JP5598890B2 - Gel-like clay film or dry clay film produced from it - Google Patents

Description

  The present invention relates to a flexible film-like material mainly composed of clay and additives as main components other than water, and more particularly to a gel-like clay film and a dry clay film produced therefrom. It is. In the technical field of heat-resistant materials, flame retardants / non-flammable materials, and surface protection materials, the present invention is a flexible, preferably highly heat-resistant, preferably non-flammable, film-like material having easy handling properties. It was developed based on the strong demand for development. It is a new material with high flexibility, heat resistance, and non-flammability, and can be easily adhered to the surface of other substances. New materials and technologies that can be easily used to form heat-resistant materials, flame retardants / non-flammable materials, and surface protection materials can be easily formed by drying after adhesion. It is to provide.

  Conventionally, surface protective materials have been used for the purpose of improving heat resistance, corrosion resistance, weather resistance, scratch resistance, friction resistance, and the like by coating the surface of a substance. Generally, the surface protective material has a configuration in which a plastic film is used as a base material and an adhesive layer is provided on one surface of the film (see Patent Document 1). A protective layer is obtained by bonding the film to a material to be protected.

  In addition, surface protection materials with excellent heat resistance include those in which a liquid tackifier is added at room temperature to an ethylene / vinyl acetate copolymer containing vinyl acetate, or on one side of a substrate made of a thermoplastic resin. In addition, there is a surface protective material in which a mixture of an ethylene / vinyl acetate copolymer and a specific polyethylene resin is laminated (see Patent Document 2).

  However, since these conventional surface protection materials use plastic, it is difficult to prevent them from burning completely. Further, since the heat resistance of the surface protective material itself is low and it is bonded to the protected material via the adhesive layer, there is a problem of contamination of the protected material during long-term storage or high temperature. The protected material from which the protective material has peeled has a problem that adhesive residue or cloudiness of the adhesive layer occurs.

  As a surface protective material having heat resistance, a film using clay has been proposed (see Patent Document 3). This is a self-supporting film that has excellent heat resistance and transparency as a surface protection material. However, when bonding to a protected material such as glass or metal as a surface protective material, for example, epoxy adhesive, cyanoacrylate adhesive, modified silicone adhesive, urethane resin adhesive, vinyl acetate resin Although it is necessary to adhere through an adhesive layer such as an emulsion adhesive, it still does not provide sufficient adhesive strength, peels off the material to be protected, and does not exhibit a function as a protective layer.

  The clay film is excellent in heat resistance, transparency, etc., but it does not have water resistance or water vapor barrier property, and the clay film absorbs water in places where water or water droplets adhere and under high humidity, It gelled, detached from the material to be protected, and could not function as a protective layer, and could only be used in a limited environment. The intercalation ions of natural clay are usually rich in sodium ions, and there is no natural smectite containing potassium ions as intercalation ions.

  A surface protective material using polysilazane or the like has been proposed as a surface protective material not containing an organic substance (see Patent Document 4). This type of protective material does not use an organic substance in the protective layer, and is excellent in heat resistance. However, since the thickness of the protective layer is as thin as several μm, it is difficult to obtain a thick protective layer.

  As a surface protective material using a raw material derived from nature, a mica sheet can be mentioned, but this is a laminated mica sheet, which is a natural raw material, and may be depleted in the future. Moreover, this may peel from a to-be-protected material by cleavage. In order to prevent cleavage, there are products to which various binders are added, but there are also products that have insufficient heat resistance due to the addition of binders. Since it is a raw material derived from nature, quality control is not easy because of variations in quality.

  As described above, the surface protection material that can be used under high temperature and high humidity and that can easily adjust the thickness of the protective layer has not been developed. Therefore, there has been a strong demand for the development of a protective material that can easily adjust the thickness of the protective layer under high temperature and high humidity.

JP 2001-323239 A Japanese Patent Laid-Open No. 09-132864 JP 2007-63118 A JP 2000-25156 A

Under such circumstances, in view of the above prior art, the present inventors have conventionally been flexible and preferably highly heat resistant in the technical fields of heat-resistant materials, flame-retardant materials / non-flammable materials, and surface protection materials. Based on the strong demand for the development of film-like materials that are preferably non-combustible and easy to handle, clay that has film-forming properties in the process of intensive research aimed at developing these materials. the use, this additive was added, the total weight ratio of the clay to the whole film and that a large excess, and replace the particular ions interlayer ions usually sodium, containing water in an amount of a range of water It has been found that by using a gel clay film, a film that can be easily adhered to the surface of another substance can be obtained.

  In addition, the present inventors can easily form a dry clay film by adhering the hydrated gel clay film to another substance, followed by drying. The present inventors have found that this is a material having high heat resistance and nonflammability.

  In addition, the inventors of the present invention are the types of clay having film-forming properties, the total weight ratio of the clay and the additive, the mixing ratio of the clay and the additive, the clay pretreatment method, the presence or absence of the additive, and the type thereof. The inventors have found suitable conditions such as a suitable thickness, and further found out an adhesion method and imparting water resistance to enhance the practicality as a surface protective material, and have completed the present invention.

  An object of the present invention is to provide a novel film material comprising a water-containing gel-like clay film having excellent performance and function as a heat-resistant material, a flame retardant / non-combustible material, and a surface protection material, and a dry clay free-standing film. is there.

The present invention for solving the above-described problems comprises the following technical means.
(1) A hydrogel clay film having mechanical strength and flexibility that can be used as a self-supporting film, in which clay is the main component among components other than water, and it contains a water-soluble polymer as an additive. In the clay intercalation ions, the proportion of potassium ions is at least 70 percent with respect to the sum of the clay intercalation ions, and the water-soluble polymer is any one of sodium carboxymethylcellulose, polyacrylic acid, and sodium polyacrylate. A gel-like clay film that is transparent, has a property of adhering to the surface of an object, and is a gel-like clay self-supporting film.
(2) The gelled clay film according to (1), wherein the clay is mainly composed of smectite.
(3) The gel-like clay film according to (1), wherein the weight of water relative to the dry weight of the free-standing film is in the range of 50% to 150%.
(4) water-soluble polymer, polyacrylic acid, or a sodium carboxymethylcellulose, gelatinous clay film according to (1).
(5) The abundance ratio of clay to additive is in the range of 80/20 to 95/5 in clay / additive ratio (mass ratio) , according to any one of (1) to (4) above Gel-like clay film.
(6) The gel according to any one of (1) to (5), wherein the gel is a gel-like clay film attached to the surface of an object as a protected material and has a property of sticking to the surface of the object. Clay film.
(7) The gelled clay film according to (6), wherein the object is glass or metal.
(8) A dry clay film obtained by removing moisture from the gel clay film according to (6) or (7), wherein the thickness of the dry clay film is 0.01 mm or more and 0.1 mm or less. A dry clay film characterized by having a total light transmittance of at least 90 percent.
(9) The dry clay film according to (8), wherein the thickness is 0.01 mm or more and 0.1 mm or less.
(10) The adhesive layer according to (8), wherein the dry clay film has adhesion that prevents the dry clay film from peeling off from the surface of the protected material in a tape peeling test (JIS D0202) of the dry clay film attached to the surface of the object as the protected material. Dry clay film.
(11) The dry clay film according to (8), wherein the total light transmittance is 90% or more and 95% or less.
(12) The dry clay film according to (8), wherein the total light transmittance after heat treatment at 350 ° C. for 24 hours under normal air conditions is 80% or more and 90% or less.
(13) The dry clay film according to (8), wherein the total light transmittance after performing a hydrothermal treatment at 230 ° C. for 24 hours is 80% or more and 90% or less.
(14) The dry clay film according to (8), which is nonflammable.
(15) A sticking member comprising the gel-like clay film or the dry clay film according to any one of (1) to (14).
(16) The sticking member according to (15), wherein the member is a coating material, a heat insulating material, a heat resistant material, or a flame retardant / incombustible material.

