[0039]
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 diameter and aspect ratio of the inorganic layered compound (A) can be measured, for example, by the following method.
[0040]
The average particle diameter of the inorganic layered compound (A) can be measured by a method using a diffraction / scattering method, a method using a dynamic light scattering method, a method using a change in electrical resistance, a method using image processing after photographing in a liquid microscope, or the like. .
[0041]
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.
[0042]
However, the dynamic light scattering method is difficult to evaluate when the resin coexists because the apparent liquid viscosity changes from that of a pure solvent, and the electric resistance change method is limited in the electrolyte concentration of the liquid. The method based on image processing after medium microscope photography has a problem of resolution and is limited in use.
[0043]
For this reason, when the inorganic layered compound (A) -containing layer 3 contains a component other than the inorganic layered compound (A), for example, when measuring the average particle size of the inorganic layered compound (A) in the presence of a resin, In the case where a solution containing a resin, for example, an aqueous resin liquid is transparent and has substantially no scattering, and scattering derived from the particles of the inorganic layered compound (A) is dominant, the inorganic layered compound ( Since information on only the particle size distribution of the particles of A) can be obtained, a method using a diffraction / scattering method is preferably used.
[0044]
Therefore, the particle size of the inorganic layered compound (A) used in the present invention is a particle size obtained by a diffraction / scattering method in a dispersion medium. When the inorganic layered compound (A) -containing layer 3 further contains a resin in addition to the inorganic layered compound (A), the inorganic layered compound (A) -containing layer 3 (that is, the inorganic layered compound (A) and the resin It is extremely difficult to measure the true particle size in the layer comprising the resin composition comprising), but the inorganic layered compound (A) is sufficiently swollen with the same type of dispersion medium as used in the diffraction / scattering method. When cleaved and combined with the resin 32 in the inorganic layered compound (A) -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 this corresponds to the particle size of the cleaved inorganic layered compound (A) in the dispersion medium.
[0045]
Below, the method to measure the average particle diameter of an inorganic layered compound (A) by the said diffraction / scattering method is demonstrated.
The particle size distribution and average particle size of the inorganic layered compound (A) obtained by the diffraction / scattering method are calculated from the diffraction / scattering pattern obtained when light is passed through the dispersion of the inorganic layered compound (A). By calculating the particle size distribution that is most consistent with the diffraction / scattering pattern, etc.
[0046]
A commercially available apparatus can be used as a diffraction / scattering pattern measuring apparatus used in the diffraction / scattering method. Specifically, for example, laser diffraction / light scattering particle size measuring devices LS230, LS200, LS100 manufactured by Coulter, Inc .; laser diffraction particle size distribution measuring devices SALD2000, SALD2000A, SALD3000 manufactured by Shimadzu Corporation; laser diffraction manufactured by Horiba, Ltd. -Scattering type particle size distribution measuring apparatus LA910, LA700, LA500; Nikkiso Microtrac SPA, Microtrac FRA, etc.
[0047]
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)) in the inorganic layered compound (A) having swelling / cleavage will be described.
[0048]
The aspect ratio (Z) is a ratio obtained from the relationship represented by Z = L / a. Here, L represents the particle size (volume-based median diameter) of the inorganic layered compound (A) obtained by the particle size measurement method by the diffraction / scattering method described above in the dispersion, and a represents the value shown in FIG. The unit thickness of the cleaved inorganic layered compound (A), that is, the thickness of the unit crystal layer 31 of the inorganic layered compound (A) is shown.
[0049]
For the “unit thickness a” of the inorganic layered compound (A), refer to the powder X-ray diffraction method (“Guide for Instrumental Analysis (a)” (1985, published by Kagaku Dojinsha, supervised by Jiro Shiokawa), p. 69. ) And the like, based on the measurement of the inorganic layered compound (A) alone. More specifically, as schematically shown in the graph shown in FIG. 4, the Bragg equation (nλ = 2Dsinθ) is calculated from the angle θ corresponding to the peak at the lowest angle among diffraction peaks observed by X-ray diffraction. , N = 1, 2, 3,...) Is defined as “unit thickness a”.
[0050]
Moreover, when the said inorganic layered compound (A) content layer 3 contains components (for example, resin 32) other than an inorganic layered compound (A), the composition which forms this inorganic layered compound (A) content layer 3 A method based on powder X-ray diffraction of the product (resin composition) and the inorganic layered compound (A) alone can be used.
[0051]
When the inorganic layered compound (A) -containing layer 3 contains the resin 32 in addition to the inorganic layered compound (A), the resin composition corresponding to the inorganic layered compound (A) -containing layer 3 is obtained by removing the solvent from the dispersion. When powder X-ray diffraction is performed, it is usually possible to obtain the interplanar spacing of the inorganic layered compound (A) in the resin composition as “planar spacing d” shown in FIG.
[0052]
More specifically, as schematically shown in the graph of FIG. 5, of the diffraction peaks observed on the lower angle (larger interval) side than the diffraction peak position corresponding to the above-mentioned “unit thickness a”. The interval corresponding to the peak on the lowest angle side is “surface interval d” (where a <d).
[0053]
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 distance d” overlapping with the halo (or background). , The area of the portion excluding the base line on the lower angle side than 2θd is a peak corresponding to the “plane distance d”. Here, “θd” is a diffraction angle corresponding to “(unit thickness a) + (width of single resin chain)”. For details of the method for determining the “plane distance d”, see, for example, pages 35 and 271 and pages 271 and below of “Encyclopedia of Clay” (1985, Asakura Shoten Publishing, Shuichi Iwao, etc.). It will become clearer.
[0054]
Thus, 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 reference diffraction peak (that is, the diffraction peak corresponding to “plane spacing d”). The relative ratio with respect to the integrated intensity is preferably 2 or more, and more preferably 10 or more.
[0055]
Usually, the difference k (k = (d−a)) between the “surface distance d” and the “unit thickness a” is the length of the resin single chain constituting the resin composition when converted to a length. It is equal to or greater than the width (k = (da) ≧ width of single resin chain). Such “resin single chain width” can be determined by simulation calculation (for example, see “Introduction to Polymer Chemistry” (1981, pp. 103-110)). In the case of alcohol, it is 4 to 5 cm (2 to 3 cm for water molecules).
[0056]
When the inorganic layered compound (A) -containing layer 3 contains the resin 32, it is extremely difficult to directly measure the “true aspect ratio” of the inorganic layered compound (A) in the inorganic layered compound (A) -containing layer 3. is there. Accordingly, when the inorganic layered compound (A) -containing layer 3 includes the resin 32, the above-described “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 it is not necessarily equal to the “true aspect ratio”, it is reasonable to approximate the “true aspect ratio” with this “aspect ratio (Z)” for the following reason.
[0057]
That is, a <d between the “surface distance d” obtained by the powder X-ray diffraction method of the resin composition and the “unit thickness a” obtained by the powder X-ray diffraction measurement of the inorganic layered compound (A) alone. And the value of k ((da) value) is equal to or greater than the width of the single resin chain in the resin composition, the inorganic layered compound (A The resin 32 is inserted between the layers. 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 layer 32 of the inorganic layered compound (A) -containing layer 3 in the resin 32. There is sufficient validity to approximate the “true aspect ratio” of the inorganic layered compound (A) with the “aspect ratio (Z)” in the dispersion of the inorganic layered compound (A).
