JP4997493B2 - Clay film manufacturing method - Google Patents

Description

  The present invention relates to a method for producing a clay film, and more particularly, a method for producing a film made of only clay or a clay and an additive, wherein a clay paste is applied to the surface of an object at a certain thickness, It is related with the manufacturing method of the clay film | membrane characterized by obtaining a clay film | membrane by drying and peeling. In the technical field of clay film production technology and its products, in the conventional method, it is difficult to produce a clay oriented film having mechanical strength that can be used as a self-supporting film in a short time, and the production time can be shortened. Although strongly demanded, the present invention provides a clay film that has a mechanical strength that can be used as a self-supporting film, and that can manufacture a self-supporting clay film that has excellent thermal stability and flexibility in a short time. Provide technology. Further, in the conventional method, only a flat clay film can be produced, and a variety of forms has been strongly demanded. However, the present invention is a production of a clay film capable of producing various forms of clay films. Provide technology. Further, in the conventional method, the size of the obtained clay film is limited, and there has been a strong demand for expansion of the size. However, the present invention provides a clay film that can continuously produce a long clay film. Providing manufacturing technology.

  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 is about 250 ° C. at the highest Teflon (registered trademark), and metal packing must be used at a temperature higher than this, but the metal packing is made of an organic polymer material. In comparison, there was a problem of poor flexibility.

  It is known that clay is 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. A fixed orientation sample for X-ray diffraction has been prepared (see Non-Patent Document 1).

  Recently, a clay thin film using a Langmuir-Blodgett method has been produced (see, for example, Non-Patent Document 2). However, in this method, the clay thin film is formed on the surface of a substrate made of a material such as glass, and a clay thin film having strength as a self-supporting film cannot be obtained.

  Furthermore, conventionally, for example, various methods for preparing functional clay thin films 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 (see Patent Document 1), utilizing a reaction between a layered clay mineral and phosphoric acid or a phosphate group, A method for producing a layered clay mineral thin film in which the bond structure of the layered clay mineral is oriented and fixed by performing a heat treatment that promotes the reaction (see Patent Document 2), containing a complex compound of a smectite clay mineral and a bivalent or higher metal. There are many cases including an aqueous composition for film treatment (see Patent Document 3). However, until now, there has been no development example of a clay oriented film that has mechanical strength that can be used as a self-supporting film and that has a highly oriented laminate of clay particles.

JP-A-5-254824 JP 2002-30255 A JP-A 63-64913 Haruo Shiramizu “Clay Mineralogy-Basics of Clay Science”, Asakura Shoten, p. 57 (1988) Umezawa Yasushi, Clay Science, Vol. 42, No. 4, 218-222 (2003)

  Therefore, the inventors have made various attempts to produce a clay alignment film. In the process, a clay dispersion aqueous solution is prepared, and a small amount of a water-soluble additive is mixed therewith to obtain a uniform dispersion liquid. Then, the dispersion is allowed to stand horizontally to deposit clay particles, and the liquid as the dispersion medium is separated into various solid-liquid separation methods, such as centrifugation, filtration, vacuum drying, freeze vacuum drying, or heating. It has been found that a clay film in which clay particles are oriented can be obtained by separating the film by evaporation or the like and forming it into a film shape and then peeling it from the support.

  However, in the above method, for example, it takes about 5 hours to produce a clay film, and it is difficult to produce in a short time. In the above method, the obtained clay film is a flat plate. Furthermore, in the above method, the size of the clay film to be obtained is regulated by the size of the container in which the dispersion is put, and a size exceeding this cannot be made.

  Under such circumstances, the present inventors have a mechanical strength that can be used as a self-supporting film in view of the above prior art, and have excellent flexibility and a high temperature exceeding 250 ° C. The goal of developing a new clay film that can be used under temperature conditions is the result of extensive research, and as a result, a paste with a predetermined viscosity is applied to the surface of an object to a certain thickness, dried, and peeled off. The inventors have found that the intended purpose can be achieved and have completed the present invention. It is an object of the present invention to provide a novel clay film production technique that makes it possible to produce various types of long clay films in a short time.