Next, the present invention will be described in more detail.
The present invention is a hydrogel clay film having mechanical strength and flexibility that can be used as a self-supporting film, the clay being a main component among components other than water, including additives, Among the ions, the proportion of potassium ions is at least 70 percent with respect to the sum of ions between clay layers, is transparent, has a property of adhering to the surface of an object, and is a gel-like clay free-standing film It is. In the present invention, it is a preferred embodiment that the clay is mainly composed of smectite and that the weight of water relative to the dry weight of the free-standing film is in the range of 50 to 150 percent.

  In the present invention, the additive is a water-soluble polymer, and the water-soluble polymer is at least one of polyacrylic acid, polyacrylate, or sodium carboxymethylcellulose. The abundance ratio is in the range of 80/20 to 95/5 in clay / additive ratio, the clay is silylated, has the property of sticking to the surface of the object, the object is made of glass, Or it is a metal as a preferable embodiment.

  The present invention is also a dry clay film from which the water content of the gel clay film has been removed, wherein the total light transmittance is at least 90 percent. Furthermore, the present invention is characterized by the point of the sticking member comprising the gel clay film or the dry clay film.

  In the present invention, the thickness is 0.01 mm or more and 0.1 mm or less, the tape does not peel in the tape peeling test (JIS D0202), and the total light transmittance is 90% or more and 95% or less. The total light transmittance after performing heat treatment at 350 ° C. for 24 hours under normal air conditions is 80% or more and 90% or less, and hydrothermal treatment was performed at 230 ° C. for 24 hours. It is preferable that the total light transmittance later is 80% or more and 90% or less, that it is nonflammable, and that the member is a coating material, a heat insulating material, a heat resistant material, or a flame retardant / nonflammable material. This is an embodiment.

  The production method of the hydrogel clay film and the dried clay free-standing film of the present invention will be described. For example, a uniform dispersion prepared by adding clay such as synthetic smectite to water and vigorously shaking, and a water solution such as polyacrylic acid. The water-soluble polymer is added to water and mixed with a uniform paste prepared by vigorous shaking. The resulting mixture is sufficiently mixed, and the paste is deaerated with a vacuum deaerator.

  For example, a paste film having a uniform thickness produced by applying the obtained paste onto an FEP sheet is formed to have a predetermined thickness. The FEP sheet is dried, for example, in a forced convection oven to produce a transparent and uniform film. This is left to stand for about a day and night, and the produced clay film is peeled off from the FEP sheet, whereby a self-supporting clay film having a predetermined thickness and having a predetermined thickness without distortion is obtained.

  Next, the obtained self-supporting clay film is immersed in a potassium salt solution such as a saturated potassium chloride solution for about 50 hours, then taken out, washed with water, and further immersed in water for about 30 minutes. Thus, a gel-like transparent clay film is obtained. Next, moisture on the gel-like clay film is removed by drying on the FEP sheet to produce a dry clay free-standing film.

  As for the characteristics of the dry clay free-standing film, for example, even when bent to a diameter of 2 millimeters, it has flexibility that does not cause defects such as cracks, and the total light transmittance is 90% or more and has a high water absorption rate. It has heat resistance to heat treatment of at least 230 ° C., has adhesion to a slide glass, and the ratio of potassium ions is 70% or more with respect to the sum of clay interlayer ions.

  The present invention relates to a clay having a film-forming property, a flexible gel-like clay film mainly composed of additives and water, and a dry clay obtained by sticking the clay film to the surface of the object and removing the water. It is a membrane. The gel-like clay film is a hydrous gel-like compound that can be used as a self-supporting film, with clay as a main component among components other than water, and preferably the clay is a clay containing smectite as a main component.

  The gel-like clay film has a weight of water in the range of 50% to 150% with respect to the weight of the free-standing film, and preferably includes an additive, more preferably the additive is a water-soluble polymer, and more preferably. The water-soluble polymer is at least one of polyacrylic acid and sodium polyacrylate, and preferably the clay / additive ratio is in the range of 80/20 to 95/5 in terms of clay / additive ratio. is there.

  In the gel-like clay film, the clay is silylated, and preferably the proportion of potassium ions in the interlayer ions of the clay is 70% or more with respect to the sum of the clay interlayer ions, Examples of the object that adheres to the surface include glass and metal. The dry clay film preferably has a thickness of 0.01 mm or more and 0.1 mm or less.

  The dry clay film of the present invention did not peel even when the tape peel test was performed, had a total light transmittance of 90% to 95%, and was subjected to heat treatment at 350 ° C. for 24 hours under normal air conditions. The later total light transmittance is 80% or more and 90% or less.

  The dry clay film has a total light transmittance of 80% or more and 90% or less after being subjected to a hydrothermal treatment at 230 ° C. for 24 hours, and is nonflammable. Further, cracks are generated at a bending diameter of 2 mm. It is a film material that can be used.

  The film material of the clay film of the present invention is a hydrogel clay film having mechanical strength and flexibility that can be used as a self-supporting film. Clay is a collection of fine particles formed by breaking down rocks by weathering or hydrothermal action. In soil science, it refers to particles of 0.002 mm or less. In this, film forming property is confirmed in a part of (swelling) mica, illite, vermiculite, bentonite and smectite.

  Here, the smectite refers to a product obtained by purifying a highly plastic component of bentonite (refined bentonite). Montmorillonite, hectorite, etc. are a kind of smectite. Synthetic smectite refers to smectite obtained by performing a hydrothermal synthesis process on a raw material, which is all artificially obtained from the raw material.

  Preferred examples of the clay having film-forming properties used in the present invention include, but are not limited to, clays mainly composed of smectite, and similarly, any clay having the same effect as this can be used. Can be used.

The additives used in the present invention, carboxymethyl cellulose sodium, polyacrylic acid, polyacrylic acid sodium may be used. As being good suitable, sodium carboxymethylcellulose, and polyacrylic acid salts, polyacrylic acid, one or more of sodium polyacrylate and the like.