[0058]
As described above, the true particle size measurement of the inorganic layered compound (A) in the resin 32 of the inorganic layered compound (A) -containing layer 3 is extremely difficult, but the resin 32 of the inorganic layered compound (A) -containing layer 3 is difficult. It can be considered that the particle size of the inorganic layered compound (A) therein corresponds to the particle size L of the inorganic layered compound (A) in the dispersion.
[0059]
However, since it is considered that the particle size L of the inorganic layered compound (A) in the dispersion obtained by the diffraction / scattering method is much less likely to exceed the long diameter (Lmax) of the inorganic layered compound (A). The possibility that the “true aspect ratio (Lmax / a)” is lower than the “aspect ratio (Z)” used in the present invention (Lmax / a <Z) is theoretically quite low.
[0060]
Therefore, for the two reasons described above, 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 diameter” indicates the “particle diameter L determined by the diffraction / scattering method”. .
[0061]
In the present invention, the components other than the inorganic layered compound (A) that can be used for the inorganic layered compound (A) -containing layer 3 are not particularly limited, and examples thereof include organic polymers, inorganic polymers, Surfactant, organometallic complex, etc. are mentioned. These components may be used alone or in combination as appropriate.
[0062]
Specific examples of the inorganic polymer include polyphosphazene, polythiazyl, polysilane, polymeric sulfur, polysilazane, polysulfide, and the like (1989, edited by The Society of Polymer Science, published by Maruzen Co., Ltd.). It is done.
[0063]
Specific examples of the organic polymer include polyolefin resins, polyester resins, amide resins, acrylic resins, styrene resins, acrylonitrile resins, cellulose resins, halogen-containing resins, and hydrogen bonds. Resin, liquid crystal resin, polyphenylene oxide resin, polymethylene oxide resin, polycarbonate resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, and the like.
[0064]
Furthermore, as an example of a preferable resin, a high hydrogen bond resin having a hydrogen bond 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 during bending can be improved.
[0065]
The high hydrogen bonding resin is a resin having a hydrogen bonding group or an ionic group. The content of hydrogen bonding groups or ionic groups in the high hydrogen bonding resin (the total amount of both when both are included) is usually in the range of 20 mol% to 60 mol%, preferably It exists in the range of 30 mol%-50 mol%. The content of these hydrogen bonding groups and ionic groups can be measured by, for example, nuclear magnetic resonance (for example, 1H-NMR, 13C-NMR, etc.).
[0066]
Specific examples of the hydrogen bonding group possessed by the high hydrogen bonding resin include a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Examples of the ionic group include ionic groups such as a carboxylate group, a sulfonate ion group, a phosphate ion group, an ammonium group, and a phosphonium group. Among these hydrogen bonding groups and ionic groups, particularly preferred 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.
[0067]
Specific examples of the high hydrogen bonding resin include, for example, polyvinyl alcohol, polysaccharides, an ethylene-vinyl alcohol copolymer described later, polyacrylic acid and esters thereof, sodium polyacrylate, polystyrene sulfonic acid, polystyrene sulfonic acid. Sodium, polyethyleneimine, polyallylamine and its quaternary ammonium salt, polyvinyl thiol, polyglycerin and the like can be mentioned.
[0068]
The polyvinyl alcohol (PVA) is, for example, a copolymer of vinyl alcohol and vinyl acetate, and a polymer obtained by hydrolysis or transesterification (saponification) of the acetate portion of the vinyl acetate polymer; trifluoro And polymers obtained by saponifying vinyl acetate polymer, vinyl formate polymer, vinyl pivalate polymer, t-butyl vinyl ether polymer, trimethylsilyl vinyl ether polymer, and the like. For details of the PVA, for example, “World of PVA” edited by the Poval Society (1992, Kobunshi Publishing Co., Ltd.); “Poval” (1981, Kobunshi Publishing Co., Ltd., Nagano et al.) It will become clearer by referring to etc.
[0069]
The saponification rate of the PVA is preferably 70 mol% or more, more preferably 85 mol% or more, particularly preferably 98 mol% or more, and most preferably a complete saponified product. 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. Moreover, as said PVA, unless the objective of this invention is inhibited, you may modify | denature with a small amount of copolymerization monomers.
[0070]
Polysaccharides are biopolymers synthesized in biological systems by condensation polymerization of various monosaccharides, and in the present invention, those obtained by chemically modifying the biopolymers are also included. Specific examples of the polysaccharide include cellulose; cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose; amylose; amylopectin; pullulan; curdlan; xanthan; chitin;
[0071]
The ethylene-vinyl alcohol copolymer (EVOH) is EVOH having a vinyl alcohol fraction in the range of 40 mol% to 80 mol%, and preferably has a vinyl alcohol fraction of 45 mol% to 75 mol. EVOH in the range of mol%. The melt index (MI) of the EVOH is not particularly limited, but is preferably 0.1 g / 10 min to 50 g / 10 min under conditions of a temperature of 190 ° C. and a load of 2,160 g. The above EVOH may be modified with a small amount of a copolymerization monomer as long as the object of the present invention is not impaired.
[0072]
Only one kind of these resins may be used, or two or more kinds may be appropriately mixed and used. Among these resins, PVA and modified products thereof, polysaccharides, ethylene-vinyl alcohol copolymers and modified products thereof are particularly suitable.
[0073]
The modified PVA and the ethylene-vinyl alcohol copolymer are other unsaturated monomers that can be copolymerized with a vinyl acetate resin in the production process of PVA, such as ethylene, propylene, Olefins such as α-hexene and α-octene, unsaturated acids such as (meth) acrylic acid, crotonic acid, (anhydrous) maleic acid, fumaric acid and itaconic acid, and alkyl esters and alkali salts thereof, vinyl sulfonic acid Sulfonic acid-containing monomers such as styrene sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid and alkali salts thereof, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and trimethyl-2- (1 -(Meth) acrylamide-1,1-dimethylethyl) ammonium chloride Loride, trimethyl-3- (1- (meth) acrylamidopropyl) ammonium chloride, 1-vinyl-2-ethylimidazole, other quaternizable cationic monomers, styrene, alkyl vinyl ether, (meth) acrylamide, etc. Can be mentioned.
[0074]
The ratio of these copolymer components is not particularly limited, but is preferably about 50 mol% or less, preferably about 30 mol% or less with respect to the vinyl alcohol unit. Various forms obtained by an arbitrary method such as random copolymerization, block copolymerization, and graft copolymerization are used.
[0075]
Among these copolymers, a block copolymer obtained by copolymerizing a polycarboxylic acid component with respect to the PVA component is particularly preferably used, and is particularly preferable when the polycarboxylic acid component is polymethacrylic acid. Further, the block copolymer is particularly preferably an AB type block copolymer in which a polyacrylic acid chain is extended to one end of the PVA chain, and the PVA block component (a) and polyacrylic acid are used. The case where the weight ratio (a) / (b) of the block component (b) is 50/50 to 95/5 is preferable, and in the case where it is 60/40 to 90/10, particularly preferable gas barrier properties (heat resistant gas barrier properties) are obtained. It is complete and has a remarkable complete connection with the substrate. Further, among other modified products, one particularly preferable embodiment is a silyl group-modified PVA resin comprising a saponified vinyl ester polymer modified with at least one compound having a silyl group in the molecule. .
