JP2006265517A - Gas-barrier material and gas-barrier method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an optically transparent gas-barrier material usable under high-temperature conditions exceeding 350°C and thus usable for leak prevention at production line piping junctions and the diaphragms of batteries and/or electrolyzers, etc., in various chemical industry sectors, and to provide a gas-barrier method using the gas-barrier material. <P>SOLUTION: The gas-barrier material is obtained by the following process: A layered inorganic compound singly or the layered inorganic compound and a small amount of an additive are dispersed or dissolved in water or a liquid as water-based dispersion medium to prepare a homogeneous inorganic layered compound dispersion, which is left at rest to sediment inorganic layered compound particles, and the liquid as the dispersion medium is separated by a solid/liquid separatory means, thus forming the particles in membrane. This gas-barrier material thus obtained consists of a self-standing membrane where the laminate of the particles is highly aligned. Another version of this gas-barrier material consists of a laminate thereof. Any of these gas-barrier materials is usable as a covering material for pipings and flat plate members. The gas-barrier method involves using any of these gas-barrier materials. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a gas shielding material comprising a film containing an inorganic layered compound as a main constituent, and a gas shielding method using the shielding material, and more specifically, a machine that can be used as a self-supporting film. The present invention relates to a gas shielding material having high strength and a highly improved orientation lamination of inorganic layered compound particles, and a gas shielding method using the shielding material alone or in combination. In the technical field of gas shielding material or water vapor shielding material, it has been difficult to obtain a material that has been extremely gas shielding, transparent, and usable under high temperature conditions. However, the present invention provides a new material and new technology such as a gas shielding material having high thermal stability and excellent flexibility, and a gas shielding method using the shielding material.

  In general, various production processes under high temperature conditions are used in many chemical industry fields. In the pipe connection parts of these production lines, measures are taken to prevent liquid and gas leaks, for example, by packing or welding. Until now, for example, packing excellent in flexibility has been made using an organic polymer material. However, the heat resistance of the liquid crystal polyester is the highest at 350 ° C., and at a temperature higher than this, a metal packing must be used, but the metal packing is compared with that of an organic polymer material, There was a problem that it was inferior in flexibility. An aluminum foil or an aluminum vapor deposition film has a high gas barrier property but is not transparent. Moreover, since aluminum foil is a metal, it cannot be used as a sealing material wound around the screw portion. In addition, there is a silica vapor deposition film that is transparent and excellent in gas barrier properties. However, since the base material of this silica vapor deposition film is an organic compound film, it cannot be used under high temperature conditions exceeding 350 ° C. In addition to being used as a packing, these gas shielding materials may be used by being wound around a joint screw portion, wound around a tube, or attached to a flat plate member. Recently, the production of substances using a microreactor has been studied in order to increase the efficiency of the reaction. In a microreactor, it is important to make the reactor smaller in order to increase efficiency, and therefore the sealing method must be made compact. In this respect, when a metal packing is used, a mechanism for strongly pressing the sealing surface such as a flange is required, which is not preferable from the viewpoint of reducing the reactor. In addition, when it is necessary to increase the temperature as a whole, it is often the case that the heat resistance of the packing portion limits the normal operating temperature of the entire microreactor, and therefore development of a heat resistant sealing material has been demanded.

  It is known that inorganic layered compounds such as swellable clays are dispersed in water or alcohol, and the dispersion is spread on a glass plate, allowed to stand, and dried to form a film with uniform particle orientation. As a result of this film formation, a fixed orientation sample for X-ray diffraction has been prepared (see Non-Patent Document 1). However, when a film is formed on a glass plate, it is difficult to peel the inorganic layered compound thin film from the glass plate, and there is a problem that it is difficult to obtain a self-supporting film, such as a crack in the film when peeled off. Even if the film is peeled off, the obtained film is brittle and insufficient in strength, and it has been difficult to prepare a film having a uniform thickness without pinholes.

  In addition to the molding material, water-soluble polymers are used as dispersants, thickeners, binders, inorganic materials, and gas shielding materials. For example, a carboxyl group-containing high hydrogen gas-bonding resin (A) having two or more carboxyl groups in the molecule, such as polyacrylic acid, and a hydroxyl group having two or more hydroxyl groups in the molecular chain, such as starches. A composition of 100 parts by weight of a mixture having a weight ratio A / B = 80/20 to 60/40 of the high hydrogen gas binding resin (B) and 1 to 10 parts by weight of an inorganic layered compound such as clay mineral is formed. It is known that when a film having a thickness of 0.1 to 50 μm formed from this composition is subjected to heat treatment and electron beam treatment, the film obtains gas barrier properties (see Patent Document 1). However, in this case, there is a problem that the water-soluble polymer resin is the main component and the heat resistance is not high.

  In addition, by laminating a layer made of a resin composition containing an inorganic stratiform compound and a resin between two polyolefin resin layers, a laminated film that is excellent in moisture resistance and gas barrier properties and applied to food packaging is obtained. (See Patent Document 2). However, in this case, the layer of the resin composition containing the inorganic stratiform compound is used as a part of the multilayer film and is not used alone as a self-supporting film. Moreover, the volume ratio (inorganic layered compound / resin) of this resin composition is specified in the range of 5/95 to 90/10, and 10% or more of the resin is contained.

Recently, Langmuir-Blodgett
An inorganic layered compound thin film is applied by applying (Method) (for example, see Non-Patent Document 2). However, in this method, the inorganic layered compound thin film is formed on the surface of a substrate made of a material such as glass, and an inorganic layered compound thin film having strength as a self-supporting film cannot be obtained. Furthermore, conventionally, for example, various methods for preparing a functional inorganic layered compound thin film have been reported. For example, a method for producing a clay thin film comprising forming an aqueous dispersion of a hydrotalcite-based intercalation compound into a film and drying the reaction (see Patent Document 3), utilizing a reaction between a clay mineral and phosphoric acid or a phosphate group, and the reaction A method for producing a clay mineral thin film in which the bond structure of the clay mineral is oriented and fixed by applying a heat treatment for promoting the coating (see Patent Document 4), and for a film treatment containing a complex compound of a smectite clay mineral and a bivalent or higher metal There are many cases including an aqueous composition (see Patent Document 5). However, until now, there has been no development example of an inorganic layered compound alignment film that has mechanical strength that can be used as a free-standing film and that has a highly oriented laminate of clay particles to impart gas barrier properties.

  As described above, there has been no film that has a mechanical strength that can be used as a self-supporting film and has a gas barrier property by highly orienting the lamination of inorganic layered compound particles. On the other hand, in the cosmetics and pharmaceutical fields, suitable spherical organic complex clay minerals (see, for example, Patent Document 6 and Patent Document 7), and manufacture of therapeutic drugs for wet athlete's footworms in which clay minerals, acids, and enzymes are mixed (for example, It has been proposed to combine an inorganic layered compound and an organic compound such as Patent Document 8 and Patent Document 9). However, the fact is that these organic composite clay minerals have not been used as free-standing films, and in this technical field, a new inorganic layered compound film having mechanical strength that can be used as a free-standing film has been developed. There was a strong demand for practical application.