  The weight of water relative to the total weight of the membrane is in the range of 50 to 150 percent and exists as a gel-like and stable free-standing membrane. In other weight ranges of water, it can exist as a gel-like free-standing film, but the mechanical strength and adhesion to the material to be protected are reduced.

  The mixing ratio of clay and additive is preferably in the range of 80/20 to 95/5 for clay / additive. When there is too little clay, there exists a problem that the mechanical strength of a film | membrane will become weak. Moreover, when there is too much clay, there exists a problem that the whole film | membrane does not become a gel form and does not exist as a self-supporting film | membrane.

  The clay is preferably silylated. A clay film-forming material is generally hydrophilic and excellent in water dispersibility. In the case of producing a composite containing clay, in order to improve the affinity with plastic, a modified clay in which the clay is modified and the hydrophilicity / hydrophobicity is controlled is used.

  In the silylation treatment, a hydroxyl group is present at the terminal of the clay crystal, and the hydroxyl group and the added silylating agent react to make the terminal hydrophobic. In these cases as well, hydrophilicity / hydrophobicity can be controlled by the type and introduction ratio of the silylating agent.

  The silylating agent used for silylation is not particularly limited, but methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, Examples include dodecyltrimethoxysilane and octadecyltrimethoxysilane.

  As a method for introducing the silylating agent into the clay, for example, the raw clay and the raw clay are mixed with 2 weight percent of the silylating agent, and they are manufactured by milling for one hour with a ball mill. This is not a limitation.

  As clay interlayer ions, a large amount of sodium or calcium is usually contained. Among these, the film having a higher sodium ion ratio is superior in film forming properties. However, synthetic clay does not contain calcium, and most of the interlayer ions are sodium ions. Clays that are high in sodium tend to absorb moisture from the atmosphere, swell easily, and reduce the mechanical strength of the film.

  Moreover, it is possible to improve water resistance by exchanging sodium ions contained in the membrane for other ions after film formation. In particular, potassium ion and calcium ion are suitable. Ion exchange into potassium ions and calcium ions can be easily achieved by immersing the material after film formation in an aqueous solution containing a large excess of those ions and then washing with water.

  Ion exchange is also preferably achieved by a column method using an ion exchange resin. When the proportion of potassium ions among the interlayer ions of the synthetic clay is 70% or more with respect to the sum of the clay interlayer ions, the water resistance of the membrane is improved. Thus, it is possible to improve the water resistance of the membrane mainly by exchanging sodium ions contained in the clay with other inorganic ions.

  The above-mentioned clay having film-forming properties other than water and a flexible film mainly composed of additives, absorbs water to form a gel, and transfers it to a glass surface or a metal surface. It can be adhered and dried to obtain a protective layer. Examples of the drying method include natural drying at room temperature, drying on a hot plate heated from room temperature to 40 ° C., and drying in a constant temperature dryer at room temperature to 60 ° C.

  The film material of the clay film of the present invention preferably has a thickness of 0.01 mm or more and 0.1 mm or less. If the thickness is too thin, there is a problem that the mechanical strength becomes too weak. In addition, if the thickness is too thick, there is a problem that flexibility is poor. About the thickness of the clay film of this invention, the film | membrane of arbitrary thickness can be obtained by increasing / decreasing the solid weight used for a dispersion liquid.

  Moreover, the water of the obtained gel-like clay film can be brought into close contact before being removed by drying, dried by the above-described drying method, and easily laminated. A film having an arbitrary thickness can be obtained by increasing or decreasing the amount used per unit area of the dispersion used during film formation.

  The dried clay film is not peeled off from the glass and metal surface even if the cellophane tape is peeled off after the cellophane tape is made to adhere to it after the scratch is peeled off according to JIS D0202. , Are in close contact.

  The dry clay film was adhered to glass and the total light transmittance was measured as it was. As a result, the total light transmittance was at least 90 percent, and was 90 percent or more and 95 percent or less. In this case, the measurement was performed using the total light transmittance of only glass as a blank.

  The total light transmittance was 80% or more and 90% or less after the dry clay film was heat-treated at 350 ° C. for 24 hours under normal air conditions while being in close contact with the glass and metal surfaces. Although a decrease in the total light transmittance was confirmed as compared with that before the heat treatment, it had a transmittance of 80% or more, and it was found that the transparency was not impaired by the heat treatment.

  The total light transmittance after the glass with the dried clay film adhered thereto was subjected to hydrothermal treatment at 230 ° C. for 24 hours was 80% or more and 90% or less. Although a decrease in the total light transmittance was confirmed as compared with that before the hydrothermal treatment, the transmittance was 80% or more, and it was found that the transparency was not impaired by the hydrothermal treatment.

  The dry clay film contains up to 20 percent of the clay / additive mix ratio, but was found to be nonflammable without self-combustion even when heated in an open flame. The dry clay film of the present invention is a flexible film having a film forming property with components other than water and an additive as a main component. Preferably, the clay is a clay having smectite as a main component. It is.

  The additive is one or more of polyacrylic acid, sodium polyacrylate, the weight of water relative to the weight of the free-standing film ranges from 50 percent to 90 percent, and the abundance ratio of clay and additive is The clay / additive ratio ranges from 80/20 to 95/5.

  The dry clay film of the present invention is a film material in which the sum of the proportions of potassium ions and sodium ions in the interlayer ions of clay is 70% or more and the thickness is 0.01 mm or more and 0.1 mm or less. .

  Thus, the film material of the present invention can be easily adhered to the glass and metal surfaces, and even when subjected to a hydrothermal treatment at 230 ° C. and a heat treatment at 350 ° C., the membrane substrate does not deteriorate such as thermal decomposition, It is a nonflammable film that maintains transparency. Furthermore, the film material 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.

  Further, the film of the present invention is suitably used as a heat insulating material, a heat resistant material, a flame retardant / incombustible material, and a surface protective material, taking advantage of its flexibility, heat resistance, incombustibility / incombustibility, and transparency.

  The film material of the present invention can be widely used as a surface protective material. For example, surface protection of gauge glass, surface protection of heat-resistant glass, protective film for improving scratch resistance of glass surface, metal surface protection It can be used as a material.

The present invention has the following effects.
(1) As a main component other than water, it is possible to provide a film-like new material having flexibility with clay and additives as main components.
(2) A protective layer comprising a transparent gel-like clay film and a dry clay free-standing film can be provided.
(3) The dry clay free-standing film of the present invention is very simple to construct and can be coated without an adhesive layer.
(4) The dry clay free-standing film of the present invention can easily impart a heat-resistant layer to the surface of the material to be protected.
(5) The dry clay free-standing film of the present invention can easily impart a non-combustible layer to the surface of the material to be protected.
(6) The dry clay free-standing film of the present invention can provide a scratch-resistant layer on the surface of the material to be protected.
(7) According to the present invention, it is a new material with high flexibility, excellent heat resistance and nonflammability, and can be easily adhered to the surface of other substances, and easily by a method of drying following adhesion. A gel-like or dry clay film capable of forming a film can be provided.
(8) According to the present invention, it is possible to provide a new material / new technology that can be suitably used for a heat-resistant material, a flame retardant / non-combustible material, and a surface protective material.