[0076]
A method for obtaining a modified polymer having such a composition is not particularly limited, but a compound having a silyl group in the molecule is reacted with a vinyl alcohol polymer such as PVA or modified polyvinyl acetate obtained by a conventional method. And introducing a silyl group into the polymer, or activating the terminal of PVA or a modified product thereof, introducing an unsaturated monomer having a silyl group in the molecule into the polymer terminal, and the unsaturated monomer A copolymer from vinyl ester monomers and unsaturated monomers having a silyl group in the molecule, such as graft copolymerization with vinyl alcohol polymer molecular chain, Various methods such as saponification of this, or introduction of a silyl group at the terminal, such as polymerization of a vinyl ester in the presence of a mercaptan having a silyl group and saponification of the vinyl ester It is effectively used.
[0077]
The modified PVA resin obtained by such various methods may be any 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 these. Those having a reactive substituent such as a silanol group or a salt thereof, which is a hydrolyzate, are particularly preferable.
[0078]
Examples of compounds having a silyl group in the molecule used to obtain these modified PVA resins include organo compounds such as trimethylchlorosilane, dimethylchlorosilane, methyltrichlorosilane, vinyltrichlorosilane, diphenyldichlorosilane, and triethylfluorosilane. Organosilicon esters such as halosilane, trimethylacetoxysilane and dimethyldiacetoxysilane, organoalkoxysilanes such as trimethylmethoxysilane and dimethyldimethoxysilane, organosilanols such as trimethylsilanol and diethylsilanediol, N-amiethyltrimethoxysilane and the like Examples thereof include organoalkyl isocyanates such as aminoalkylsilane and trimethylsilicon isocyanate, and others. The degree of modification by these silylating agents can be arbitrarily adjusted according to the type, amount and reaction conditions of the silylating agent used.
[0079]
Examples of 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 include vinyltrimethoxysilane, vinyltrimethylsilane. Many vinyl silane compounds such as alkyl or allyl substitutes of vinyl alkoxy silane such as vinyl alkoxy silane, vinyl methyl dimethoxy silane, vinyl triisopropoxy silane, etc. And a polyalkylene glycolated vinyl silane in which a part or all of the alkoxy group is substituted with a polyalkylene glycol such as polyethylene glycol. Furthermore, (meth) acrylamide-alkylsilanes such as 3- (meth) acrylamino-propyltrimethoxysilane, 3- (meth) acrylamide-propyltriethoxysilane, and the like can also be preferably used.
[0080]
On the other hand, for a method of polymerizing a vinyl ester in the presence of a mercaptan or the like having a silyl group and then saponifying and introducing a silyl group at the terminal, an alkoxysilylalkyl mercaptan such as 3- (trimethoxysilyl) -propyl mercaptan is used. Preferably used.
[0081]
The suitability range varies depending on the degree of modification in the modified PVA resin of the present invention, that is, the content of silyl groups, the degree of saponification, etc., but it becomes an important factor for gas barrier properties. 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 with respect to the vinyl alcohol unit in the polymer. 2 mol% or less is particularly preferably used. The lower limit is not particularly limited, but the effect is particularly remarkable when it is 0.1 mol% or more.
[0082]
The silylation rate indicates the ratio of the introduced silyl group after silylation to the amount of hydroxyl group contained in the PVA resin before silylation.
[0083]
The modified PVA resin into which the silyl group is introduced is dissolved in an alcohol solvent by the presence of the introduced silyl group by heating and dissolving with an alcohol or a mixed solvent of alcohol / water. On the other hand, the modified PVA resin dissolved in the solvent crosslinks by introducing a part of the introduced silyl group through a dealcoholization reaction and a dehydration reaction. In addition, the presence of water is essential for the above reaction, and it is preferable to use a mixed solvent of alcohol / water.
[0084]
Of course, these various PVA-based resins may be used alone, but as long as they do not hinder the purpose of the present invention, they can be copolymerized with other monomers that can be copolymerized or mixed with other monomers. It can be used in combination with a resin compound. Examples of such resins include polyacrylic acid or esters thereof, polyester resins, polyurethane resins, polyamide resins, epoxy resins, melamine resins, and others.
[0085]
In addition, when the above resin is a high hydrogen bond resin, for the purpose of improving water resistance, a crosslinking agent capable of undergoing a crosslinking reaction with the high hydrogen bond resin is further included as a component other than the inorganic layered compound (A). Can be used.
[0086]
As the above-mentioned cross-linking agent, it is possible to impart a high level of water resistance such as boilability and retort property to the inorganic layered compound (A) -containing layer 3 while maintaining flexibility. Particularly preferred are organometallic complexes. A metal organic compound is a compound that can undergo a cross-linking reaction with a high hydrogen bond resin by coordination bond, hydrogen bond, ionic bond, etc., and has high cross-linking reactivity with the high hydrogen bond resin, for example, an inorganic metal Crosslinking efficiency can be improved as compared with a salt. When the inorganic layered compound (A) -containing layer 3 is laminated by, for example, coating with a coating liquid containing the above-described composition, if the reactivity is too high, the crosslinking reaction proceeds in the coating liquid, It is no longer suitable for. However, organometallic compounds are suitable for coating because their reactivity can be easily controlled by changing their ligands.
[0087]
Preferable examples of the metal organic compound include a titanium organic compound, a zirconium organic compound, an aluminum organic compound, and a silicon organic compound. Only one kind of these metal organic compounds may be used, or two or more kinds may be appropriately mixed and used.
[0088]
Specific examples of the titanium organic compound include titanium orthoesters such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate; titanium acetylacetonate, titanium tetra Titanium chelates such as acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate, titanium triethanolamate, titanium ethylacetoacetate; titanium acylates such as polyhydroxytitanium stearate; It is done.
[0089]
Specific examples of the zirconium organic compound include, for example, zirconium normal propyrate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, zirconium acetylacetonate bisethylacetoacetate and the like. Can be mentioned.
[0090]
Specific examples of the aluminum organic compound include aluminum acetylacetonate and aluminum organic acid chelate.
[0091]
Specific examples of the silicon organic compound include compounds having the ligands exemplified for the titanium organic compound and the zirconium organic compound described above.
[0092]
One type of the metal organic compound may be used, or two or more types may be appropriately mixed and used. Among the metal organic compounds, a metal organic compound (organometallic complex) having a chelating ligand such as acetylacetonate and having a coordination bond with the high hydrogen bonding resin is crosslinked. The reactivity is moderately preferable, and among these, a titanium chelate compound is particularly preferable in terms of stability in a coating solution when the resulting composition is applied. In addition, the titanium chelate compound exhibits a particularly excellent effect in improving water resistance.
[0093]
Moreover, as the crosslinking agent for the hydrogen bonding group, a coupling agent such as a titanium coupling agent, a silane coupling agent, a melamine coupling agent, an epoxy coupling agent, an isocyanate coupling agent; An epoxy compound, a copper compound, a zirconium compound, and the like may be used.
[0094]
From the viewpoint of improving water resistance, among these exemplified compounds, zirconium compounds, water-soluble epoxy compounds, and silane coupling agents are relatively suitably used.
[0095]
Specific examples of the zirconium compound include zirconium halides such as zirconium oxychloride, hydroxyzirconium chloride, zirconium tetrachloride and zirconium bromide; zirconium salts of mineral acids such as zirconium sulfate, basic zirconium sulfate and zirconium nitrate; Zirconium salts of organic acids such as zirconium formate, zirconium acetate, zirconium propionate, zirconium caprylate, zirconium stearate; ammonium zirconium carbonate, sodium zirconium sulfate, ammonium zirconium acetate, sodium zirconium oxalate, zirconium zirconium citrate, zirconium citrate Zirconium complex salts such as ammonium; and the like.
[0096]
Specific examples of the water-soluble epoxy compound include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, glycidyl ether epoxy resin, heterocyclic epoxy resin, glycidyl amine epoxy resin, aliphatic epoxy resin, and the like.