The present invention for solving the above-described problems comprises the following technical means.
(1) In a method for producing a film consisting of only clay or clay and an additive, a clay paste having a predetermined solid-liquid ratio in which clay is dispersed in a liquid is prepared, and this clay paste is applied to the surface of an object. A method for producing a clay film having mechanical strength that can be used as a free-standing film by drying and peeling, and capable of producing a clay film having a complicated shape,
The clay paste is a clay paste having a solid-liquid ratio of 2-15 weight percent in which clay is dispersed in water or a water-based dispersion, and the clay paste is not only a flat plate but also an inclined surface or It is possible to uniformly apply to a vertical surface, and the form of the object to which the clay paste is applied is a flat plate, a cube, a rectangular parallelepiped, a tube, a cylinder, a cone, a sphere, or a combination thereof, and a thermal cycle test (100-600 No abnormalities at 30 ° C., air permeability coefficient at room temperature is less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , no pinholes, gas barrier properties and heat resistance. A method for producing a characteristic clay film.
(2) The main component of clay is one or more of mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite and nontronite, (1) A method for producing a clay film as described in 1.
(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 method for producing a clay film according to (1).
(4) A clay paste having a predetermined solid-liquid ratio is prepared by preparing a dilute clay dispersion and then concentrating to a predetermined concentration or mixing and kneading clay and a dispersion medium at a predetermined ratio. The method for producing a clay film according to (1).
(5) The method for producing a clay film according to (1), wherein the clay paste is applied to the surface of the object in a thickness of 0.03 millimeters to 10 millimeters.
(6) The method for producing a clay film according to (1), wherein the clay paste is dried under a temperature condition of 30 ° C to 90 ° C.
(7) A clay film produced by the method according to any one of (1) to (6) above, 1) composed of clay or clay and an additive, and 2) mechanical strength usable as a self-supporting film. having, 3) pin no holes, 4) even at high temperatures up to 250 ° C. or higher 500 ° C. with a bus rear resistance and heat resistance of the gas-liquid, 5) a sharp set of bottom reflection peak (001), ( 002), (003), (004), and (005) are confirmed by X-ray diffraction charts observed at positions of 1.24, 0.62, 0.42, 0.31, and 0.21 nm, respectively. A clay film characterized by having a uniform orientation of clay particles.
(8) A heat-resistant, high-barrier member comprising the clay film according to (7) as a constituent element.

Next, the present invention will be described in more detail.
The present inventors have so far prepared a dilute and uniform dispersed aqueous solution containing clay and additives, left this dispersed aqueous solution horizontally, slowly deposited clay particles, and is a 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. A method for producing a clay film that obtains a clay film having a highly oriented laminate of clay particles as a self-supporting film by adopting manufacturing conditions for obtaining a sufficient strength to be used as a self-supporting film with a uniform thickness Although the above-described production method has been developed, for example, when the heating evaporation method is used, there is a problem that it is difficult to produce a clay film in a short time, for example, it takes about 5 hours for solid-liquid separation. In addition, in the above production method, only a flat clay film can be produced, and the size of the obtained clay film is defined by the size of the container in which the dispersion is placed and has a size exceeding this. There was a problem that it was difficult to fabricate.

  Therefore, the inventors have a higher solid-liquid ratio than conventional clay dispersions, or are prepared by adding additives such as thickeners, which are higher in viscosity and lower in fluidity than clay dispersions. By using clay paste, and by using clay paste, it can be dried in a shorter time than the conventional synthesis method, and the fluidity of clay paste is low, so the coating film does not flow out, so coating It has been found that the object to be formed does not have to be in the form of a partitioned container, and furthermore, since the fluidity of the clay paste is low, it can be applied not only to a flat plate but also to an inclined surface.

  In the conventional production method, an aqueous dispersion having a fluid-solid ratio of 1-2% by weight was used so that clay can be poured into a container uniformly. On the other hand, the solid-liquid ratio of the clay paste used in the present invention is 2-15 weight percent, preferably 4-7 weight percent. Since the clay paste is thicker than the conventional aqueous dispersion, drying is quick, and it takes about 5 hours to dry in the conventional manufacturing method. However, by making the solid-liquid ratio of the clay paste about 6%, for example. It can be dried in about 20 minutes. Examples of the preparation method of the clay paste include the following two methods. The first method is a method in which clay is dispersed in a dispersion medium by shaking, and the dispersion medium is slowly evaporated at, for example, 50 ° C. under mild drying conditions to increase the solid-liquid ratio to a set value. The second method is a method of directly kneading a dispersion medium having a set solid-liquid ratio and clay particles.