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

(1) Manufacture of synthetic clay thin film (saponite)
As clay, 80 parts by weight of synthetic smectite (saponite) (Smecton SA, manufactured by Kunimine Kogyo Co., Ltd.) was added to distilled water, and this was put into a plastic sealed container together with a Teflon (registered trademark) rotor, and 25 ° C. The mixture was shaken vigorously for 1 hour to obtain a uniform dispersion having a solid-liquid ratio of about 2 percent.

  Further, 20 parts by weight of sodium polyacrylate (degree of polymerization: 22000-70000, manufactured by Wako Pure Chemical Industries, Ltd.) is added to distilled water, and this is put into a plastic sealed container together with a Teflon (registered trademark) rotor, 25 The mixture was shaken vigorously at 1 ° C. for 1 hour to obtain a uniform paste having a solid-liquid ratio of about 0.2 weight percent.

  These two liquids were mixed, mixed with a homogenizer for 1 hour, and then the paste was deaerated with a vacuum deaerator. Next, this paste was applied on the FEP sheet. For paste application, a stainless steel gravel was used. A spacer film was used as a guide to mold a uniform thickness paste film. Here, the thickness of the paste was 5 mm.

  The FEP sheet was dried in a forced convection oven kept at 60 ° C. and a relative humidity of 10 percent to obtain a transparent and uniform film. After standing for a whole day and night, the produced clay film was peeled from the FEP sheet to obtain a self-supporting film having no distortion and having a thickness of about 51 micrometers and having excellent flexibility.

  The obtained transparent self-supporting film was immersed in a saturated potassium chloride solution at 25 ° C. for 50 hours, then taken out, washed with distilled water three times, and immersed in distilled water for 30 minutes to obtain a gel-like transparent clay film. . Moreover, the water | moisture content of the gel-like transparent clay film | membrane was removed by natural drying on the FEP sheet | seat, and the dry clay self-supporting film | membrane was obtained.

(2) Characteristics of dried clay free-standing film The flexibility of the obtained dried clay free-standing film was measured using a mandrel type bending tester (ISO 1519). As a result, no defects such as cracks occurred even when bent to 2 mm in diameter. The total light transmittance was 91.28%, and the haze was 8.67%. The water absorption test of the dried clay free-standing film was conducted according to JIS K7209 and the water absorption was measured. The water absorption was 142%.

(3) Heat resistance of dry clay free-standing film The above-mentioned dry clay free-standing film was heat-treated in a forced convection oven at 230 ° C for 1 hour, but there was no significant change in appearance, cracks, pinholes, etc., Degradation such as thermal decomposition was not observed. The total light transmittance after the heat treatment was 91.03 percent, and the haze was 8.67 percent.

  When this film was analyzed by TG-DTA in a normal air atmosphere, no peak of heat generation was observed in the DTA curve between 300 ° C. and 400 ° C., and the large loss due to combustion in the TG curve. Is not observed, and it can be seen that combustion does not occur only when heated in a normal air atmosphere (FIG. 1). Further, it can be seen from this result that even when the film is subjected to heat treatment at 230 ° C. or higher, the film base material does not deteriorate such as thermal decomposition.

(4) Affixing the gel clay film to the glass The gel clay film or the dried clay self-supporting film immersed in distilled water so that the gel clay film is hydrated so that no air bubbles enter the slide glass. I put it quietly. It was air-dried or placed on a hot plate heated to 40 ° C. or left to stand overnight in an oven at 40 ° C. and 10% relative humidity to remove moisture from the gel-like clay film to obtain a dried clay film.

(5) Characteristics of Dry Clay Film When the total light transmittance and haze of the dried clay film on the slide glass were measured, the total light transmittance was 91.20%, and the haze was 7.22%. At the time of measurement, the measurement was performed using the total light transmittance of the slide glass as a blank. When this dried clay film was heat-treated at 350 ° C. for 24 hours, the total light transmittance was 90.11% and the haze was 9.22%.

(6) Adhesiveness by tape peel test A cross-cut tape peel test was performed according to JIS D0202 for the dry clay film adhered on the slide glass. As a result, peeling of the dry clay film from the glass surface was not confirmed, and it was confirmed that the dry clay film was in close contact with the glass surface.

(7) Hydrothermal treatment of dry clay film adhered to glass Move the dried clay film adhered to the slide glass to a heat-resistant container, add distilled water to it, seal it, and perform hydrothermal treatment at 230 ° C for 24 hours. As a result, the total light transmittance was 81.90%, and the haze was 70.39%. Further, in the portion where the dry clay film was not attached, the glass was whitened and the thickness was reduced to about 1/5. In the pasted portion, almost no thinning of the glass occurred, and whitening was reduced.

(8) Affixing the gel-like clay film to the metal surface The gel-like clay film obtained by immersing the gel-like clay film or the dried clay free-standing film in distilled water to prevent moisture from entering the metal surface. I put it quietly. A silver plate was used as the metal surface. It was air-dried or placed on a hot plate heated to 40 ° C. or left to stand overnight in an oven at 40 ° C. and 10% relative humidity to remove moisture from the gel-like clay film to obtain a dried clay film.

(9) Adhesiveness by tape peel test A cross-cut tape peel test was performed according to JIS D0202 for the dry clay film adhered to the surface of the silver plate. As a result, peeling of the dry clay film from the surface of the silver plate was not confirmed, and it was confirmed that the dry clay film was in close contact with the glass surface.

(10) Corrosion resistance test of silver plate The silver plate to which the above dry clay film was attached was immersed in an aqueous solution of ammonium sulfide prepared by 0.2 weight percent (manufactured by Wako Pure Chemical Industries, Ltd.) for 1 hour, and the state of corrosion was observed. Observed. FIG. 2 shows a photograph of a corrosion test of a silver plate to which a dry clay film is attached. The surface to which the dried clay film was applied was slightly discolored, and no significant change was observed. The surface on which the dry clay film was not attached was discolored and the surface was observed to be corroded.

(11) Extraction and measurement of interlayer ions The dried clay free-standing film was extracted with ammonium acetate, and interlayer ions were measured by ICP-AES. The extraction method involves weighing about 0.1 g of a dry clay film, placing it in a Teflon (registered trademark) container, adding 10 ml of ammonium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) prepared to 1 mol / dm ³ , and at 25 ° C. The mixture was shaken overnight to extract interlayer ions. After extraction, it was filtered using a 0.45 μm membrane filter, and interlayer ions were measured for the filtrate using ICP-AES.

(12) Measurement result As a result of measurement by the above extraction, potassium ions were not detected from the dry clay free-standing film before potassium treatment, and most of the interlayer ions were sodium ions. Interlayer ions of the dried clay film immersed in the saturated potassium aqueous solution were approximately 10 or more in the potassium / sodium ratio, and it was confirmed that sodium ions were exchanged for potassium ions. Moreover, it was confirmed that the ratio of potassium ions is 70% or more with respect to the sum of clay interlayer ions.