[0097]
Specific examples of silane coupling agents include amino silane coupling agents, vinyl or methacryloxy silane coupling agents, epoxy silane coupling agents, methyl silane coupling agents, chloro silane coupling agents, and mercapto types. A silane coupling agent etc. are mentioned.
[0098]
The mixing ratio of the crosslinking agent to the high hydrogen bonding resin is not particularly limited, but the number of moles of the crosslinkable functional group in the high hydrogen bonding resin (that is, hydrogen bonding group and ionic group). HN, and when the number of moles of the cross-linking group in the cross-linking agent (or the cross-linking group containing a ligand when the cross-linking agent is a metal organic compound) is CN, the high hydrogen The ratio K (K = CN / HN) of the number of crosslinkable groups of the crosslinking agent to the number of moles of the crosslinkable functional group possessed by the binding resin should be in the range of 0.001 to 10. Preferably, it is more preferable to use it within the range of 0.01-1.
[0099]
In addition, when a urethane resin is used for the thermosetting resin layer 2 in particular, the inorganic layered compound (A) -containing layer 3 improves the adhesion and adhesiveness with the thermosetting resin layer 2. It is preferable that the surfactant is further included. The surfactant is not particularly limited as long as it can improve the adhesion and adhesiveness between the inorganic layered compound (A) and the thermosetting resin layer 2, but for example, Examples include anionic surfactants, cationic surfactants, zwitterionic surfactants and nonionic surfactants.
[0100]
Examples of the anionic surfactant include aliphatic monocarboxylates, carboxylic acid types such as N-acyloyl glutamate, alkylbenzene sulfonates, naphthalene sulfonate-formaldehyde condensates, and sulfonic acids such as sulfosuccinic acid dialkyl esters. Hydrocarbon anionic surfactants, such as sulfuric acid ester type such as alkyl sulfate, alkyl sulfate polyoxyethylene salt, phosphoric acid ester type such as alkyl phosphate, boric acid ester type such as alkyl borate, Fluorine anionic surfactants such as sodium perfluorodecanoate and sodium perfluorooctyl sulfonate, and silicone anionic surfactants having an anionic group such as a polymer having a polydimethylsiloxane group and a carboxylic acid metal salt Agents.
[0101]
Examples of the cationic surfactant include amine salt types such as alkylamine salts, quaternary ammonium salt types such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, and alkyldimethylbenzylammonium salts.
[0102]
Examples of zwitterionic surfactants include carboxybetaine types such as N, N-dimethyl-N-alkylaminoacetic acid betaine, and glycine types such as 1-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine. It is done.
[0103]
Nonionic surfactants include ester types such as glycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester, polydimethylsiloxane group and alkylene oxide adduct condensation polymer, polysiloxane-polyoxyalkylene copolymer, Ether type such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether and polyoxyethylene polyoxypropylene block polymer, ester ether type such as polyethylene glycol fatty acid ester and polyoxyethylene sorbitan fatty acid ester, alkanol such as aliphatic alkanolamide Examples include amide types and fluorine types such as perfluorodecanoic acid-diglycerin ester and perfluoroalkylalkylene oxide compounds.
[0104]
Among the above surfactants, in particular, ether type nonionic surfactants such as alkali metal salts of carboxylic acids having an alkyl chain of 6 to 24 carbon atoms, polydimethylsiloxane-polyoxyethylene copolymer, etc. (Silicone-based nonionic surfactants) and fluorine-type nonionic surfactants (fluorine-based nonionic surfactants) such as perfluoroalkylethylene oxide compounds are preferred.
[0105]
When the inorganic layered compound (A) -containing layer 3 is formed, for example, when a coating liquid is used, the content of the surfactant is 0.001 wt.% From the viewpoint of effects. % To 5% by weight, preferably 0.003% to 0.5% by weight, more preferably 0.005% to 0.1% by weight. It is particularly preferable to set the values as described above.
[0106]
Moreover, the said inorganic layered compound (A) content layer 3 may contain conventionally well-known various additives, such as a ultraviolet absorber, a coloring agent, and antioxidant, in the range which does not impair the effect of this invention. Good.
[0107]
The composition ratio of the inorganic layered compound (A) in the inorganic layered compound (A) -containing layer 3 is not particularly limited, but all components (composition) of the inorganic layered compound (A) -containing layer 3 are not particularly limited. It is preferable that the weight ratio of the inorganic layered compound (A) to (the total component (composition) of the inorganic layered compound (A) / inorganic layered compound (A) -containing layer 3) is in the range of 0.1 to 1. More preferably, it is in the range of 0.3 to 1.
[0108]
Moreover, when the structural component (composition) which comprises the said inorganic layered compound (A) content layer 3 contains resin, especially a high hydrogen bond resin, the weight ratio (inorganic of an inorganic layered compound (A) with respect to said resin The layered compound / resin is preferably in the range of 1/9 to 9/1, and more preferably in the range of 3/7 to 8/2. Further, when 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 solution used for the coating are not particularly limited. In general, the total amount of the two is preferably in the range of 4 to 15% by weight.
[0109]
When the inorganic layered compound (A) -containing layer 3 contains components other than the inorganic layered compound (A) (hereinafter referred to as other components) such as the high hydrogen bonding resin, these inorganic layered compounds (A ) And other components (method for producing a composition comprising the above-mentioned inorganic layered compound (A) and other components) is not particularly limited, but is uniform during blending or easy to operate. From the viewpoint of (1), for example, (1) a solution obtained by dissolving other components in a solvent and a dispersion obtained by previously swelling or cleaving the inorganic layered compound (A) in a dispersion medium are mixed, and then the solvent and the dispersion medium are removed. (2) A method in which a dispersion obtained by swelling or cleaving the inorganic layered compound (A) with a dispersion medium is added to other components, the other components are dissolved in the dispersion, and then the dispersion medium is removed; (3) No solution in other components dissolved in solvent 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 obtain a dispersion, and then the solvent is removed; (4) resin and inorganic layered compound (A) And the like may be employed.
[0110]
When the other component includes a crosslinking agent for crosslinking the high hydrogen bonding resin, the crosslinking agent is added and mixed after mixing the high hydrogen bonding resin and the inorganic layered compound (A). However, it may be added at the same time as the high hydrogen bonding resin or inorganic layered compound (A), or may be previously dissolved or dispersed in the solvent or dispersion medium. When the crosslinking agent contains a metal organic compound, the crosslinking agent is preferably added after being dissolved in alcohols. Moreover, when forming the said inorganic layered compound (A) content layer 3 by coating, it is preferable to make the said coating liquid acidic from the surface of the stability of the coating liquid containing the said metal organic compound, pH5 or less Is more preferable, and 3 or less is particularly preferable. There is no particular lower limit to the pH of the coating solution, but it is usually 0.5 or more.
[0111]
Among the above-described methods, the methods (1) to (3) are more preferable because a large aspect ratio of the inorganic layered compound (A) can be easily obtained. Further, when adopting the above methods (1) to (3), it is preferable from the viewpoint of dispersibility of the inorganic layered compound (A) that the treatment is performed using a high-pressure dispersion apparatus.
[0112]
Examples of the high-pressure dispersing device include an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and other examples include a Manton Gorin type high-pressure dispersing device such as a homogenizer manufactured by Izumi Food Machinery. It is done. A composition mixture containing the inorganic layered compound (A) and the other components such as a resin is subjected to a high-pressure dispersion treatment, particularly 100 kgf / cm. ² By carrying out the high-pressure dispersion treatment under the above pressure conditions, a composition in which the inorganic layered compound (A) and the other components are uniformly dispersed and a coating liquid containing the composition can be obtained.