Japanese Patent Laid-Open No. 10-231434 JP 7-251489 A JP-A-6-95290 JP-A-5-254824 JP 2002-30255 A JP-A 63-64913 Japanese Patent Publication No. 07-17371 Japanese Patent Laid-Open No. 52-15807 Japanese Patent Publication No.61-3767 Haruo Shiramizu “Clay Mineralogy-Basics of Clay Science”, Asakura Shoten, p. 57 (1988) Umezawa Yasushi, Clay Science, Vol. 42, No. 4, 218-222 (2003)

  Under such circumstances, the present inventors have a mechanical strength that can be used as a self-supporting film in view of the above-described prior art, and have excellent flexibility and a high temperature exceeding 350 ° C. With the goal of developing a new gas barrier film that can be used under temperature conditions, an inorganic layered compound dispersion aqueous solution is prepared in the process of intensive research, and a small amount of water-soluble polymer is mixed with this to obtain a uniform dispersion. Then, the dispersion is allowed to stand horizontally to deposit the inorganic layered compound particles, and the liquid as the dispersion medium can be separated into various solid-liquid separation methods, such as centrifugation, filtration, vacuum drying, and freeze-drying. Alternatively, the inorganic layered compound in which the inorganic layered compound particles are oriented by separating from the support by separation by a heating evaporation method, etc., and forming into a film shape, followed by drying, heating or cooling as necessary. It found that to obtain, further extensive research, and completed the present invention. The present invention provides a flexible gas shielding material having a mechanical strength that can be used as a self-supporting film by orienting and densely laminating an inorganic layered compound, and having light transmission properties and excellent thermal stability. An object of the present invention is to provide a gas shielding method using a shielding material.

The present invention for solving the above-described problems comprises the following technical means.
(1) A gas shielding material comprising a film containing a layered inorganic compound as a main constituent, wherein the film is composed of 1) a layered inorganic compound alone or a layered inorganic compound and an additive. The gas shielding material as described above, wherein the weight ratio to the total solid exceeds 90%, 3) has a gas barrier property, and 4) has a mechanical strength usable as a self-supporting film.
(2) The layered inorganic compound is one or more of mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, and nontronite, as described in (1) above Gas shielding material.
(3) The additive is epsilon caprolactam, dextrin, starch, cellulosic resin, gelatin, agar, flour, gluten, alkyd resin, polyurethane resin, epoxy resin, fluororesin, acrylic resin, methacrylic resin, phenolic resin, polyamide resin, It is one or more of polyester resin, polyimide resin, polyvinyl resin, polyethylene glycol, polyacrylamide, polyethylene oxide, protein, deoxyribonucleic acid, ribonucleic acid and polyamino acid, polyhydric phenol, and benzoic acid compound The gas shielding material according to (1).
(4) Addition reaction, condensation reaction, polymerization reaction, etc. in the additive molecule, between the additive molecule, between the additive and the inorganic layered compound, between the inorganic layered compound crystals, by any method such as heating and light irradiation. The gas shielding material according to (1), wherein a chemical reaction is performed to generate a new chemical bond to improve gas barrier properties or mechanical strength.
(5) In the differential thermal analysis, the weight loss in the temperature range of 200 ° C. to 600 ° C. is less than 10 percent, and the basic structure of the layered inorganic compound constituting the gas shielding material does not change, (1) To (4).
(6) The above (1), wherein the permeability coefficient for air, oxygen gas, nitrogen gas, hydrogen gas, and helium gas at room temperature is less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ^−1. To (4).
(7) After heat treatment at 600 ° C. for 24 hours, the gas permeability coefficient of helium gas, hydrogen gas, oxygen gas, nitrogen gas, and air at room temperature is less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ The gas shielding material according to any one of (1) to (4), wherein:
(8) The gas shielding material according to any one of (1) to (4), wherein a water permeability coefficient of pure water at room temperature is 2 × 10 ⁻¹⁰ cm / sec or less.
(9) The gas shielding material according to any one of (1) to (8), wherein the gas shielding material is a sealing material, a packing material, or a packaging material.
(10) A gas shielding method comprising performing a gas shielding treatment using the gas shielding material according to any one of (1) to (8).
(11) A gas shielding method comprising performing a gas shielding treatment using a multilayer film including the gas shielding material according to any one of (1) to (8).
(12) The gas shielding method according to (10) or (11), wherein the gas shielding material is used as a sealing material, a packing material, or a packaging material.

Next, the present invention will be described in more detail.
The present inventors prepared an aqueous dispersion of an inorganic layered compound, mixed an appropriate amount of an organic reagent such as a water-soluble polymer, and obtained a uniform dispersion, and then the dispersion was subjected to various solid-liquid separation methods. For example, after drying by centrifugation, filtration, vacuum drying, freeze vacuum drying or heat evaporation method, an inorganic layered compound film is obtained on the support, and the inorganic layered compound film is peeled off from the support, whereby the inorganic layered compound is obtained. The inventors have found that a self-supporting film in which particles are oriented and densely laminated can be obtained, and further, a manufacturing method and conditions for obtaining a sufficient strength to be used as a self-supporting film with a uniform thickness. That is, the present invention prepares a dilute and uniform dispersed aqueous solution containing an inorganic layered compound and a water-soluble polymer, and allows the dispersed aqueous solution to stand horizontally to slowly deposit inorganic layered compound particles, and to disperse the dispersion medium. The liquid is separated by various solid-liquid separation methods such as centrifugation, filtration, vacuum drying, freeze vacuum drying or heat evaporation, and formed into a film, and then peeled off from the support. In addition, by adopting manufacturing conditions for obtaining sufficient strength to be used as a free-standing film with a uniform thickness, an inorganic layered compound film in which the lamination of inorganic layered compound particles is highly oriented can be obtained as a free-standing film It is characterized by.

  The inorganic layered compound used in the present invention is a natural or synthetic product, preferably one or more of mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite and nontronite, More preferably, any of natural smectite and synthetic smectite or a mixture thereof is exemplified. The water-soluble polymer used in the present invention has a polar group in the main chain or side chain, and is therefore hydrophilic, cationic or anionic, and highly soluble in water. If there is no particular limitation, for example, epsilon caprolactam, dextrin, starch, cellulosic resin, gelatin, agar, flour, gluten, alkyd resin, polyurethane resin, epoxy resin, fluororesin, acrylic Resin, methacrylic resin, phenolic resin, polyamide resin, polyester resin, imide resin, polyvinyl resin, polyethylene glycol, polyacrylamide, polyethylene oxide, protein, glucose oxidase, peroxidase, deoxyribonucleic acid, ribonucleic acid and polyamido Acid, polyhydric phenols are exemplified with one or more of 3,5-dihydroxybenzoic acid. The inorganic layered compound such as smectite used in the present invention is also hydrophilic and is well dispersed in water. Such a water-soluble polymer and the inorganic layered compound have an affinity for each other, and when they are mixed in water, they are easily combined and combined.

  In the method for producing a gas shielding material of the present invention, first, a uniform dispersion in which an inorganic layered compound and a water-soluble polymer are added to water or a liquid that is a dispersion medium mainly composed of water must be prepared. Don't be. As a method for preparing this dispersion, a method of adding a water-soluble polymer after dispersing the inorganic layered compound, a method of dispersing the inorganic layered compound in a solution containing the water-soluble polymer, an inorganic layered compound, and a water-soluble polymer At the same time, any of the above-mentioned liquids may be used as a dispersion. However, in order to disperse the inorganic layered compound, the inorganic layered compound is dispersed in water or a liquid that is a dispersion medium mainly composed of water. It is preferable to add a water-soluble polymer. In this case, first, an inorganic layered compound such as smectite is added to water or a liquid that is a dispersion medium containing water as a main component to prepare a dilute and uniform inorganic layered compound dispersion. The inorganic layered compound concentration in this inorganic layered compound dispersion is suitably from 0.5 to 10 weight percent, more preferably from 1 to 3 weight percent. At this time, if the inorganic layered compound concentration is too thin, there is a problem that it takes too long to dry. In addition, when the inorganic layered compound concentration is too high, the inorganic layered compound is not dispersed well, so that there is a problem that the orientation of the inorganic layered compound particles is poor and a uniform film cannot be formed.