(13) Affixing a dry clay free-standing film When the above-mentioned dry clay free-standing film is placed on a glass and lightly pressed, the dry clay free-standing film is peeled off from the glass, and a cross-cut tape peeling test is performed according to JIS D0202. I couldn't. In order to obtain sufficient adhesion, it is necessary to be a gel-like clay film, and it was difficult to obtain a protective layer with a dry clay free-standing film.

(1) Manufacture of synthetic clay thin film (saponite)
As clay, 80 parts by weight of synthetic smectite (Smecton SA, manufactured by Kunimine Kogyo Co., Ltd.) is added to distilled water, and this is put into a plastic sealed container together with a Teflon (registered trademark) rotor, and at 25 ° C. for 1 hour. Shake vigorously to obtain a uniform dispersion with a solid-liquid ratio of about 2 percent.

  Moreover, about 25 weight percent polyacrylic acid aqueous solution (polymerization degree 8000, Wako Pure Chemical Industries, Ltd.) 20 weight part is added to said dispersion liquid, it mixes with a homogenizer for 1 hour, and solid-liquid ratio is about 1.24%. A dispersion was obtained.

  Next, this paste was deaerated with a vacuum deaerator. The degassed paste was applied on the FEP sheet. A stainless steel gravel was used for applying the paste. A spacer film was used as a guide to mold a uniform thickness paste film. Here, the thickness of the paste was 5 mm.

  The FEP sheet was dried in a forced convection oven kept at 60 ° C. and a relative humidity of 10 percent to obtain a transparent and uniform film. After standing for a whole day and night, the produced clay film was peeled from the FEP sheet to obtain a self-standing film having excellent flexibility with a thickness of about 60 micrometers without distortion.

  The obtained transparent self-supporting film was immersed in a saturated potassium chloride solution at 25 ° C. for 50 hours, then taken out, washed with distilled water three times, and immersed in distilled water for 30 minutes to obtain a gel-like transparent clay film. . Moreover, the water | moisture content of the gel-like transparent clay film | membrane was removed by natural drying on the FEP sheet | seat, and the dry clay self-supporting film | membrane was obtained.

(2) Characteristics of Dried Clay Free-standing Film The flexibility of the dried clay free-standing film was measured using a mandrel-type bending tester (ISO 1519). As a result, no defects such as cracks occurred even when bent to 2 mm in diameter. The total light transmittance was 91.00% and haze was 25.18%.

(3) Heat resistance of dry clay free-standing film The above-mentioned dry clay free-standing film was heat-treated in a forced convection oven at 230 ° C for 1 hour, but there was no significant change in appearance, cracks, pinholes, etc., Degradation such as thermal decomposition was not observed. The total light transmittance after the heat treatment was 90.80%, and the haze was 23.60%.

(4) Affixing the gel clay film to the glass The gel clay film or the dried clay self-supporting film immersed in distilled water so that the gel clay film is hydrated so that no air bubbles enter the slide glass. I put it quietly. It was air-dried or placed on a hot plate heated to 40 ° C. or left to stand overnight in an oven at 40 ° C. and 10% relative humidity to remove moisture from the gel-like clay film to obtain a dried clay film.

(5) Characteristics of Dry Clay Film When the total light transmittance and haze of the dried clay film on the slide glass were measured, the total light transmittance was 90.66% and the haze was 5.12%. At the time of measurement, the measurement was performed using the total light transmittance of the slide glass as a blank.

(6) Adhesiveness by tape peel test A cross-cut tape peel test was performed according to JIS D0202 for the dry clay film adhered on the slide glass. As a result, peeling of the dry clay film from the glass surface was not confirmed, and it was confirmed that the dry clay film was in close contact with the glass surface.

(7) Hydrothermal treatment of dry clay film adhered to glass Move the dried clay film adhered to the slide glass to a heat-resistant container, add distilled water to it, seal it, and perform hydrothermal treatment at 230 ° C for 24 hours. As a result, the total light transmittance was 83.75%, and the haze was 77.11%.

(8) Extraction and measurement of interlayer ions The dried clay free-standing film was extracted with ammonium acetate, and interlayer ions were measured by ICP-AES. The extraction method involves weighing about 0.1 g of a dry clay film, placing it in a Teflon (registered trademark) container, adding 10 ml of ammonium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) prepared to 1 mol / dm ³ , and at 25 ° C. The mixture was shaken overnight to extract interlayer ions. After extraction, it was filtered using a 0.45 μm membrane filter, and interlayer ions were measured for the filtrate using ICP-AES.

(9) Measurement results As a result of measurement by the above extraction, potassium ions were not detected from the dry clay free-standing film before potassium treatment, and most of the interlayer ions were sodium ions. Interlayer ions of the dried clay film immersed in the saturated potassium aqueous solution were approximately 10 or more in the potassium / sodium ratio, and it was confirmed that sodium ions were exchanged for potassium ions. Moreover, it was confirmed that the ratio of potassium ions is 70% or more with respect to the sum of clay interlayer ions.

(10) Affixing the dry clay free-standing film When the dry clay self-supporting film is placed on the glass and lightly pressed, the dry clay self-supporting film is peeled off from the glass, and a cross-cut tape peeling test is performed according to JIS D0202. I could not. In order to obtain sufficient adhesion, it is necessary to be a gel-like clay film, and it was difficult to obtain a protective layer with a dry clay free-standing film.

(1) Manufacture of synthetic clay thin film (Steven Site)
As clay, 80 parts by weight of synthetic smectite (Stevensite) is added to distilled water, and this is placed in a plastic sealed container together with a Teflon (registered trademark) rotor, shaken vigorously at 25 ° C. for 1 hour, A uniform dispersion with a ratio of about 2 percent was obtained. Further, 20 parts by weight of sodium polyacrylate (degree of polymerization 22000-70000, manufactured by Wako Pure Chemical Industries, Ltd.) is added to distilled water, and this is put in a plastic sealed container together with a Teflon (registered trademark) rotor, The mixture was shaken vigorously at 25 ° C. for 1 hour to obtain a uniform paste having a solid-liquid ratio of about 0.2 weight percent.

  These two liquids were mixed, mixed with a homogenizer for 1 hour, and then the paste was deaerated with a vacuum deaerator. Next, this paste was applied on the FEP sheet. A stainless steel gravel was used for applying the paste. A spacer film was used as a guide to mold a uniform thickness paste film. Here, the thickness of the paste was 5 mm.

  The FEP sheet was dried in a forced convection oven kept at 60 ° C. and a relative humidity of 10 percent to obtain a transparent and uniform film. After standing for a whole day and night, the produced clay film was peeled from the FEP sheet to obtain a self-standing film having excellent flexibility with a thickness of about 60 micrometers without distortion.