  The clay used in the present invention is natural or synthetic, preferably, for example, one or more of mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, and nontronite, and more preferably. Examples include natural smectite and synthetic smectite, or a mixture thereof. In addition, the additive used in the present invention is not particularly limited as long as it has a polar group in the main chain or side chain and is therefore hydrophilic and highly dispersible in water. Preferably, 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, Examples include 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 compounds. Clay such as smectite used in the present invention is also hydrophilic and is well dispersed in water.

  Examples of the dispersion medium include water alone or, if necessary, water with a small amount of additives, that is, additives such as organic substances or salts. The purpose of adding the additive is to change the dispersibility of the paste, change the viscosity of the clay paste, change the easiness of drying of the clay film, improve the uniformity of the clay film, and the like. Examples of the additive include acetamide and ethanol.

  In the method for producing a clay film of the present invention, the application of the clay paste to the object is not particularly limited as long as it can be uniformly applied, but preferably using, for example, a spatula, a brush, a nozzle or other tools. Make sure there are no bubbles. Since the clay paste has a high viscosity, it can be uniformly applied not only to a horizontal surface but also to an inclined surface or a vertical surface. Therefore, not only a flat plate, but also a clay film can be produced when the surface shape of the object to be applied is not a flat plate, and it is not particularly limited as long as the paste can be uniformly applied, for example, a cube, a rectangular parallelepiped, a tube, By applying paste to the outer or inner surface of an object in the shape of a cylinder, cone, sphere or combination thereof, drying, and peeling, a clay film with a complex shape that could not be produced by conventional methods can be produced. it can. When applying the clay paste to the inclined surface, it is important to use a clay paste having a high viscosity and low fluidity in order to maintain the uniformity of the coating film.

  The applied thickness of the clay paste is 0.03 millimeters to 10 millimeters, preferably 0.1 millimeters to 1 millimeter. At this time, if the coating thickness is too thin, the produced clay film is too thin, and sufficient mechanical strength may not be obtained. On the other hand, if it is too thick, drying takes time and the drying time may be prolonged. Regarding the thickness of the clay film of the present invention, a film having an arbitrary thickness can be obtained by adjusting the solid-liquid ratio of the clay paste or the film thickness of the clay paste to be applied.

  Regarding the drying conditions in the method for producing a clay film of the present invention, the temperature condition is 30 ° C. to 90 ° C., preferably 50 ° C. to 70 ° C. It is possible to dry in a forced convection oven. However, even an open system can be dried by supplying heat from a surrounding heat source. It is also possible to dry with light such as infrared rays. At this time, if the drying temperature is too low, the drying time may become longer. On the other hand, if the drying temperature is too high, convection of the liquid in the clay paste is promoted by rapid drying, and the uniformity of the film may be lost.

  In addition, when the additive composite clay film does not spontaneously peel off from a support such as a tray, it is preferably dried, for example, under a temperature condition of about 80 to 300 ° C. to facilitate peeling and obtain a self-supporting film. At this time, if the temperature is too low, peeling may not occur easily. When the temperature is too high, the action of the additive is weakened by the thermal deterioration, and the orientation of the clay laminate may be inferior. In the present invention, a dispersion or paste of a raw material mainly composed of clay can be deaerated. If the deaeration treatment is not performed in advance, there may be a problem that pores derived from bubbles are easily formed in the clay layer. The drying conditions are set so as to be sufficient to dry and remove the liquid component. At this time, if the drying speed is too slow, there is a problem that it takes time to dry. Further, when the drying rate is too high, there is a problem that convection of the dispersion occurs and the uniformity of the clay layer is lowered. When forming the clay film, it is important to make the gap between clay particles as small as possible and to have a dense structure. An X-ray diffraction chart of the clay thin film of the present invention is shown in FIG. A series of sharp bottom surface reflection peaks (001), (002), (003), (004), (005) are positioned at 1.24, 0.62, 0.42, 0.31, and 0.21 nm, respectively. It was observed that the orientation of the clay thin film particles was well aligned. The present invention is characterized by maintaining a high gas barrier property and flexibility up to a high temperature of 300 ° C. by making the gap between clay particles as small as possible to have a dense structure and no pinhole.

  The material of the object to be applied is not particularly limited, but it preferably has sufficient heat resistance, is not easily deformed, has high thermal conductivity, and has high peelability of clay, such as stainless steel, aluminum, A thing made from copper etc. is illustrated.