  Next, a water-soluble polymer or a solution containing the same is weighed and added to the inorganic layered compound dispersion to prepare a uniform dispersion containing the inorganic layered compound and the water-soluble polymer. As described above, the inorganic layered compound and the water-soluble polymer are both hydrophilic and well dispersed in water. In addition, since the inorganic layered compound and the water-soluble polymer have an affinity for each other, they are easily combined and complexed when mixed in water. The weight ratio of the water soluble polymer to the total solids is less than 10 percent, preferably 0.005 percent to 0.1 percent. At this time, if the proportion of the water-soluble polymer is too low, the effect of use does not appear, and if the proportion of the water-soluble polymer is too high, the water-soluble polymer is unevenly distributed in the prepared membrane. As a result, the uniformity of the resulting film is reduced and the effect of using the polymer is diminished.

  Next, the dispersion containing the inorganic layered compound and the water-soluble polymer is allowed to stand horizontally, and the inorganic layered compound particles are slowly deposited, and for example, the liquid as the dispersion medium is slowly evaporated to form a film. To do. The composite inorganic layered compound membrane thus formed is preferably selected from various solid-liquid separation methods such as centrifugation, filtration, vacuum drying, freeze vacuum drying and heat evaporation, or these methods. Are combined and dried to obtain a dried water-soluble polymer composite inorganic layered compound film. Among these methods, for example, when using a heat evaporation method, the dispersion liquid that has been degassed in advance by evacuation is poured onto a support such as a flat tray, preferably a plastic or metal tray. In a forced air oven in a forced air blow oven, under a temperature condition of 30 ° C. to 70 ° C., preferably under a temperature condition of 30 ° C. to 50 ° C., for about 3 hours to half a day, preferably 3 hours to 5 hours And drying to obtain a water-soluble polymer composite inorganic layered compound film.

  When the dispersion containing the inorganic layered compound and the water-soluble polymer is not degassed in advance, there may be a problem that pores derived from bubbles are easily formed in the obtained composite inorganic layered compound film. The drying conditions are set so that the liquid content is sufficient to be removed by evaporation. At this time, if the temperature is too low, there is a problem that it takes time to dry. On the other hand, if the temperature is too high, convection of the dispersion occurs, and the film does not have a uniform thickness, and the degree of orientation of the inorganic layered compound particles decreases. Regarding the thickness of the water-soluble polymer composite inorganic layered compound film of the present invention, a film having an arbitrary thickness can be obtained by adjusting the amount of solid used in the dispersion.

  In the present invention, the layering of the inorganic layered compound particles is highly oriented means that the unit layer of inorganic layered compound particles (thickness of about 1 nanometer) is stacked with the direction of the layer surface being the same, and the direction perpendicular to the layer surface Means to have a high periodicity. In order to obtain such an orientation of the inorganic layered compound particles, a dilute and uniform dispersion containing the inorganic layered compound and the water-soluble polymer is allowed to stand horizontally, and the inorganic layered compound particles are slowly deposited, It is important that the liquid as the dispersion medium is slowly evaporated to form a film in which inorganic layered compound particles are densely laminated. Indicating suitable production conditions in this process, the concentration of the inorganic layered compound in the inorganic layered compound dispersion is preferably 0.5 to 10 weight percent, more preferably 1 to 3 weight percent, and heating The drying condition is preferably 3 hours to half a day in a forced air oven under a temperature condition of 30 ° C. to 70 ° C., more preferably a temperature condition of 30 ° C. to 50 ° C. More preferably, the drying is performed for about 3 to 5 hours.

  In addition, when the water-soluble polymer composite inorganic layered compound film does not naturally peel off from a support such as a tray, it is preferably dried, for example, at a temperature of about 80 ° C. to 300 ° C. to facilitate peeling. Get a self-supporting membrane. At this time, if the temperature is too low, there is a problem that peeling does not easily occur. When the temperature is too high, the action of the water-soluble polymer becomes weak due to its thermal deterioration, and the orientation of the inorganic layered compound laminate is poor.

The clay film of the present invention itself uses a layered silicate as a main raw material (90% by weight or more), and as a basic constitution, for example, a natural layer having a layer thickness of about 1 nm, a particle diameter of 1 μm, and an aspect ratio of about 300 Alternatively, the composition is composed of 90% by weight or more of a synthetic swellable layered silicate, and 10% by weight of a natural or synthetic additive of low molecular weight or high molecular weight having a molecular size of several nm. This clay film is produced, for example, by densely laminating layered crystals having a thickness of about 1 nm, oriented in the same direction. The obtained clay film has a thickness of 3 to 100 μm, preferably 3 to 30 μm, and has a gas barrier performance of 30 μm in thickness and an oxygen permeability of less than 0.1 cc / m ² · 24 hr · atm, and a hydrogen permeability of 0 0.1 cc / m ² · 24 hr · atm or less, the water shielding property is a water shielding coefficient of 2 × 10 ⁻¹¹ cm / s or less, and the light transmittance is a transmittance of visible light (500 nm) of 75% or more. The area can be increased to 100 × 40 cm or more, has high heat resistance, and no deterioration in gas barrier properties is observed even after heat treatment at 1000 ° C. for 24 hours.

  Thus, the inorganic layered compound film of the present invention has a highly oriented layer of inorganic layered compound particles and can be used as a self-supporting film, has excellent flexibility, no pinholes, and 350 ° C. This is characterized in that the gas / liquid barrier property is maintained even at a high temperature up to 1000 ° C. Moreover, the inorganic layered compound film of the present invention can be easily cut into an arbitrary size and shape such as a circle, a square, and a rectangle with, for example, scissors and a cutter.

  Therefore, the inorganic layered compound film of the present invention can be widely used as a self-supporting film excellent in flexibility under high temperature conditions. For example, packing such as a pipe connection part of a production line in the chemical industry field or the like It can be used as a heat-resistant / high-barrier member for similar products. Further, the water-soluble polymer is a polar polymer, and similarly interacts with the inorganic layered compound having polarity to produce a thin film excellent in flexibility and strength. Therefore, easy breakage due to pulling, twisting, etc. of the inorganic layered compound thin film is suppressed, thereby obtaining an inorganic layered compound film having excellent characteristics that can be used as a self-supporting film. Furthermore, the inorganic layered compound film of the present invention can be used by being wound around a joint screw portion, wound around a tube, or stuck on a flat plate member, in addition to being used as a packing.

  Multilayering is illustrated as an example of attaching the inorganic layered compound film to a flat plate member. That is, it is possible to improve the gas barrier performance and mechanical strength by multilayering the inorganic layered compound composite film with the film B made of other materials. For example, a film obtained by laminating a fluororesin film with an adhesive as one kind of an inorganic layered compound composite film and a plastic film is exemplified. Since the fluororesin film has low moisture permeability, the multilayer film of the fluororesin film and the inorganic layered compound composite film can be used as a film having high moisture barrier properties and high gas barrier properties. Here, the material of the film B is not particularly limited as long as the formability of the multilayer film with the clay film is good, but preferably, for example, metal foil, thin glass, various plastic films, paper, etc. Illustrated. Furthermore, it is also possible to use a multilayer film including three or more layers including an inorganic layered compound composite film.

  The inorganic layered compound film of the present invention can be used as a self-supporting film, can be used under high temperature conditions exceeding 350 ° C., has excellent flexibility, and has a pinhole structure. It is a dense material that does not exist and has a feature of excellent barrier properties. Therefore, the inorganic layered compound film of the present invention can be widely used as a coating material, packing and separator having excellent flexibility under high temperature conditions exceeding 350 ° C., for example. It can be used to prevent leaks at the line pipe connection parts, diaphragms of batteries and electrolyzers, gas pipe coating, flat plate member coating, and the like.