  The obtained transparent self-supporting film was immersed in a saturated potassium chloride solution at 25 ° C. for 50 hours, then taken out, washed with distilled water three times, and immersed in distilled water for 30 minutes to obtain a gel-like transparent clay film. . Moreover, the water | moisture content of the gel-like transparent clay film | membrane was removed by natural drying on the FEP sheet | seat, and the dry clay film | membrane was obtained.

(2) Characteristics of Dried Clay Free-standing Film The flexibility of the dried clay free-standing film was measured using a mandrel-type bending tester (ISO 1519). As a result, no defects such as cracks occurred even when bent to 2 mm in diameter. The total light transmittance was 91.34%, and the haze was 4.77%. When the water absorption test of the dried clay free-standing film was conducted according to JIS K7209 and the water absorption was measured, the water absorption was 69.2%.

(3) Heat resistance of dry clay free-standing film Dried clay free-standing film was heat-treated in a forced convection oven at 230 ° C for 1 hour, but there was no significant change in appearance, cracks, pinholes, etc., and thermal decomposition. Degradation such as was not recognized. The total light transmittance was 91.21%, and the haze was 4.65%.

  When this film was analyzed by TG-DTA in a normal air atmosphere, no exothermic peak was observed in the DTA curve between 300 ° C. and 400 ° C., and a large weight loss due to combustion was observed in the TG curve. However, it is understood that combustion does not occur only by heating in a normal air atmosphere (FIG. 3). Further, it can be seen from this result that even when the film is subjected to heat treatment at 230 ° C. or higher, the film base material does not deteriorate such as thermal decomposition.

(4) Attaching gel-like clay film to glass Gel-like clay film or gel-like clay film dipped in distilled water is immersed gently in distilled water so that air bubbles do not enter the slide glass. It was put on. It was naturally dried or placed on a hot plate heated to 40 ° C., or left still in an oven at 40 ° C. and 10% relative humidity for 24 hours to remove the moisture of the gel clay film to obtain a dried clay film.

(5) Characteristics of dry self-supporting film When the total light transmittance and haze of the dried clay film on the slide glass were measured, the total light transmittance was 91.20%, and the haze was 7.22%. In the measurement, the total light transmittance of the slide glass was subtracted as a blank and measured.

(6) Adhesiveness by tape peel test A cross-cut tape peel test was performed according to JIS D0202 for the dry clay film adhered on the slide glass. As a result, peeling of the dry clay film from the glass surface was not confirmed, and it was confirmed that the dry clay film was in close contact with the glass surface.

(7) Hydrothermal treatment of dried clay film adhered to glass The dried clay film adhered to the slide glass was transferred to a heat-resistant container, and distilled water was added thereto and sealed, followed by hydrothermal treatment at 230 ° C. for 24 hours. However, the total light transmittance was 91.47%, and the haze was 46.75%.

(8) Extraction and measurement of interlayer ions The dried clay free-standing film was extracted with ammonium acetate, and interlayer ions were measured by ICP-AES. The extraction method involves weighing about 0.1 g of a dry clay film, placing it in a Teflon (registered trademark) container, adding 10 ml of ammonium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) prepared to 1 mol / dm ³ , and at 25 ° C. The mixture was shaken overnight to extract interlayer ions. After extraction, it was filtered using a 0.45 μm membrane filter, and interlayer ions were measured for the filtrate using ICP-AES.

(9) Measurement results As a result of measurement by the above extraction, potassium ions were not detected from the dry clay free-standing film before potassium treatment, and most of the interlayer ions were sodium ions. Interlayer ions of the dry clay free-standing film immersed in the saturated potassium aqueous solution were approximately 10 or more in the potassium / sodium ratio, and it was confirmed that sodium ions were exchanged for potassium ions. Moreover, it was confirmed that the ratio of potassium ions is 70% or more with respect to the sum of clay interlayer ions.

(10) Affixing the dry clay free-standing film When the dry clay self-supporting film is placed on the glass and lightly pressed, the dry clay self-supporting film is peeled off from the glass, and a cross-cut tape peeling test is performed according to JIS D0202. I could not. In order to obtain sufficient adhesion, it is necessary to be a gel-like clay film, and it was difficult to obtain a protective layer with a dry clay free-standing film.

(1) Manufacture of synthetic clay thin film (Steven Site)
As clay, 80 parts by weight of synthetic smectite (Stevensite) is added to distilled water, and this is placed in a plastic sealed container together with a Teflon (registered trademark) rotor, shaken vigorously at 25 ° C. for 1 hour, A uniform dispersion with a ratio of about 2 percent was obtained.

  Moreover, about 25 weight percent polyacrylic acid aqueous solution (polymerization degree 8000, Wako Pure Chemical Industries, Ltd.) 20 weight part is added to said dispersion liquid, it mixes with a homogenizer for 1 hour, and solid-liquid ratio is about 1.24%. A dispersion was obtained.

  Next, this paste was deaerated with a vacuum deaerator. The degassed paste was applied on the FEP sheet. A stainless steel gravel was used for applying the paste. A spacer film was used as a guide to mold a uniform thickness paste film. Here, the thickness of the paste was 5 mm.

  The FEP sheet was dried in a forced convection oven kept at 60 ° C. and a relative humidity of 10 percent to obtain a transparent and uniform film. After standing for a whole day and night, the produced clay film was peeled from the FEP sheet to obtain a self-standing film having excellent flexibility with a thickness of about 62 micrometers without distortion.

  The obtained transparent self-supporting film was immersed in a saturated potassium chloride solution at 25 ° C. for 50 hours, then taken out, washed with distilled water three times, and immersed in distilled water for 30 minutes to obtain a gel-like transparent clay film. . Moreover, the water | moisture content of the gel-like transparent clay film | membrane was removed by natural drying on the FEP sheet | seat, and the dry clay self-supporting film | membrane was obtained.

(2) Characteristics of Dried Clay Free-standing Film The flexibility of the dried clay free-standing film was measured using a mandrel-type bending tester (ISO 1519). As a result, no defects such as cracks occurred even when bent to 2 mm in diameter. The total light transmittance was 90.22%, and the haze was 10.90%.

(3) Heat resistance of dry clay free-standing film Dried clay free-standing film was heat-treated in a forced convection oven at 230 ° C for 1 hour, but there was no major change in appearance, cracks, pinholes, etc., and no heat. Degradation such as decomposition was not observed. The total light transmittance was 88.50%, and the haze was 10.98%.

(4) Attaching gel-like clay film to glass Gel-like clay film or gel-like clay film dipped in distilled water is immersed gently in distilled water so that air bubbles do not enter the slide glass. It was put on. It was naturally dried or placed on a hot plate heated to 40 ° C., or left still in an oven at 40 ° C. and 10% relative humidity for 24 hours to remove the moisture of the gel clay film to obtain a dried clay film.

(5) Characteristics of Dry Clay Film When the total light transmittance and haze of the dried clay film on the slide glass were measured, the total light transmittance was 91.01%, and the haze was 5.12%. At the time of measurement, the measurement was performed using the total light transmittance of the slide glass as a blank.