[0113]
As shown in FIG. 7, the high-pressure dispersion treatment in the present invention means that a high-shearing or high-pressure dispersion treatment is performed by causing a composition mixed solution mixed with particles to be dispersed or a dispersion medium to pass through and collide with a plurality of thin tubes 11. Dispersion treatment is performed under special conditions such as high pressure.
[0114]
In such a high-pressure dispersion treatment, the composition mixed solution is preferably passed through a narrow tube 11 having a tube diameter of 1 μm to 1,000 μm, and the maximum pressure condition is 100 kgf when passing through the thin tube 11. / Cm ² The above pressure is preferably applied, and further 500 kgf / cm. ² More preferably, the above pressure is applied, 1,000 kgf / cm ² It is particularly preferable that the above pressure is applied. Further, when the composition mixed solution passes through the narrow tube 11, the maximum arrival speed of the composition mixed solution preferably reaches 100 m / s or more, and the heat transfer rate is preferably 100 kcal / hr or more.
[0115]
The principle of the high-pressure treatment in the high-pressure dispersion treatment apparatus used for the high-pressure dispersion treatment will be schematically explained. First, the composition mixture is sucked by the pump 12 into the feeder tube 13 having a tube diameter larger than that of the thin tube 11. It is captured. Subsequently, a high pressure is applied to the composition mixture in the feeder tube 13 by the pump 12. At this time, the composition mixed solution in the feeder tube 13 is pushed out toward the thin tube 11 by a backflow prevention valve (not shown) provided in the feeder tube 13. Accordingly, the composition mixed solution is in a high pressure and high speed state in the thin tube 11, and the inorganic layered compound (A) particles of the composition mixed solution collide with each other and the inner wall of the thin tube 11, thereby (A) The diameter and thickness of the particles, particularly the thickness, are subdivided and more uniformly dispersed, and taken out from the discharge pipe 14 to the outside.
[0116]
For example, when the flow velocity at the point where the maximum velocity is instantaneously reached is, for example, 300 m / s with respect to the composition mixed solution which is the processing sample in the narrow tube 11 portion, the volume is 1 × 10 ^-3 m ^Three 1 / (3 × 10 ^Five ) When it passes in sec and the temperature of the composition mixture rises by 35 ° C., energy is transferred to the composition mixture by pressure loss. As for the heat transfer rate, the specific gravity of the composition mixture is 1 g / cm. ^Three 3.8 × 10 at specific heat of 1 cal / g ° C. ^Four kcal / hr.
[0117]
The method for laminating the inorganic layered compound (A) -containing layer 3 according to the present invention on the thermosetting resin layer 2 is not particularly limited, but the inorganic layered compound (A) -containing layer 3 is constituted. A coating liquid (composition liquid mixture) containing a constituent component (for example, an inorganic layered compound (A) alone or a composition comprising the inorganic layered compound (A) and other components) and a liquid, and a thermosetting resin layer After coating (coating) on the surface of 2 and forming a coating film, for example, the coating film is dried and heat-treated to remove the liquid from the coating film (coating method), or the inorganic layered For example, a method of laminating a film composed of the components constituting the compound (A) -containing layer 3 on the surface of the thermosetting resin layer 2 is preferably used.
[0118]
More specifically, the coating liquid containing the component constituting the inorganic layered compound (A) -containing layer 3 and the liquid is the component constituting the inorganic layered compound (A) -containing layer 3 as described above. As described above, it is a liquid dispersed or dissolved in a liquid such as a solvent or a dispersion medium. From the viewpoint of gas barrier properties of the resulting laminate, the liquid is preferably a dispersion medium that swells or cleaves the above-described inorganic layered compound (A). When the liquid is a dispersion medium, the inorganic layered compound (A) is dispersed in the liquid in a swollen or cleaved state.
[0119]
Examples of the method used for coating the coating liquid include gravure methods such as a direct gravure method, a reverse gravure method, and a micro gravure method; a roll coating method such as a two-roll beat coat method and a bottom feed three-reverse coat method; Various conventionally known methods such as doctor knife method; die coating method; dip coating method; spray coating method; spin coating method; bar coating method;
[0120]
Moreover, when using the method of (1)-(3) mentioned above as a manufacturing method of the said composition, after removing the solvent and dispersion medium which were used for formation of the said inorganic layered compound (A) content layer 3 from a system, Heat aging the obtained laminate at, for example, 110 ° C. or more and 220 ° C. or less can particularly improve the water resistance of the finally obtained laminate, that is, the gas barrier property after the water resistance environment test. To preferred. The aging time is not limited, but the inorganic layered compound (A) -containing layer 3 needs to reach at least the set temperature. For example, in the case of a method using contact with a heating medium such as a hot air dryer, 1 second or more and 100 minutes or less. Is preferred.
[0121]
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 a particularly excellent effect in improving water resistance when the other component contains a high hydrogen bonding resin.
[0122]
In the present invention, as shown in FIG. 3, the inorganic layered compound (A) -containing layer 3 is such that the inorganic layered compound (A) faces each other, for example, the unit crystal layers 31 due to the shape of the layer. And dispersed and oriented in the resin 32 of the inorganic layered compound (A) -containing layer 3 in a swollen or cleaved state, for example, so as to be substantially parallel to the surface direction of the inorganic layered compound (A) -containing layer 3. Therefore, a maze effect can be produced, and excellent gas barrier properties (including heat-resistant gas barrier properties) can be obtained.
[0123]
Moreover, in this invention, the inorganic compound (B) used for the said inorganic compound (B) content layer 4 is an alkali metal, alkaline-earth metal, a transition element, a periodic table 3B group element, 4B group element, 5B group At least one element selected from the group consisting of elements, ie, periodic table 1A group, 2A group, 3A group, 3B group, 4A group, 4B group, 5A group, 5B group, 6A group, 7A group, and 8 group An inorganic compound containing at least one element selected from the group consisting of elements belonging to the above, preferably an element having an atomic number of 12 or more among elements selected from the group consisting of the above elements.
[0124]
The inorganic compound (B) -containing layer 4 has high hardness and excellent chemical resistance, and is used as a barrier layer together with the inorganic layered compound (A) -containing layer 3. The laminated body according to the present invention has a gas barrier property ( (Including heat-resistant gas barrier properties) and, if necessary, light barrier properties (light-shielding properties). Moreover, the said inorganic compound (B) content layer 4 has low water vapor permeability, and can provide the water vapor | steam barrier property excellent in the said laminated body.
[0125]
The composition of the inorganic compound (B) -containing layer 4 may be appropriately set depending on the required physical properties, and is not particularly limited. However, in order to improve the heat-resistant gas barrier property which is the object of the present invention, the inorganic The compound (B) is at least one selected from the group consisting of metals, metal oxides, nitrides, and hydroxides, including at least one element selected from the group consisting of the above elements. Preferably, it is at least one selected from the group consisting of metals, metal oxides, and nitrides.
[0126]
Specific examples of the inorganic compound (B) include aluminum, silver, gold, platinum, palladium, silicon oxide, aluminum oxide, aluminum hydroxide, titanium oxide, titanium hydroxide, zirconium oxide, Zirconium hydroxide, composite of aluminum oxide and silicon oxide, composite of zinc oxide and silicon oxide, composite of calcium oxide and silicon oxide, boron oxide and silicon oxide These composites, silicon nitrides such as polysilazane, etc. are mentioned, but are not particularly limited. Only one kind of these inorganic compounds (B) may be used, or two or more kinds may be appropriately mixed and used.