  Helium gas molecules are the smallest of all gas species, so helium gas is the most difficult to shield. The inorganic layered compound film of the present invention exhibits high gas barrier properties not only against various gases, that is, air, oxygen gas, nitrogen gas, hydrogen gas, but also helium gas. Therefore, the inorganic layered compound film of the present invention is considered to have a shielding property against any gas including an organic gas. In addition, after forming a composite clay film, it can also be used as a protective film for the support without peeling off from the surface of the support, thereby providing an effect of improving the anticorrosion, antifouling and heat resistance of the support. . Since this protective film has an effect of blocking oxygen gas in particular, it is expected to prevent the support from being oxidized. For example, it can be used as a rust preventive for metal structural members and metal joints.

Next, characteristic values of the material of the present invention will be described.
(1) Density As shown in the table below, the conventional material has a highest density of 1.51 in the plastic-filler nanocomposite product. On the other hand, the material of the present invention has a density exceeding 1.51 and exhibits a measured value of density of 2.0 or more, for example, about 2.10. Thus, the material of the present invention has a density greater than 1.51, in particular a high density on the order of 1.60 to 2.50.

(2) Flexibility The softest material in the past is a commercially available sheet made of clay and pulp fiber, and its bending resistance is JIS L1096: 1999 “General Textile Test Method” as the value of the bending resilience test. The value measured according to method A is 8.0 (mN). On the other hand, the hardest clay film is HR50 / 5-80H, the front surface is 5.3 (mN), and the back surface is 17.1 (mN). On the other hand, the material of the present invention has a bending rebound test value of about 2.0 mN and at least a value lower than 8.0 mN. Since it can be said that the bending resistance threshold of the conventional material and the material of the present invention is 8.0 mN, the material of the present invention can be distinguished (identified) from the conventional material by this value.

(3) Properties of raw clay In the present invention, the raw clay preferably has, for example, an aspect ratio (based on the number of particles) of primary particles of about 320, and particularly has a methylene blue adsorption amount and a cation exchange capacity. Higher ones are used. As a specific example, for example, methylene blue adsorption amount is 130 mmol / 100 g, cation exchange capacity is 110 meq / 100 g, 2% aqueous dispersion pH is 10.2, 4% aqueous dispersion viscosity is 350 mPa · s, and aqueous dispersion median diameter is Those having various physical properties of 1.13 μm are exemplified. However, it is not limited to these, and these can be used in the same manner as long as they have the same or equivalent physical properties as standard values. As these raw clays, clay from Tsukiyama, Yamagata Prefecture and materials using this as the main raw material are preferably used.

(4) Other characteristics The material of the present invention has no abnormality in the thermal cycle test (100-600 ° C., 30 cycles) (high heat resistance), and the electrical resistance has a volume resistivity (500 V) of 2.3 × 10. ⁷ Ωm (JIS K6911: 1995) (high insulation), for example, used as a flexible substrate material. The material of the present invention has, for example, the following characteristic values as other characteristics. Oxygen ^{permeability: <0.00008cm 3 / 20μm · m} 2 day · atm, hydrogen ^{permeability: 0.002cm 3 / 20μm · m 2} day · atm, fracture extends: 2.2%, tear test (JISK6252: 2001) : 33.4 N / mm, oxygen index (JIS K7201: 1995):> 94.0, specific heat: 1.19 J / g · K, thermal diffusivity: 1.12 × 10 ⁻⁷ m ² / s, thermal conductivity : 0.27 W / m · K, thermal expansion coefficient (−100 to 100 ° C.): 0.1 × 10 ⁻⁴ K ⁻¹ , thermal expansion coefficient (100 to 200 ° C.): −0.06 × 10 ⁻⁴ K ^-1 , Gas corrosion resistance test: No abnormality. These values show suitable characteristic values of the material of the present invention, and the present invention is not limited to these values. If these are standard values, these are equivalent or equivalent, It is included in the scope of the present invention.

  According to the present invention, (1) an inorganic layered compound film having a uniform orientation of inorganic layered compound particles and a method for producing the same can be provided. (2) The inorganic layered compound film can be used as a self-supporting film. It can be used as a packing or electrolyte partition material that is chemically stable even at high temperatures exceeding (3) and can be used at high temperatures exceeding 350 ° C., and can provide a flexible, translucent inorganic layered compound film. (4) The special effect that the covering material of piping and a flat plate member can be provided is produced.

  Next, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

(1) Manufacture of inorganic layered compound thin film 1.0 g of Kunimine Kogyo Co., Ltd. natural montmorillonite “Kunipia P” as inorganic layered compound is added to 60 cm ³ of distilled water, and Teflon (registered trademark) is rotated in a plastic sealed container. It was put together with the child and shaken vigorously to obtain a uniform dispersion. The dispersion was poured into a polypropylene tray having a flat bottom surface, a square bottom surface, and a length of about 10 cm on one side, and kept at 50 ° C. in a forced air oven with the tray kept horizontal. The film was dried for 5 hours under the above temperature conditions to obtain a translucent thin film having a thickness of about 40 micrometers. Further, this was subjected to a heat treatment at 1000 ° C. for 24 hours.

(2) Characteristics of inorganic layered compound thin film In the differential thermal analysis of this inorganic layered compound thin film (heating rate 5 ° C./min), the weight loss in the temperature range of 200 ° C. to 600 ° C. is 3.7%. Since the reduction width is small, it can be seen that the layered inorganic compound constituting the gas shielding material does not change from the basic structure by heating up to 600 ° C.

The air permeability coefficient of the thin film was measured with Gasperm-100 manufactured by JASCO Corporation. As a result, it was confirmed that the permeation coefficients of air, oxygen gas, nitrogen gas, hydrogen gas, and helium gas at room temperature were less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ in any gas. It was found that the gas barrier performance was exhibited. Helium gas molecules are the smallest of all gases, and since this thin film has a high gas barrier property against helium gas, this thin film has a high gas barrier against any gas regardless of the type of gas. It is possible to show performance. Moreover, as a result of measuring the air permeability coefficient of the thin film that was heat-treated at 1000 ° C. for 24 hours, it was confirmed that it was less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ^−1. No reduction in gas barrier performance was observed.

Next, the water permeability coefficient was measured for the purpose of confirming the water shielding performance of the thin film. The hydraulic conductivity was measured using a universal type hydraulic conductivity measuring device type D manufactured by Hojun Co., Ltd. As a result, the water permeability coefficient of this thin film was measured to be 1 × 10 ⁻¹¹ cm / sec, and it was found that the water shielding performance was exhibited.

(3) Manufacture of sodium polyacrylate composite inorganic layered compound thin film As an inorganic layered compound, 1 gram of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) is added to 60 cm ³ of distilled water, and in a plastic sealed container, It was put together with a Teflon (registered trademark) rotor and shaken vigorously to obtain a uniform dispersion. To this dispersion, 1 cm ^{3 of} an aqueous solution containing sodium polyacrylate (made by Wako Pure Chemical Industries, Ltd., degree of polymerization 2700-7500) as a water-soluble polymer in a predetermined ratio is added, and natural montmorillonite and poly A dispersion containing sodium acrylate was obtained. At this time, dispersions with different weight ratios of natural montmorillonite and sodium polyacrylate were prepared by changing the predetermined ratio. The weight ratio of natural montmorillonite to sodium polyacrylate was 0.98 g / 0.02 g (sodium polyacrylate 2%) to 1.00 g / 0.0000002 g (sodium polyacrylate 0.00002%). Next, a dispersion containing natural montmorillonite and sodium polyacrylate is poured into a brass tray having a flat bottom, a round bottom, and a diameter of about 15 cm. And then depositing the inorganic layered compound particles slowly and keeping the tray horizontal, drying in a forced air oven for 5 hours under a temperature condition of 50 ° C. and having a thickness of about 30 micrometers A uniform water-soluble polymer composite inorganic layered compound thin film was obtained. The formed composite inorganic layered compound thin film was peeled from the tray to obtain a self-supporting water-soluble polymer composite inorganic layered compound thin film excellent in flexibility. Further, this was subjected to a heat treatment at 500 ° C. for 24 hours.