(6) Adhesiveness by tape peeling test A cross-cut tape peeling test was performed according to JIS D0202 on the dried clay film adhered on the slide glass. As a result, peeling of the dry clay film from the glass surface was not confirmed, and it was confirmed that the dry clay film was in close contact with the glass surface.

(7) Hydrothermal treatment of dry clay film adhered to glass Move the dried clay film adhered to the slide glass to a heat-resistant container, add distilled water to it, seal it, and perform hydrothermal treatment at 230 ° C for 24 hours. As a result, the total light transmittance was 89.78%, and the haze was 77.85%.

(8) Extraction and measurement of interlayer ions The dried clay free-standing film was extracted with ammonium acetate, and interlayer ions were measured by ICP-AES. The extraction method involves weighing about 0.1 g of a dry clay film, placing it in a Teflon (registered trademark) container, adding 10 ml of ammonium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) prepared to 1 mol / dm ³ , and at 25 ° C. The mixture was shaken overnight to extract interlayer ions. After extraction, it was filtered using a 0.45 μm membrane filter, and interlayer ions were measured for the filtrate using ICP-AES.

(9) Measurement results As a result of measurement by the above extraction, potassium ions were not detected from the dry clay free-standing film before potassium treatment, and most of the interlayer ions were sodium ions. Interlayer ions of the dried clay film immersed in the saturated potassium aqueous solution were approximately 10 or more in the potassium / sodium ratio, and it was confirmed that sodium ions were exchanged for potassium ions. Moreover, it was confirmed that the ratio of potassium ions is 70% or more with respect to the sum of clay interlayer ions.

(10) Affixing the dry clay free-standing film When the dry clay self-supporting film is placed on the glass and lightly pressed, the dry clay self-supporting film is peeled off from the glass, and a cross-cut tape peeling test is performed according to JIS D0202. I could not. In order to obtain sufficient adhesion, it is necessary to be a gel-like clay film, and it was difficult to obtain a protective layer with a dry clay free-standing film.

(1) Manufacture of synthetic clay thin film (saponite)
As clay, 80 parts by weight of synthetic smectite (Smecton SA, manufactured by Kunimine Kogyo Co., Ltd.) is added to distilled water, and this is put into a plastic sealed container together with a Teflon (registered trademark) rotor, and at 25 ° C. for 1 hour. Shake vigorously to obtain a uniform dispersion with a solid-liquid ratio of about 2 percent.

  Further, 20 parts by weight of about 10 weight percent sodium carboxymethyl cellulose (MP Biomedicals) was added to the above dispersion and mixed with a homogenizer for 1 hour to obtain a dispersion having a solid-liquid ratio of about 1.30 percent.

  Next, this paste was deaerated with a vacuum deaerator. The degassed paste was applied on the FEP sheet. A stainless steel gravel was used for applying the paste. A spacer film was used as a guide to mold a uniform thickness paste film. Here, the thickness of the paste was 5 mm.

  The FEP sheet was dried in a forced convection oven kept at 60 ° C. and a relative humidity of 10 percent to obtain a transparent and uniform film. After standing for a whole day and night, the produced clay film was peeled from the FEP sheet to obtain a self-standing film having excellent flexibility with a thickness of about 60 micrometers without distortion.

  The obtained transparent self-supporting film was immersed in a saturated potassium chloride solution at 25 ° C. for 50 hours, then taken out, washed with distilled water three times, and immersed in distilled water for 30 minutes to obtain a gel-like transparent clay film. . Moreover, the water | moisture content of the gel-like transparent clay film | membrane was removed by natural drying on the FEP sheet | seat, and the dry clay self-supporting film | membrane was obtained.

(2) Characteristics of Dried Clay Free-standing Film The flexibility of the dried clay free-standing film was measured using a mandrel-type bending tester (ISO 1519). As a result, no defects such as cracks occurred even when bent to 2 mm in diameter. The total light transmittance was 91.26 percent, and the haze was 10.51 percent.

(3) Heat resistance of dry clay free-standing film Dried clay free-standing film was heat-treated in a forced convection oven at 230 ° C for 1 hour, but there was no major change in appearance, cracks, pinholes, etc., and no heat. Degradation such as decomposition was not observed.

(4) Attaching gel-like clay film to glass Gel-like clay film or gel-like clay film dipped in distilled water is immersed gently in distilled water so that air bubbles do not enter the slide glass. It was put on. It was naturally dried or placed on a hot plate heated to 40 ° C., or left still in an oven at 40 ° C. and 10% relative humidity for 24 hours to remove the moisture of the gel clay film to obtain a dried clay film.

(5) Characteristics of Dry Clay Film When the total light transmittance and haze of the dried clay film on the slide glass were measured, the total light transmittance was 96.95% and the haze was 13.10%. In the measurement, the total light transmittance of the slide glass was subtracted as a blank and measured.

(6) Adhesiveness by tape peel test A cross-cut tape peel test was performed according to JIS D0202 for the dry clay film adhered on the slide glass. As a result, peeling of the dry clay film from the glass surface was not confirmed, and it was confirmed that the dry clay film was in close contact with the glass surface.

(7) Affixing the dried clay free-standing film When the dried clay free-standing film is placed on the glass and lightly pressed, the dried clay free-standing film is peeled off from the glass and subjected to a cross-cut tape peeling test according to JIS D0202. I could not. In order to obtain sufficient adhesion, it is necessary to be a gel-like clay film, and it has been difficult to obtain a protective layer with a dry clay free-standing film.

(1) Manufacture of synthetic clay thin film (Steven Site)
As clay, 80 parts by weight of synthetic smectite (Stevensite) is added to distilled water, and this is placed in a plastic sealed container together with a Teflon (registered trademark) rotor, shaken vigorously at 25 ° C. for 1 hour, A uniform dispersion with a ratio of about 2 percent was obtained.

  Further, 20 parts by weight of about 10 weight percent sodium carboxymethyl cellulose (MP Biomedicals) was added to the above dispersion and mixed with a homogenizer for 1 hour to obtain a dispersion having a solid-liquid ratio of about 1.30 percent.

  Next, this paste was deaerated with a vacuum deaerator. The degassed paste was applied on the FEP sheet. A stainless steel gravel was used for applying the paste. A spacer film was used as a guide to mold a uniform thickness paste film. Here, the thickness of the paste was 5 mm.

  The FEP sheet was dried in a forced convection oven kept at 60 ° C. and a relative humidity of 10 percent to obtain a transparent and uniform film. The clay film produced after standing overnight was peeled off from the FEP sheet to obtain a self-supporting film having a thickness of about 58 micrometers and free from distortion.

  The obtained transparent self-supporting film was immersed in a saturated potassium chloride solution at 25 ° C. for 50 hours, then taken out, washed with distilled water three times, and immersed in distilled water for 30 minutes to obtain a gel-like transparent clay film. . Moreover, the water | moisture content of the gel-like transparent clay film | membrane was removed by natural drying on the FEP sheet | seat, and the dry clay self-supporting film | membrane was obtained.