[0127]
A method for forming the inorganic compound (B) -containing layer 4 composed of these inorganic compounds (B) is not particularly limited, but a vapor deposition method such as physical vapor deposition or chemical vapor deposition; a sol-gel method;
[0128]
For example, when the inorganic compound (B) -containing layer 4 is made of aluminum, silicon oxide, aluminum oxide, or the like, a vapor deposition method is suitably used for forming the inorganic compound (B) -containing layer 4. .
[0129]
The inorganic compound (B) -containing layer 4 comprises a composite of aluminum oxide and silicon oxide, a composite of zinc oxide and silicon oxide, a composite of calcium oxide and silicon oxide, In the case of a complex of elemental oxide and silicon oxide, binary evaporation using a plurality of evaporation sources can be employed.
[0130]
Examples of the sol-gel method include a method of converting a metal alkoxide such as tetraethylorthosilicate and titanium tetraisopropoxide into a metal oxide (hydroxide) by, for example, dealcoholization reaction. As the sol-gel method, for example, the inorganic compound (B) -containing layer 4 made of silicon oxide, titanium oxide or the like is used for layer formation.
[0131]
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 composed of a compound obtained by combining an organic compound with the inorganic compound (B) by a chemical vapor deposition method, or an active hydrogen compound by a sol-gel method. And may further contain an organic compound such as an isocyanate compound.
[0132]
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 later the inorganic layered compound (A). Although there is a method of laminating on the content layer 3, it is preferably vapor deposition or coating of the components constituting the inorganic compound (B) content layer 4 on the inorganic stratiform compound (A) content layer 3. As a specific method in the case of coating, the method of coating the coating liquid containing the structural component which comprises the said inorganic compound (B) content layer 4 on the inorganic layered compound (A) content layer 3 etc. can be used. .
[0133]
Thus, the shape of the laminated body of this invention obtained is not specifically limited, For example, a container (a bottle, tray shape, etc.), a film (a sheet | seat is included), a tube, etc. are mentioned. Moreover, it can be set as the various shapes according to the shape of the said support body 1, for example, A film shape is preferable among them.
[0134]
Further, the layer thickness of each layer of the laminate may be appropriately set according to the required barrier performance other than the heat-resistant gas barrier property, the application, and the like, and is not particularly limited, but the heat resistance which is the object of the present invention. The layer thickness of the thermosetting resin layer 2 is in the range of 0.001 μm to 1000 μm, and the layer thickness of the inorganic layered compound (A) -containing layer 3 from the viewpoint of sufficiently exhibiting gas barrier properties and drying properties and adhesion. Is preferably in the range of 0.001 μm to 10 μm, and the layer thickness of the inorganic compound (B) -containing layer 4 is preferably in the range of 0.001 μm to 2 μm.
[0135]
When the laminate is a film laminate, the layer thickness of the thermosetting resin layer 2 is preferably in the range of 0.001 μm to 200 μm, more preferably in the range of 0.001 μm to 20 μm. The layer thickness of the inorganic layered compound (A) -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 inorganic compound (B) containing layer The layer thickness of 4 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.
[0136]
In this invention, while providing the inorganic layered compound (A) containing layer 3 which has the structure mentioned above, each layer is arranged in the order mentioned above, so that the inorganic compound (B) containing layer 4 is a thin film as described above. A sufficient heat-resistant gas barrier property can be obtained even with a thickness. For this reason, according to this invention, since the inorganic compound (B) content layer 4 can be set thinly, the process at the time of disposal can also be facilitated.
[0137]
Moreover, when the said laminated body has the support body layer 1, the said thermosetting resin layer 2 can be made thinner. In this case, the layer 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 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 It 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.
[0138]
In the present embodiment, as shown in FIG. 1 or FIG. 2, the inorganic layered compound (A) -containing layer 3 and the inorganic compound (B) -containing layer 4 are arranged on the thermosetting resin layer 2 in this order. In the above description, the configuration in which the layers are stacked in contact with each other is described; however, the configuration may be such that other layers are stacked between the layers described above. However, if a layer made of a thermoplastic polymer is provided on the laminated surface side of the inorganic layered compound (A) -containing layer 3 and the inorganic compound (B) -containing layer 4 in the thermosetting resin layer 2, the high thermoplasticity due to high temperature. The above-mentioned inorganic layered compound (A) -containing layer 3 and inorganic compound (B) -containing layer 4 are destroyed by molecular plasticization and thermal expansion, and these inorganic layered compound (A) -containing layer 3 and inorganic compound (B) -containing layer are destroyed. 4 may deteriorate various performances, and becomes unsuitable for use at high temperatures. For example, when forming a layer made of a thermoplastic polymer, such as the support layer 1, from the thermoplastic polymer, The layer to be formed is laminated on the surface opposite to the laminated surface of the inorganic layered compound (A) -containing layer 3 and the inorganic compound (B) -containing layer 4 in the thermosetting resin layer 2. 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.
[0139]
Further, for example, when a metal such as the inorganic compound (B) is directly deposited on biaxially stretched polypropylene or the like, the adhesion strength is weak and the quality deteriorates with time. However, the said inorganic compound (B) content layer 4 is excellent in adhesiveness with the said inorganic layered compound (A) content layer 3, and it is synergistic by using it by laminating | stacking on the said inorganic layered compound (A) content layer 3. There is an effect. Accordingly, 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. Moreover, easy tearability can also be improved.
[0140]
In addition, you may mix various additives, such as a ultraviolet absorber, a coloring agent, antioxidant, for example into said each layer as needed.
[0141]
As described above, according to the present invention, the thermosetting resin layer 2 (first layer) made of a thermosetting resin, the inorganic layered compound (A) -containing layer 3 (second layer) having the inorganic layered compound (A). ), An inorganic compound having an inorganic compound (B) containing at least one element selected from the group consisting of alkali metals, alkaline earth metals, transition elements, and periodic table 3B group elements, 4B group elements, and 5B group elements ( B) It can be seen that a laminate having good thermal stability and excellent heat-resistant gas barrier properties can be obtained by laminating the inclusion layer 4 (third layer) in this order.
[0142]
The laminate of the present invention includes (Western) confectionery, miso, pickles, rice cakes, bamboo rings, rice cakes, other processed fishery products, meatballs, hamburgers, hams and sausages, pet foods, and other agricultural products, fertilizers, It is preferably used for gas barrier packaging materials in many fields such as cosmetics, fragrances, infusion packs, vacuum heat insulating materials, semiconductor packaging, oxidizing chemical packaging, precision material packaging, medical treatment, electronics, chemistry, and machinery. The laminate of the present invention is particularly required to have a high heat-resistant gas barrier property, for example, microwave heating cooking or sterilization packaging, retort / boil sterilization packaging, packaging of high-temperature products / high-temperature liquids, vacuum insulation, etc. Is particularly preferably used.
[0143]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these. Moreover, various physical properties of the laminates (film laminates) obtained in the examples and comparative examples were measured as follows.