(4) Properties of sodium polyacrylate composite inorganic layered compound thin film Differential thermal analysis of sodium polyacrylate composite inorganic layered compound thin film (heating rate 5 ° C./min)
, The weight loss in the temperature range of 200 ° C. to 600 ° C. is 3.3%, and since this weight reduction width is small, the layered inorganic compound constituting the gas shielding material is heated from the basic structure by heating up to 600 ° C. It turns out that it does not change. Polyacrylate complex inorganic layered compound thin film before heat treatment (sodium polyacrylate 0.02%)
The X-ray diffraction chart is shown in FIG. In this X-ray diffraction chart, a bottom surface reflection peak 001 was observed at d = 1.23 nm. This peak is higher in intensity and narrower in line width than a general bottom reflection peak in this kind of inorganic layered compound mineral. From this result, it can be seen that in the composite inorganic layered compound thin film obtained using polyacrylate, the montmorillonite crystals are oriented and laminated. This bottom surface reflection peak intensity is particularly high in the composite inorganic layered compound thin film using 0.005% to 0.1% sodium polyacrylate, and it can be seen that the montmorillonite crystals are highly oriented. Moreover, among these composite inorganic layered compound thin films, a TG-DTA chart of a polyacrylate composite inorganic layered compound thin film containing 0.02% sodium polyacrylate (at a heating rate of 5 ° C. per minute under an air atmosphere ) Is shown in FIG. From the TG curve of FIG. 2, a weight reduction due to dehydration of adsorbed water was observed from room temperature to 200 ° C., and a large weight loss of montmorillonite was observed from 700 to 800 ° C. At these intermediate temperatures, no thermal change or thermogravimetric change can be observed. This indicates that the composite inorganic layered compound thin film obtained using polyacrylate has high heat resistance.

The permeability coefficient of air of the composite inorganic layered compound thin film in which the use ratio of polyacrylic acid is different was measured with Gasperm-100 manufactured by JASCO Corporation. At this time, the weight ratio of natural montmorillonite and sodium polyacrylate used in preparing the composite thin film was 0.99 g / 0.002 g (sodium polyacrylate 0.2%), 1.00 g / 0.0002 g (polyacrylic). Sodium acrylate 0.02%), 1.00 g / 0.00002 g (sodium polyacrylate 0.002%)
1.00 g / 0.000002 g (0.0002% sodium polyacrylate) and 1.00 g / 0.0000002 g (0.00002% sodium polyacrylate)
It was. In all the composite thin films, the air permeability coefficient at room temperature was confirmed to be less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , indicating that gas barrier performance was exhibited. In addition, after the composite thin film was heat-treated at 500 ° C. for 24 hours, the composite thin film had all the air permeability coefficients at room temperature of less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ^−1. It was confirmed that it showed gas barrier performance even after high temperature treatment.

(1) Manufacture of Nylon Composite Inorganic Layered Compound Thin Film As an inorganic layered compound, 0.95 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) is added to 60 cm ³ of distilled water, and Teflon is placed in a plastic sealed container. It was put together with a (registered trademark) rotor and shaken vigorously to obtain a uniform dispersion. To this dispersion, 0.05 g epsilon-caprolactam powder (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a nylon monomer, and the resulting dispersion had a flat bottom and a round bottom. Pour into a brass tray with a diameter of about 15 cm, leave the dispersion horizontally, slowly deposit the inorganic layered compound particles, and keep the tray level in a forced air oven. And dried at 50 ° C. for 5 hours to obtain a uniform nylon monomer composite inorganic layered compound thin film having a thickness of about 30 μm. The produced inorganic layered compound thin film was peeled from the tray and heat-treated in a heating furnace kept at 250 ° C. for 5 hours to obtain a nylon composite inorganic layered compound film.

(2) Characteristics of inorganic layered compound thin film In the differential thermal analysis of the nylon composite inorganic layered compound thin film (heating rate 5 ° C./min), the weight loss in the temperature range of 200 ° C. to 600 ° C. is 2.6%. Since the weight reduction width is small, it can be seen that the layered inorganic compound constituting the gas shielding material does not change from the basic structure by heating up to 600 ° C.

When the air permeability coefficient of a nylon composite inorganic layered compound membrane (weight ratio of nylon monomer to the total solid is 5%) was measured with Gasperm-100 manufactured by JASCO Corporation, it was 3.2 × 10 ⁻¹⁰ cm ² at room temperature. It was confirmed that it was less than s ⁻¹ cmHg ⁻¹ , and it was found that gas barrier performance was exhibited. Moreover, it was confirmed that the air permeability coefficient of the film obtained by heat-treating the film at 500 ° C. for 24 hours was less than 3.2 × 10 ⁻¹⁰ cm ² s ⁻¹ cmHg ⁻¹ at room temperature. Also showed gas barrier performance.

(1) Manufacture of polyvinyl alcohol composite inorganic layered compound thin film As an inorganic layered compound, 0.95 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) was added to 60 cm ³ of distilled water, and in a plastic sealed container, It was put together with a Teflon (registered trademark) rotor and shaken vigorously to obtain a uniform dispersion. To this dispersion, 1 cm ³ of an aqueous solution containing 0.05 g of polyvinyl alcohol (manufactured by Kanto Chemical Co., Inc., degree of polymerization of about 500) was mixed as a water-soluble polymer. This dispersion containing natural montmorillonite and polyvinyl alcohol is poured into a brass tray having a flat bottom, circular bottom, and a diameter of about 15 cm. The layered compound particles are slowly deposited and dried in a forced air oven in a forced air oven for 5 hours under a temperature condition of 50 ° C. to obtain a uniform composite inorganic material having a thickness of about 30 μm. A layered compound thin film was obtained. Next, the produced composite inorganic layered compound thin film was peeled from the tray.

(2) Properties of polyvinyl alcohol composite inorganic layered compound thin film The air permeability coefficient of a composite inorganic layered compound thin film obtained using polyvinyl alcohol was measured with a Gasperm-100 manufactured by JASCO Corporation. It was confirmed that it was less than × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , and it was found that gas barrier performance was exhibited. Moreover, it was confirmed that the air permeability coefficient of the film obtained by heat-treating the film at 500 ° C. for 24 hours was less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ at room temperature. Also showed gas barrier performance.

(1) Manufacture of starch composite inorganic layered compound thin film As an inorganic layered compound, 0.99 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) is added to 60 cm ³ of distilled water, and a plastic sealed container is filled with Teflon. It was put together with a (registered trademark) rotor and shaken vigorously to obtain a uniform dispersion. To this dispersion, 1 cm ³ of an aqueous solution containing 0.01 g of starch (manufactured by Nacalai Tesque) as a water-soluble polymer was mixed. This dispersion containing natural montmorillonite and starch is poured into a brass tray having a flat bottom, circular bottom, and a diameter of about 15 cm. The dispersion is left to stand horizontally to form an inorganic layer. Compound particles are slowly deposited and dried in a forced air oven in a forced air oven for 5 hours under a temperature condition of 50 ° C. to form a uniform composite inorganic layer having a thickness of about 30 μm. A compound thin film was obtained. Next, the produced composite inorganic layered compound thin film was peeled from the tray.

(2) Properties of starch composite inorganic layered compound thin film The air permeability coefficient of a composite inorganic layered compound thin film obtained using starch was measured with Gasperm-100 manufactured by JASCO Corporation. It was confirmed that it was less than ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , and gas barrier performance was shown.