  In the conventional method, the clay paste has low viscosity and fluidity, so that it can be produced only in a container such as a bread, and there is a limit to the size of the clay film that can be produced. On the other hand, in the method for producing a clay film of the present invention, the production process, that is, clay paste preparation, clay paste application, drying, and peeling can be performed continuously in a series of processes. It is possible to obtain a long clay film that could not be produced until the same time, and at the same time, the production speed is improved and the production efficiency is improved. Furthermore, the peeling of the clay film from the material to be applied and the winding of the clay film into a roll can be automated, and the production efficiency can be further improved.

The clay film produced according to the present invention can be used as a free-standing film, has excellent flexibility, does not have pinholes, and has a gas / liquid barrier property even at a high temperature of 250 ° C. to 500 ° C. It is characterized by holding. Therefore, the clay film produced according to 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 and high-barrier member for similar products. The clay film produced by the method of the present invention has a thickness of 30 μm, an oxygen permeability of less than 0.1 cc / m ² · 24 hr · atm, and a hydrogen permeability of less than 0.1 cc / m ² · 24 hr · atm.

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. In contrast, the material of the present invention has a density greater than 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.

  INDUSTRIAL APPLICABILITY According to the present invention, (1) it is possible to provide a clay film production technique that can produce a clay self-supporting film having mechanical strength that can be used as a self-supporting film and having excellent thermal stability and flexibility in a short time. (2) It is possible to provide a clay film manufacturing technique capable of producing various types of clay films, and (3) to provide a clay film manufacturing technique capable of continuously producing a long clay film. The

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

As a clay, 1 gram of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) is added to 60 cm ³ of distilled water, placed in a plastic sealed container with a Teflon (registered trademark) rotor, and at 25 ° C. for 30 minutes. Shake vigorously to obtain a uniform dispersion. This dispersion was gradually dried under a temperature condition of 50 ° C. to obtain a clay paste having a solid-liquid ratio of about 6 weight percent. Next, this clay paste was applied to a brass tray shown in FIG. For application, a stainless steel gravel was used. A clay paste film having a uniform thickness was molded using the spacer shown in FIG. 1 as a guide. Here, the thickness of the paste was 0.3 mm.

The tray was dried in a forced air oven for 20 minutes under a temperature condition of 50 ° C. to obtain a translucent and uniform additive composite clay thin film having a thickness of about 10 μm. The produced clay film was peeled from the tray to obtain a self-supporting clay film having excellent flexibility. The air permeability coefficient of the obtained clay film was measured with Gasperm-100 manufactured by JASCO Corporation. As a result, it was confirmed that the air permeability coefficient at room temperature was less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , indicating gas barrier performance.

As clay, 0.90 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 with a Teflon (registered trademark) rotor at 25 ° C. Shake vigorously for 30 minutes to obtain a uniform dispersion. To this dispersion, 0.10 g of epsilon caprolactam (Wako Pure Chemical Industries, Ltd.) was added as an additive to obtain a dispersion containing natural montmorillonite and epsilon caprolactam. Next, the dispersion containing natural montmorillonite and epsilon caprolactam was gradually dried under a temperature condition of 50 ° C. to obtain a clay paste having a solid-liquid ratio of about 6 weight percent. Next, this clay paste was applied to a brass tray shown in FIG. For application, a stainless steel gravel was used. A clay paste film having a uniform thickness was molded using the spacer shown in FIG. 1 as a guide. Here, the thickness of the paste was 0.06 mm. The tray was dried in a forced air oven for 20 minutes under a temperature condition of 50 ° C. to obtain a semitransparent and uniform additive composite clay thin film having a thickness of about 2 μm. The produced clay film was peeled from the tray to obtain a self-supporting clay film having excellent flexibility.

As clay, 0.90 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 with a Teflon (registered trademark) rotor at 25 ° C. Shake vigorously for 30 minutes to obtain a uniform dispersion. To this dispersion, 0.10 g of epsilon caprolactam (Wako Pure Chemical Industries, Ltd.) was added as an additive to obtain a dispersion containing natural montmorillonite and epsilon caprolactam. Next, the dispersion containing natural montmorillonite and epsilon caprolactam was gradually dried under a temperature condition of 50 ° C. to obtain a clay paste having a solid-liquid ratio of about 6 weight percent.

Next, this clay paste was applied to a brass tray shown in FIG. For application, a stainless steel gravel was used. A clay paste film having a uniform thickness was molded using the spacer shown in FIG. 1 as a guide. Here, the thickness of the paste was 0.3 mm. The tray was dried in a forced air oven for 20 minutes under a temperature condition of 50 ° C. to obtain a translucent and uniform additive composite clay thin film having a thickness of about 10 μm. The produced clay film was peeled from the tray to obtain a self-supporting clay film having excellent flexibility. The air permeability coefficient of the obtained clay film was measured with Gasperm-100 manufactured by JASCO Corporation. As a result, it was confirmed that the air permeability coefficient at room temperature was less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , indicating gas barrier performance.