[0144]
(Thickness measurement)
The thickness of 0.5 μm or more was measured with a commercially available digital thickness gauge (contact thickness gauge, trade name: ultra-high precision deci-micro head MH-15M, manufactured by Nippon Optical Co., Ltd.). On the other hand, a thickness of less than 0.5 μm is measured by gravimetric analysis (the weight measurement value of a film of 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 coating film thickness and IR absorption was prepared and obtained from the calibration curve. Furthermore, in the case of the measurement regarding the film 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 laminate (inorganic layered compound (A) From the content layer) and the ratio of the specific element fraction of the inorganic layered compound (A) alone, the inorganic layered compound (A) -containing layer and the inorganic layered compound (A) -containing layer lower layer such as a thermosetting resin layer The method for obtaining the ratio with the layer to be obtained].
[0145]
(Oxygen permeability measurement)
Based on JIS K7126, measurement was performed at a predetermined temperature with an oxygen permeability measuring device (OX-TRAN 100A, manufactured by MOCON).
[0146]
(Particle size measurement)
Using a laser diffraction / scattering particle size distribution analyzer (LA910, manufactured by HORIBA, Ltd.), the volume-based median diameter of particles considered to be the inorganic layered compound (A) present in the resin matrix of the medium is determined as the particle size L As measured. The dispersion stock solution was measured with a paste cell at an optical path length of 50 μm, and the diluted solution of the dispersion was measured with a flow cell method at an optical path length of 4 mm.
[0147]
[Aspect ratio calculation]
Using an X-ray diffractometer (XD-5A, manufactured by Shimadzu Corporation), diffraction measurement by a powder method of an inorganic layered compound (A) alone and a composition (resin composition) containing the inorganic layered compound (A) Went. As a result, the unit thickness a of the inorganic layered compound (A) was obtained, and 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 method, the aspect ratio (Z) was calculated by the formula Z = L / a.
[0148]
[Example 1]
[Coating liquid for thermosetting resin layer]
In a 1/1 mixed solvent of toluene / methyl ethyl ketone, polyester polyol (ADCOAT AD335AE: manufactured by Toyo Morton Co., Ltd.) and toluene diisocyanate in a weight ratio of 15/1, and the total amount of polyester polyol and toluene diisocyanate It added so that solid content concentration might be 20 weight%, and it was set as the coating liquid for thermosetting resin layers.
[0149]
[Inorganic layered compound (A) -containing layer coating solution]
In a dispersion kettle with a stirrer (trade name: Despa MH-L, manufactured by Asada Tekko Co., Ltd.), ion exchange water (specific electric conductivity 1 μs / cm or less) 1000 g and polyvinyl alcohol (PVA117H; high hydrogen bonding resin); Made by Kuraray Co., Ltd., saponification degree: 99.6%, polymerization degree 1,700), and heated to 95 ° C. under low speed stirring (1,500 rpm, peripheral speed about 4 m / second). The solution (1) was obtained by stirring for time and dissolving. Subsequently, the temperature of the solution (1) was lowered to 65 ° C. with stirring, and then an aqueous alcohol solution prepared by previously mixing 400 g of ion-exchanged water and 94 g of 1-butanol was slowly added dropwise to the solution (1). . After completion of the dropping, 50 g of high-purity natural montmorillonite (trade name: Kunipia G; manufactured by Kunimine Kogyo Co., Ltd.) as an inorganic layered compound (A) was added as a powder at 65 ° C., and the stirring conditions were high-speed stirring (3000 rpm). The resin composition mixture (2) was obtained by switching to a peripheral speed of about 8 m / sec and stirring and dispersing for 90 minutes.
[0150]
Next, the above resin composition mixed solution (2) is passed through a high-pressure dispersion device (trade name: ultrahigh-pressure homogenizer M110-E / H, manufactured by Microfluidics Corporation) to 1.750 kgf / cm. ² Was processed once to obtain a uniform dispersion (3) with good dispersibility. The solid concentration of the dispersion (3) was about 7.6% by weight.
[0151]
The above dispersion (3) composed of PVA and natural montmorillonite (Kunipia G) is dried and solidified, then pulverized and subjected to powder X-ray analysis, and the interplanar spacing d of the natural montmorillonite (Kunipia G) swollen and cleaved is measured. did. As a result, the inter-surface distance d was larger than the unit thickness a, and it was found that the natural montmorillonite (Kunipia G) was sufficiently opened for the reasons described above. The aspect ratio of the natural montmorillonite (Kunipia G) whose wall was opened at this time was 200 or more.
[0152]
1500 g of the above dispersion (3) was charged into a dispersion kettle with a stirrer (trade name: Despa MH-L, manufactured by Asada Tekko Co., Ltd.) so that the pH of the system (pH of dispersion (3)) was about 3. 4 g of titanium acetylacetonate (trade name: TC100, manufactured by Matsumoto Pharmaceutical Co., Ltd.) as a metal organic compound under low speed stirring (1,500 rpm, peripheral speed) 4.10 m / min), gradually added. Thereafter, 0.15 g of a nonionic surfactant (trade name: SH3746, manufactured by Toray Dow Corning Co., Ltd.) was added while stirring, and this was used as the inorganic layered compound (A) -containing layer coating solution. .
[0153]
[Manufacture of laminates]
A biaxially stretched polyethylene terephthalate (OPET) film having a thickness of 12 μm (trade name: Espet T4102; manufactured by Toyobo Co., Ltd., with single-sided corona treatment) is used as a support layer, and on the corona-treated surface of this support layer, After applying the gravure coating solution for the thermosetting resin layer, it was dried to form a urethane resin layer (thermosetting resin layer) of about 0.1 μm.
[0154]
Next, the dispersion liquid is subjected to gravure coating with the inorganic layered compound (A) -containing layer coating liquid on the urethane resin layer, and then dried, whereby the inorganic layered compound ( A) The coating film in which the inorganic layered compound (A) content layer based on the content layer coating liquid was formed was obtained. The dry thickness of the inorganic layered compound (A) -containing layer was about 0.4 μm.
[0155]
Subsequently, aluminum deposition is performed on the inorganic layered compound (A) -containing layer of the coating film using a vacuum deposition apparatus to form an inorganic compound (B) -containing layer having a thickness of about 0.04 μm. A film laminate was obtained as a laminate. The oxygen permeability at 80 ° C. of the obtained film laminate was measured and found to be 0.2 (ml / atm · m ² ・ Day) It was excellent as follows.
[0156]
[Comparative Example 1]
In Example 1, except for not laminating the inorganic layered compound (A) -containing layer, the same operation as in Example 1 was performed to obtain a comparative film laminate. The oxygen permeability at 80 ° C. of the obtained film laminate was measured and found to be 100 (ml / atm · m ² ・ Day) More than the above.
[0157]
[Example 2]
In Example 1, a biaxially stretched polypropylene (OPP) film having a thickness of 20 μm (trade name: Bilen film-OT P2102; manufactured by Toyobo Co., Ltd., with single-sided corona treatment) is used as a support layer in place of the OPET film. Except having used, operation similar to Example 1 was performed and the film laminated body as a laminated body concerning this invention was obtained. The obtained film laminate had a low oxygen permeability at 80 ° C., and the laminate had excellent heat-resistant gas barrier properties.
[0158]
Example 3
In Example 1, on the inorganic layered compound (A) content layer of a coating film, it replaced with aluminum vapor deposition, the silicon oxide vapor deposition using a vacuum vapor deposition apparatus was performed, and the inorganic compound (about 0.04 micrometer consisting of silicon oxide ( B) Except having formed the content layer, operation similar to Example 1 was performed and the film laminated body as a laminated body concerning this invention was obtained. The obtained film laminate had a low oxygen permeability at 80 ° C., and the film laminate was excellent in heat-resistant gas barrier properties.