(1) Production of hydroxyethyl cellulose composite inorganic layered compound thin film As an inorganic layered compound, 0.99 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) was added to 60 cm ³ of distilled water, It was put together with a Teflon (registered trademark) rotor and shaken vigorously to obtain a uniform dispersion. To this dispersion, 1 cm ³ of an aqueous solution containing 0.01 g of hydroxyethyl cellulose (manufactured by Aldrich Chemical Company) as a water-soluble polymer was mixed. This dispersion containing natural montmorillonite and hydroxyethyl cellulose is poured into a brass tray having a flat bottom, circular bottom, and a diameter of about 15 cm. The layered compound particles are slowly deposited and dried in a forced air oven in a forced air oven for 5 hours under a temperature condition of 50 ° C. to obtain a uniform composite inorganic material having a thickness of about 30 μm. A layered compound thin film was obtained. Next, the produced composite inorganic layered compound thin film was peeled from the tray.

(2) Characteristics of hydroxyethyl cellulose composite inorganic layered compound thin film The air permeability coefficient of a composite inorganic layered compound thin film obtained using hydroxyethyl cellulose was measured with a Gasperm-100 manufactured by JASCO Corporation. It was confirmed that it was less than × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , and it was found that gas barrier performance was exhibited.

(1) Manufacture of gelatin composite inorganic layered compound thin film As an inorganic layered compound, 0.99 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) was added to 60 cm ³ of distilled water, and Teflon was placed in a plastic sealed container. It was put together with a (registered trademark) rotor and shaken vigorously to obtain a uniform dispersion. This dispersion was mixed with 1 cm ³ of an aqueous solution containing 0.01 g of gelatin (manufactured by Wako Pure Chemical Industries, Ltd.) as a water-soluble polymer. This dispersion containing natural montmorillonite and gelatin is poured into a brass tray with a flat bottom, circular bottom, and a diameter of about 15 cm. The dispersion is left to stand horizontally to form an inorganic layer. Compound particles are slowly deposited and dried in a forced air oven in a forced air oven for 5 hours under a temperature condition of 50 ° C. to form a uniform composite inorganic layer having a thickness of about 30 μm. A compound thin film was obtained. The produced composite inorganic layered compound thin film was peeled from the tray.

(2) Properties of Gelatin Composite Inorganic Layered Compound Thin Film The air permeability coefficient of a composite inorganic layered compound thin film obtained using gelatin was measured with Gasperm-100 manufactured by JASCO Corporation. It was confirmed that it was less than ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , and gas barrier performance was shown.

(1) Manufacture of Gluten Composite Inorganic Layered Compound Thin Film As an inorganic layered compound, 0.99 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) is added to 60 cm ³ of distilled water, and sealed in a plastic sealed container. It was put together with a (registered trademark) rotor and shaken vigorously to obtain a uniform dispersion. To this dispersion, 0.01 g of gluten (manufactured by Wako Pure Chemical Industries, Ltd.) powder as a water-soluble polymer was mixed. This dispersion containing natural montmorillonite and gluten is poured into a brass tray having a flat bottom, circular bottom, and a diameter of about 15 cm. The dispersion is left to stand horizontally to form an inorganic layer. Compound particles are slowly deposited and dried in a forced air oven in a forced air oven for 5 hours under a temperature condition of 50 ° C. to form a uniform composite inorganic layer having a thickness of about 30 μm. A compound thin film was obtained. The produced composite inorganic layered compound thin film was peeled from the tray.

(2) Characteristics of Gluten Composite Inorganic Layered Compound Thin Film When the air permeability coefficient of a composite inorganic layered compound thin film obtained using gluten was measured with a Gasper-100 manufactured by JASCO Corporation, it was 3.2 × 10 at room temperature. It was confirmed that it was less than ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , and gas barrier performance was shown.

(1) Production of polyethylene glycol composite inorganic layered compound thin film As an inorganic layered compound, 0.99 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Industries Co., Ltd.) was added to 60 cm ³ of distilled water, It was put together with a Teflon (registered trademark) rotor and shaken vigorously to obtain a uniform dispersion. This dispersion was mixed with 1 cm ³ of an aqueous solution containing 0.01 g of polyethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a water-soluble polymer. This dispersion containing natural montmorillonite and polyethylene glycol is poured into a brass tray having a flat bottom, circular bottom, and a diameter of about 15 cm. The layered compound particles are slowly deposited and dried in a forced air oven in a forced air oven for 5 hours under a temperature condition of 50 ° C. to obtain a uniform composite inorganic material having a thickness of about 30 μm. A layered compound thin film was obtained. The produced composite inorganic layered compound thin film was peeled from the tray.

(2) Properties of polyethylene glycol composite inorganic layered compound thin film The air permeability coefficient of a composite inorganic layered compound thin film obtained using polyethylene glycol was measured with a Gasperm-100 manufactured by JASCO Corporation. It was confirmed that it was less than × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , and it was found that gas barrier performance was exhibited.

(1) Manufacture of polyacrylamide composite inorganic layered compound thin film As an inorganic layered compound, 0.99 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) was added to 60 cm ³ of distilled water and placed in a plastic sealed container. And a Teflon (registered trademark) rotor and vigorously shaken to obtain a uniform dispersion. To this dispersion, 1 cm ³ of an aqueous solution containing 0.01 gram of polyacrylamide (manufactured by Aldrich Chemical Company) as a water-soluble polymer was mixed. The dispersion containing natural montmorillonite and polyacrylamide is poured into a brass tray having a flat bottom surface and a circular bottom shape, and a diameter of about 15 cm, and the dispersion is left to stand horizontally. Uniform composite with a thickness of about 30 micrometers by slowly depositing inorganic layered compound particles and drying in a forced air oven for 5 hours in a forced air oven with the tray kept horizontal An inorganic layered compound thin film was obtained. The produced composite inorganic layered compound thin film was peeled from the tray.

(2) Characteristics of polyacrylamide composite inorganic layered compound thin film The air permeability coefficient of a composite inorganic layered compound thin film obtained using polyacrylamide was measured with a Gasperm-100 manufactured by JASCO Corporation. It was confirmed to be less than 2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , and it was found that gas barrier performance was exhibited.

(1) Production of polyethylene oxide composite inorganic layered compound thin film As an inorganic layered compound, 0.99 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Industries Co., Ltd.) was added to 60 cm ³ of distilled water, It was put together with a Teflon (registered trademark) rotor and shaken vigorously to obtain a uniform dispersion. To this dispersion, 1 cm ³ of an aqueous solution containing 0.01 g of polyethylene oxide (manufactured by Aldrich Chemical Company) as a water-soluble polymer was mixed. This dispersion containing natural montmorillonite and polyethylene oxide is poured into a brass tray having a flat bottom, circular bottom, and a diameter of about 15 cm. The layered compound particles are slowly deposited and dried in a forced air oven in a forced air oven for 5 hours under a temperature condition of 50 ° C. to obtain a uniform composite inorganic material having a thickness of about 30 μm. A layered compound thin film was obtained. The produced composite inorganic layered compound thin film was peeled from the tray.

(2) Properties of polyethylene oxide composite inorganic layered compound thin film The air permeability coefficient of a composite inorganic layered compound thin film obtained using polyethylene oxide was measured with a Gasperm-100 manufactured by JASCO Corporation. It was confirmed that it was less than × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , and it was found that gas barrier performance was exhibited.