Comparative Example 1
As a clay, 1 gram of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) is added to 60 cm ³ of distilled water, placed in a plastic sealed container with a Teflon (registered trademark) rotor, and at 25 ° C. for 30 minutes. Shake vigorously to obtain a uniform dispersion. 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. While maintaining the tray level, the tray was dried for 5 hours in a forced air oven at 50 ° C. to obtain a uniform clay film having a thickness of about 30 μm. The produced clay film was peeled from the tray to obtain a self-supporting clay film having excellent flexibility.

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, it was spotted and no pinholes that could be observed with the naked eye were 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, but when it was heated to 700 ° C., there was no pinhole that could be observed with the naked eye. Occurred.

  As described above in detail, the present invention is a method for producing a film consisting of clay alone or a clay and an additive, wherein a clay paste is applied to the surface of an object to a certain thickness, dried and peeled off. The present invention relates to a method for producing a clay film characterized by obtaining a clay film. According to the present invention, a method for producing a clay film having excellent gas barrier properties, heat resistance and flexibility can be provided. The present invention produces clay films of various forms other than flat plates or long clay films in a short time, which was difficult in the technical field of clay film production technology and its products by conventional methods. It is possible to provide a technique for producing a clay film. INDUSTRIAL APPLICABILITY The present invention can be used for heat-resistant gas barrier part manufacturing technology, particularly for manufacturing a gas barrier part molded in a three-dimensional shape so as to fit a specific part, or for manufacturing a large area gas barrier part.

In this invention, it is a figure which shows the structure of the tray which is an example of the object which apply | coats a clay paste. The X-ray diffraction chart of the clay thin film of this invention is shown.

Claims (8)

In a method for producing a film consisting of only clay or clay and an additive, a clay paste having a predetermined solid-liquid ratio in which clay is dispersed in a liquid is prepared, this clay paste is applied to the surface of an object, and this is dried. A method for producing a clay film having mechanical strength that can be used as a free-standing film by peeling and capable of producing a clay film having a complicated shape,
The clay paste is a clay paste having a solid-liquid ratio of 2-15 weight percent in which clay is dispersed in water or a water-based dispersion, and the clay paste is not only a flat plate but also an inclined surface or It is possible to uniformly apply to a vertical surface, and the form of the object to which the clay paste is applied is a flat plate, a cube, a rectangular parallelepiped, a tube, a cylinder, a cone, a sphere, or a combination thereof, and a thermal cycle test (100-600 No abnormalities at 30 ° C., air permeability coefficient at room temperature is less than 3.2 × 10 ⁻¹¹ cm ² s ⁻¹ cmHg ⁻¹ , no pinholes, gas barrier properties and heat resistance. A method for producing a characteristic clay film.   The clay according to claim 1, wherein the main component of clay is one or more of mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite and nontronite. A method for producing a membrane.   Additives include 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 method for producing a clay film according to claim 1.   A clay paste having a predetermined solid-liquid ratio is prepared by preparing a dilute clay dispersion and then concentrating to a predetermined concentration or mixing and kneading clay and a dispersion medium at a predetermined ratio. The method for producing a clay film according to claim 1.   2. The method for producing a clay film according to claim 1, wherein the clay paste is applied to the surface of the object in a thickness of 0.03 millimeters to 10 millimeters.   The method for producing a clay film according to claim 1, wherein the clay paste is dried under a temperature condition of 30 ° C to 90 ° C. A clay film produced by the method according to any one of claims 1 to 6, comprising (1) a clay or a clay and an additive, and (2) a mechanical strength usable as a self-supporting film. 3) no pinholes, (4) also has a bus rear resistance and heat resistance of the gas-liquid at high temperatures up to 250 ° C. or higher 500 ° C., (5) a sharp set of bottom reflection peak (001), (002 ), (003), (004), and (005) are confirmed by X-ray diffraction charts observed at positions of 1.24, 0.62, 0.42, 0.31, and 0.21 nm, respectively. A clay film characterized by having an orientation of clay particles.   A heat-resistant, high-barrier member comprising the clay film according to claim 7 as a constituent element.