[0159]
Example 4
In Example 3, instead of the OPET film, the same OPP film as used in Example 2 was used as the support layer, and the same operation as in Example 3 was performed to obtain the laminate according to the present invention. A film laminate was obtained. The obtained film laminate had a low oxygen permeability at 80 ° C., and the film laminate was excellent in heat-resistant gas barrier properties.
[0160]
【The invention's effect】
In the laminate according to claim 1 of the present invention, as described above, the first layer, the second layer, and the third layer are laminated in this order, and the first layer is a layer 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, alkaline earth metal, transition element, and periodic table group 3B element, group 4B element, group 5B It is the structure which is a layer which has an inorganic compound (B) containing the at least 1 sort (s) of element chosen from the group which consists of elements.
[0161]
In the laminate according to claim 2 according to the present invention, as described above, the thermosetting resin is an epoxy resin, a xylene resin, an oligoester acrylate, a guanamine resin, a diallyl phthalate resin, a resorcinol resin, an epoxy acrylate resin, The configuration is at least one resin selected from the group consisting of a phenol resin, an unsaturated polyester resin, a furan resin, a polyimide resin, a urethane resin, a maleic acid resin, a melamine resin, and a urea resin.
[0162]
As described above, the laminate according to the third aspect of the present invention has a configuration in which the inorganic layered compound (A) is a compound that swells and cleaves in a solvent.
[0163]
As described above, the laminate according to claim 4 of the present invention has a configuration in which the inorganic layered compound (A) is a clay mineral.
[0164]
As described above, in the laminate according to claim 5 of the present invention, the inorganic compound (B) is at least one inorganic material selected from the group consisting of metals, metal oxides, nitrides, and hydroxides. It is the structure which is a compound.
[0165]
In the laminate according to claim 6 of the present invention, as described above, the layer having the inorganic layered compound (A) further comprises an organic polymer, an inorganic polymer, a surfactant, and an organometallic complex. It is the structure containing at least 1 type chosen from.
[0166]
As described above, the laminate according to the seventh aspect of the present invention has a configuration in which the layer having the inorganic layered compound (A) further contains a high hydrogen bonding resin.
[0167]
As described above, the laminated body according to claim 8 of the present invention has a configuration in which the support layer is provided on the surface opposite to the second layer laminated surface in the first layer.
[0168]
As described above, the laminate according to claim 9 of the present invention has a configuration in which the support layer is made of at least one base material selected from the group consisting of metal foil, paper, cloth, and synthetic resin film. is there.
[0169]
In the laminated body according to claim 10 according to the present invention, as described above, the layer thickness of the first layer is in the range of 0.001 μm to 1000 μm, and the layer thickness of the second layer is in the range of 0.001 μm to 10 μm. Among these, the thickness of the third layer satisfies the at least one condition within the range of 0.001 μm to 2 μm.
[0170]
The laminated body of Claim 11 which concerns on this invention is a structure which is a film laminated body as mentioned above.
[0171]
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. Due to the labyrinth effect of the layered compound, gas barrier properties can be imparted to the obtained laminate together with the third layer.
[0172]
In addition, in the above configuration, the first layer is made of a thermosetting resin, so that the second layer or the third layer is destroyed due to plasticization or thermal expansion due to high temperature, particularly in the conventional laminate. The destruction of the inorganic layer made of metal or the like (corresponding to the third layer) can be prevented. Therefore, according to said structure, performance, such as gas barrier property which the said 2nd layer and 3rd layer have, can fully be exhibited by heating by improving thermal stability. Therefore, according to said structure, there exists an effect that the laminated body excellent in heat-resistant gas barrier property can be provided.
[0173]
In addition to food products such as (Western) confectionery, miso, pickles, rice cakes, bamboo rings, rice cakes, processed fishery products, meatballs, hamburger, ham / sausage, pet food, agricultural chemicals / fertilizers, cosmetics, It is preferably used for gas barrier packaging materials in many fields such as fragrances, infusion packs, vacuum heat insulating materials, semiconductor packaging, oxidizing chemical packaging, precision material packaging, medical treatment, electronics, chemistry, machinery, and the like. The laminate is particularly required for high heat-resistant gas barrier properties, for example, microwave cooking or sterilization packaging, retort / boil sterilization packaging, packaging of high temperature / high temperature liquid, vacuum insulation, etc. Preferably used.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of a laminate of the present invention.
FIG. 2 is a schematic cross-sectional view showing another example of a laminate according to the present invention.
FIG. 3 is a schematic cross-sectional view showing an inorganic layered compound (A) -containing layer of the laminate of the present invention.
FIG. 4 is an X-ray diffraction graph of the inorganic layered compound (A) for calculating “unit thickness a” of the inorganic layered compound (A) in the laminate of the present invention.
FIG. 5 is an X-ray diffraction graph of the inorganic layered compound (A) for calculating the “plane spacing d” of the inorganic layered compound (A) in the laminate of the present invention.
FIG. 6 is a graph of FIG. 5 in which the “plane spacing d” of the inorganic layered compound (A) is difficult when the peak corresponding to “plane spacing d” overlaps with the halo (or background) and is difficult to detect. It 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]
1 Support layer
2 Thermosetting resin layer (first layer)
3 Inorganic layered compound (A) -containing layer (second layer)
4 Inorganic compound (B) -containing layer (third layer)
31 Unit crystal layer
32 resin

Claims (11)

The first layer, the second layer, and the third layer are laminated in this order,
The first layer is a layer made of a thermosetting resin,
The second layer is a layer having an inorganic layered compound (A),
An inorganic compound (B) in which the third layer contains at least one element selected from the group consisting of alkali metals, alkaline earth metals, transition elements, and periodic table 3B group elements, 4B group elements, and 5B group elements is a layer having,
The layered product , wherein the third layer is formed by vapor-depositing or coating a constituent component constituting the third layer on the second layer .   The thermosetting resin is epoxy resin, xylene resin, oligoester acrylate, guanamine resin, diallyl phthalate resin, resorcinol resin, epoxy acrylate resin, phenol resin, unsaturated polyester resin, furan resin, polyimide resin, urethane resin, maleic The laminate according to claim 1, wherein the laminate is at least one resin selected from the group consisting of an acid resin, a melamine resin, and a urea resin.   The laminate according to claim 1 or 2, wherein the inorganic layered compound (A) is a compound that swells and cleaves in a solvent.   The laminate according to any one of claims 1 to 3, wherein the inorganic layered compound (A) is a clay mineral.   The inorganic compound (B) is at least one inorganic compound selected from the group consisting of metals, metal oxides, nitrides, and hydroxides. The laminated body as described in.   The layer having the inorganic layered compound (A) further contains at least one selected from the group consisting of an organic polymer, an inorganic polymer, a surfactant, and an organometallic complex. The laminated body of any one.   The layered product according to any one of claims 1 to 6, wherein the layer having the inorganic layered compound (A) further contains a high hydrogen bonding resin.   The laminate according to any one of claims 1 to 7, wherein a support layer is provided on a surface opposite to the second layer laminate surface in the first layer.   The laminate according to claim 8, wherein the support layer is made of at least one substrate selected from the group consisting of metal foil, paper, cloth, and synthetic resin film.   The thickness of the first layer is in the range of 0.001 μm to 1000 μm, the thickness of the second layer is in the range of 0.001 μm to 10 μm, and the thickness of the third layer is in the range of 0.001 μm to 2 μm. The laminated body according to claim 1, wherein at least one condition is satisfied.   It is a film laminated body, The laminated body of any one of Claims 1-10 characterized by the above-mentioned.

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