(1) Manufacture of deoxyribocrine acid composite inorganic layered compound thin film As an inorganic layered compound, 0.99 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Industries Co., Ltd.) was added to 60 cm ³ of distilled water, and placed in a plastic sealed container. And a Teflon (registered trademark) rotor and vigorously shaken to obtain a uniform dispersion. To this dispersion, 0.01 g of powder of deoxyribocric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed as a water-soluble polymer. This dispersion containing natural montmorillonite and deoxyribocrine acid is poured into a brass tray having a flat bottom surface and a circular bottom shape and a diameter of about 15 cm, and the dispersion is left to stand horizontally. Uniform composite with a thickness of about 30 micrometers by slowly depositing inorganic layered compound particles and drying in a forced air oven for 5 hours in a forced air oven with the tray kept horizontal An inorganic layered compound thin film was obtained. The produced composite inorganic layered compound thin film was peeled from the tray.

(2) Characteristics of deoxyribocrate composite inorganic layered compound thin film The air permeability coefficient of a composite inorganic layered compound thin film obtained using deoxyribocrate was measured with a Gasperm-100 manufactured by JASCO Corporation. It was confirmed to be less than 2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , and it was found that gas barrier performance was exhibited.

(1) Production of poly-L-lysine hydrobromide gas salt composite inorganic layered compound thin film As an inorganic layered compound, 0.99 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) was used in 60 cm ³ of distilled water. In addition to the above, it was placed in a plastic sealed container together with a Teflon (registered trademark) rotor and shaken vigorously to obtain a uniform dispersion. To this dispersion, 0.01 g of a powder of poly-L-lysine hydrobromide gas (ICN Biochemicals Inc.) was mixed as a water-soluble polymer. This dispersion containing natural montmorillonite and poly-L-lysine hydrobromide gas salt is poured into a brass tray having a flat bottom, a round bottom and a diameter of about 15 cm. The liquid is allowed to stand horizontally, and the inorganic layered compound particles are slowly deposited, and the tray is kept in a horizontal state and dried in a forced air oven at a temperature of 50 ° C. for 5 hours to obtain a thickness. A uniform composite inorganic layered compound thin film of about 30 micrometers was obtained. The produced composite inorganic layered compound thin film was peeled from the tray.

(2) Characteristics of poly-L-lysine hydrobromide gas salt composite inorganic layered compound thin film The air permeability coefficient of a composite inorganic layered compound thin film obtained using poly-L-lysine hydrobromide gas salt When measured with Gasperm-100 manufactured by Spectroscopic Co., Ltd., it was confirmed that it was less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ at room temperature, and gas barrier performance was shown.

(1) Manufacture of composite clay film As clay, 0.95 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) is added to 60 cm ³ of distilled water, and a plastic sealed container is made of Teflon (registered trademark). It was put together with the rotor and shaken vigorously to obtain a uniform dispersion. An aqueous solution containing 0.05 g of epsilon caprolactam (manufactured by Wako Pure Chemical Industries, Ltd.) as a water-soluble polymer was added to this dispersion, and the resulting dispersion had a flat bottom and a circular bottom. Pour into a brass tray with a diameter of about 15 cm, place the dispersion horizontally, slowly deposit clay particles, and keep the tray level in a forced air oven. And dried at 50 ° C. for 5 hours to obtain a uniform composite clay film having a thickness of about 30 μm. The formed clay thin film was peeled from the tray to obtain a composite clay film.

(2) Form of utilization of composite clay film as gas barrier material The obtained composite clay film was cut to a length of 10 cm and a width of 2 cm, and the autoclave (made of SUS316, internal volume 30 cm ³ ) shown in FIG. , P2). Next, 20 cm ³ of distilled water was put into the autoclave, and the tightened parts were tightened by screwing the lid with a spanner. Next, this autoclave was put in an electric furnace maintained at 300 ° C., and the change in the weight of the autoclave with the passage of time was measured, and the remaining ratio of water relative to the initial value was calculated therefrom. FIG. 4 shows the relationship between the elapsed time and the remaining ratio of water. When the composite clay film was wound around the threaded portion, the amount of water retained did not change for 72 hours, indicating a barrier property against high-temperature and high-pressure water vapor.

(2) Use form of composite clay film as gas barrier material The obtained composite clay film is cut into 3 cm length and 2 cm width, and fixed to the side of the microreactor main body shown in FIG. did. Next, a reaction in which hydrogen was introduced into the microreactor and heated at 300 ° C. was performed. As a result, no leakage from the seal portion was confirmed, gas barrier properties against high-temperature hydrogen were shown, and the usefulness of the clay composite membrane as a gas shielding material for a microreactor was confirmed.

Comparative Example 1
20 cm ³ of distilled water was put into the autoclave (manufactured by SUS316, internal volume 30 cm ³ ) shown in FIG. 1, and the tightened parts were tightened by screwing the lid with a spanner. Next, this autoclave was put in an electric furnace maintained at 300 ° C., and the change in the weight of the autoclave with the passage of time was measured, and the remaining ratio of water relative to the initial value was calculated therefrom. FIG. 4 shows the relationship between the elapsed time and the remaining ratio of water. All water in the autoclave was lost after 45 minutes.

(1) Manufacture of composite clay film As clay, 0.32 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) is added to 60 cm ³ of distilled water, and a plastic sealed container is made of Teflon (registered trademark). It was put together with the rotor and shaken vigorously to obtain a uniform dispersion. An aqueous solution containing 0.017 g of epsilon caprolactam (manufactured by Wako Pure Chemical Industries, Ltd.) as a water-soluble polymer was added to this dispersion, and the resulting dispersion had a flat bottom surface and a circular bottom shape. Pour into a brass tray with a diameter of about 15 cm, place the dispersion horizontally, slowly deposit clay particles, and keep the tray level in a forced air oven. And dried at 50 ° C. for 5 hours to obtain a uniform composite clay film having a thickness of about 10 μm. The formed clay thin film was peeled from the tray to obtain a composite clay film.

(2) Form of utilization of composite clay film as gas barrier material The obtained composite clay film is cut out to an appropriate size, and sandwiched between two plastic films as shown in FIG. A three-layer multilayer film was produced. The plastic film was a fluororesin (ethylene tetrafluoride), and the thickness of one layer was 50 micrometers. When the permeability coefficient of helium of this multilayer film was measured with Gasperm-100 manufactured by JASCO Corporation, it was confirmed that it was less than 5.9 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ at room temperature. It has been found that the membrane exhibits gas barrier performance.

Comparative Example 2
As shown in FIG. 6, two plastic films were bonded to each other with an adhesive to produce a two-layer multilayer film. The plastic film was a fluororesin (ethylene tetrafluoride), and the thickness of one layer was 50 micrometers. When the permeability coefficient of helium of this multilayer film was measured with Gasperm-100 manufactured by JASCO Corporation, it was 1.1 × 10 ⁻¹⁹ cm ² at room temperature.
It was confirmed to be s ⁻¹ cmHg ⁻¹ .

As a clay, add 0.95 g of synthetic saponite “Sumekton” (Kunimine Industries Co., Ltd.) to 60 cm ³ of distilled water, put it in a plastic sealed container with a Teflon (registered trademark) rotor, shake vigorously, A uniform dispersion was obtained. Pour this dispersion into a brass tray with a flat bottom, circular bottom, and a diameter of about 15 cm, leave the dispersion horizontally, and slowly deposit clay particles. At the same time, the tray was kept horizontal and dried in a forced air oven at 50 ° C. for 5 hours to obtain a circular translucent clay thin film having a thickness of about 30 μm. From observation with an electron microscope, the metal plate and the clay thin film interface were in contact with each other without any gap, and were not easily peeled off when touched by hand.

As clay, 2,765 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Industry Co., Ltd.) and 0.691 grams of synthetic mica (Somasif ME-100, manufactured by Corp Chemical Co., Ltd.) are added to 100 cm ³ of distilled water. The mixture was placed in a plastic sealed container together with a Teflon (registered trademark) rotor and shaken vigorously at 25 ° C. for 2 hours to obtain a uniform dispersion. To this dispersion, 0.144 g of epsilon caprolactam (manufactured by Wako Pure Chemical Industries, Ltd.) was added as an additive, and shaken vigorously to obtain a uniform dispersion containing natural montmorillonite and epsilon caprolactam. This was gradually dried to obtain a clay paste. Next, this clay paste was deaerated with a vacuum deaerator. Next, this clay paste was applied to a brass tray. For application, a stainless steel gravel was used. Using a spacer as a guide, a clay paste film having a uniform thickness was formed. Here, the thickness of the paste was 2 mm. The tray was dried in a forced air oven at 60 ° C. for 1 hour to obtain a uniform additive composite clay film having a thickness of about 40 μm. The produced clay film was peeled from the tray to obtain a self-supporting clay film having excellent flexibility.

  This film was heated in an electric furnace. Heated from room temperature to 700 ° C. at a rate of 100 ° C. per hour. Next, it was kept at 700 ° C. for 24 hours. Then, it stood to cool in an electric furnace. As a result of this heat treatment, the film was observed to be blackened and swelled like spots. However, when it was lifted, spot breakage occurred, and no pinhole that could be observed with the naked eye was generated.

2.765 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) and 0.691 grams of synthetic mica (Somasif ME-100, manufactured by Co-op Chemical Co., Ltd.) are added to 100 cm ³ of distilled water as clay. The mixture was placed in a plastic sealed container together with a Teflon (registered trademark) rotor and shaken vigorously at 25 ° C. for 2 hours to obtain a uniform dispersion. As an additive, 0.324 g of epsilon caprolactam (manufactured by Wako Pure Chemical Industries, Ltd.) was added to this dispersion and shaken vigorously to obtain a uniform dispersion containing natural montmorillonite and epsilon caprolactam. This was gradually dried to obtain a clay paste. Next, this clay paste was deaerated with a vacuum deaerator. Next, this clay paste was applied to a brass tray. For application, a stainless steel gravel was used. Using a spacer as a guide, a clay paste film having a uniform thickness was formed. Here, the thickness of the paste was 2 mm. The tray was dried in a forced air oven under a temperature condition of 60 ° C. for 1 hour to obtain a uniform additive composite clay thin film having a thickness of 40 μm. The produced clay film was peeled from the tray to obtain a self-supporting clay film having excellent flexibility.

  This film was heated in an electric furnace. Heated from room temperature to 700 ° C. at a rate of 100 ° C. per hour. Next, it was kept at 700 ° C. for 24 hours. Then, it stood to cool in an electric furnace. As a result of this heat treatment, the film was observed to be blackened and swelled like spots. Further, when it was lifted, spot breakage occurred, and when it was heated to 600 ° C., no pinhole that could be observed with the naked eye was generated. Occurred.

  As described above in detail, the present invention is a gas shielding material characterized by being a film containing an inorganic layered compound as a main constituent, and a gas shielding method using the shielding material, and can be used as a self-supporting film. The present invention relates to a gas shielding material having mechanical strength and highly improved orientation lamination of inorganic layered compound particles, and a gas shielding method using the shielding material or a multilayer film containing the shielding material. The inorganic layered compound film can be used as a self-supporting film, can be used under high temperature conditions exceeding 350 ° C., has excellent flexibility, and is dense without pinholes. It is a simple material and has the characteristics of excellent barrier properties. Therefore, the inorganic layered compound film of the present invention can be widely used as a packing or separator having excellent flexibility under high temperature conditions exceeding 350 ° C. It can be used for preventing leakage of batteries and for diaphragms of batteries and electrolyzers. Further, it can be used as a sealing material for a microreactor. Further, the clay film of the present invention can be used as a pipe seal material that shields gas, solution, oil, etc., a fuel seal material around a rocket or jet engine, a fuel cell diaphragm, and the like. In addition, after removing the solvent and forming a composite clay film, it can also be used as a protective film for the support without peeling off from the support surface, thereby preventing corrosion, antifouling and heat resistance of the support. There is an improvement effect.

It is a figure which shows the X-ray-diffraction chart of the composite inorganic layered compound thin film (The weight ratio with respect to the total solid of the used sodium polyacrylate used was 0.02%) prepared using the polyacrylate of this invention. TG-DTA chart of composite inorganic layered compound thin film prepared using polyacrylate of the present invention (weight ratio of sodium polyacrylate used is 0.02% with respect to the total solid) (heating rate 5 ° C./min) It is a figure which shows under an air atmosphere. It is a side view which shows the structure of an autoclave. How the remaining ratio of the water in the autoclave in the electric furnace kept at 300 ° C. with respect to the initial amount changes with time when the screw part is sealed with the composite clay film and when it is not. FIG. It is a figure which shows the cross-section of a multilayer film. It is a figure which shows the cross-section of a multilayer film. It is a figure which shows the usage condition of the gas barrier seal of the film | membrane of this invention to a micro reactor gas entrance / exit part.

Claims (12)

  A gas shielding material comprising a film comprising a layered inorganic compound as a main constituent, wherein the film is composed of (1) the layered inorganic compound alone or the layered inorganic compound and an additive, and (2) the entire layered inorganic compound. The gas shielding material as described above, wherein the weight ratio to the solid exceeds 90%, (3) has a gas barrier property, and (4) has a mechanical strength usable as a self-supporting film.   The gas shielding material according to claim 1, wherein the layered inorganic compound is one or more of mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, and nontronite. .   Additives are epsilon caprolactam, dextrin, starch, cellulosic resin, gelatin, agar, flour, gluten, alkyd resin, polyurethane resin, epoxy resin, fluororesin, acrylic resin, methacrylic resin, phenolic resin, polyamide resin, polyester resin, Polyimide resin, polyvinyl resin, polyethylene glycol, polyacrylamide, polyethylene oxide, protein, deoxyribonucleic acid, ribonucleic acid and polyamino acid, polyhydric phenol, benzoic acid compound, characterized in that, The gas shielding material according to claim 1.   Chemical reaction such as addition reaction, condensation reaction, polymerization reaction, etc. can be carried out within the additive molecule, between additive molecules, between additive and inorganic layered compound, and between inorganic layered compound crystals by any method such as heating and light irradiation. The gas shielding material according to claim 1, wherein the gas barrier material or mechanical strength is improved by performing a new chemical bond.   5. The differential thermal analysis is characterized in that the basic structure of the layered inorganic compound constituting the gas shielding material does not change when the weight loss in the temperature range of 200 ° C. to 600 ° C. is less than 10%. The gas shielding material according to crab. 5. The permeation coefficient for air, oxygen gas, nitrogen gas, hydrogen gas, and helium gas at room temperature is less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ^−1. The gas shielding material according to crab. After heat treatment at 600 ° C. for 24 hours, the gas permeability coefficient of helium gas, hydrogen gas, oxygen gas, nitrogen gas and air at room temperature is less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ The gas shielding material according to any one of claims 1 to 4. 5. The gas shielding material according to claim 1, wherein the water permeability coefficient of pure water at room temperature is 2 × 10 ⁻¹⁰ cm / sec or less.   The gas shielding material according to any one of claims 1 to 8, wherein the gas shielding material is a sealing material, a packing material, or a packaging material.   A gas shielding method, comprising performing a gas shielding treatment using the gas shielding material according to claim 1.   A gas shielding method comprising performing a gas shielding treatment using a multilayer film including the gas shielding material according to claim 1.   The gas shielding method according to claim 10 or 11, wherein the gas shielding material is used as a sealing material, a packing material, or a packaging material.

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