(2) Characteristics of Dried Clay Free-standing Film The flexibility of the dried clay free-standing film was measured using a mandrel-type bending tester (ISO 1519). As a result, no defects such as cracks occurred even when bent to 2 mm in diameter. The total light transmittance was 91.26 percent, and the haze was 10.51 percent.

(3) Heat resistance of dry clay free-standing film Dried clay free-standing film was heat-treated in a forced convection oven at 230 ° C for 1 hour, but there was no major change in appearance, cracks, pinholes, etc., and no heat. Degradation such as decomposition was not observed.

(4) Attaching gel-like clay film to glass Gel-like clay film or gel-like clay film dipped in distilled water is immersed gently in distilled water so that air bubbles do not enter the slide glass. It was put on. It was naturally dried or placed on a hot plate heated to 40 ° C., or left still in an oven at 40 ° C. and 10% relative humidity for 24 hours to remove the moisture of the gel clay film to obtain a dried clay film.

(5) Characteristics of Dry Clay Film When the total light transmittance and haze of the dried clay film on the slide glass were measured, the total light transmittance was 96.95% and the haze was 13.10%. At the time of measurement, the measurement was performed using the total light transmittance of the slide glass as a blank.

(6) Adhesiveness by tape peel test A cross-cut tape peel test was performed according to JIS D0202 for the dry clay film adhered on the slide glass. As a result, peeling of the dry clay film from the glass surface was not confirmed, and it was confirmed that the dry clay film was in close contact with the glass surface.

(7) Affixing the dried clay free-standing film When the dried clay free-standing film is placed on the glass and lightly pressed, the dried clay free-standing film is peeled off from the glass and subjected to a cross-cut tape peeling test according to JIS D0202. I could not. In order to obtain sufficient adhesion, it is necessary to be a gel-like clay film, and it is difficult to obtain a protective layer with a dry clay film.

(Comparative Example 1)
(1) Production of Synthetic Clay Film Using Carboxymethylcellulose Ammonium As clay, 80 parts by weight of synthetic smectite (Smecton SA, manufactured by Kunimine Kogyo Co., Ltd.) is added to distilled water. It was put together with a registered trademark rotor and shaken vigorously at 25 ° C. for 1 hour to obtain a uniform dispersion having a solid-liquid ratio of about 2 percent.

  Further, 20 parts by weight of carboxymethyl cellulose ammonium (manufactured by Daicel Chemical Industries, Ltd.) is added to distilled water, and this is put into a plastic sealed container together with a Teflon (registered trademark) rotor and shaken vigorously at 25 ° C. for 1 hour. As a result, a uniform paste having a solid-liquid ratio of about 10 weight percent was obtained.

  These two liquids were mixed, mixed with a homogenizer for 1 hour, and then the paste was deaerated with a vacuum deaerator. Next, this paste was applied on the FEP sheet. A stainless steel gravel was used for applying the paste. A spacer film was used as a guide to mold a uniform thickness paste film. Here, the thickness of the paste was 5 mm.

  The FEP sheet was dried in a forced convection oven kept at 60 ° C. and a relative humidity of 10 percent to obtain a transparent and uniform film. After standing overnight, the produced clay film was peeled off from the FEP sheet to obtain a self-supporting transparent self-supporting film having a thickness of about 75 micrometers without distortion.

  The obtained transparent self-supporting film was immersed in a saturated potassium chloride solution at 25 ° C. for 50 hours, then taken out, washed with distilled water three times, and immersed in distilled water for 30 minutes to obtain a gel-like transparent clay film. . Moreover, the water | moisture content of the gel-like transparent clay film | membrane was removed by natural drying on the FEP sheet | seat, and the dry clay self-supporting film | membrane was obtained.

(2) Characteristics of Dried Clay Free-standing Film The flexibility of the dried clay free-standing film was measured using a mandrel-type bending tester (ISO 1519). As a result, no defects such as cracks occurred even when bent to 2 mm in diameter. The total light transmittance was 87.20 percent and the haze was 9.80 percent.

(3) Adhesiveness of dry clay free-standing film The obtained gel-like clay film was gently placed on a slide glass so that no bubbles would enter. It was naturally dried or placed on a hot plate heated to 40 ° C., or left still in an oven at 40 ° C. and 10% relative humidity for 24 hours to remove the moisture of the gel clay film to obtain a dried clay film. The dry clay film was subjected to a cross-cut tape peeling test according to JIS D0202. As a result, peeling from the glass surface was confirmed, and the adhesion was not good. It was confirmed that the adhesion was lower than when polyacrylate was used.

(Comparative Example 2)
(1) Preparation of synthetic clay film using methyl vinyl ether maleic anhydride As clay, 80 parts by weight of synthetic smectite (Smecton SA, manufactured by Kunimine Kogyo Co., Ltd.) is added to distilled water. It was put together with a Teflon (registered trademark) rotor and shaken vigorously at 25 ° C. for 1 hour to obtain a uniform dispersion having a solid-liquid ratio of about 2 percent.

  Further, 20 parts by weight of methyl vinyl ether maleic anhydride (manufactured by Daicel Chemical Industries, Ltd.) is added to distilled water, and this is put into a plastic sealed container together with a Teflon (registered trademark) rotor, and at 25 ° C. for 1 hour. Shake vigorously to obtain a uniform paste with a solid-liquid ratio of about 10 weight percent.

  These two liquids were mixed, mixed with a homogenizer for 1 hour, and then the paste was deaerated with a vacuum deaerator. Next, this paste was applied on the FEP sheet. A stainless steel gravel was used for applying the paste. A spacer film was used as a guide to mold a uniform thickness paste film. Here, the thickness of the paste was 5 mm.

  The FEP sheet was dried in a forced convection oven kept at 60 ° C. and a relative humidity of 10 percent to obtain a transparent and uniform film. After standing overnight, the produced clay film was peeled from the FEP sheet to obtain a self-supporting transparent self-supporting film having a thickness of about 69 micrometers without distortion.

  The obtained transparent self-supporting film was immersed in a saturated potassium chloride solution at 25 ° C. for 50 hours, then taken out, washed with distilled water three times, and immersed in distilled water for 30 minutes to obtain a gel-like transparent clay film. . Moreover, the water | moisture content of the gel-like transparent clay film | membrane was removed by natural drying on the FEP sheet | seat, and the dry clay self-supporting film | membrane was obtained.

(2) Characteristics of Dried Clay Free-standing Film The flexibility of the dried clay free-standing film was measured using a mandrel-type bending tester (ISO 1519). As a result, no defects such as cracks occurred even when bent to 2 mm in diameter.

(3) Adhesiveness of dry clay free-standing film The obtained gel-like clay film was gently placed on a slide glass so that no bubbles would enter. It was naturally dried or placed on a hot plate heated to 40 ° C., or left still in an oven at 40 ° C. and 10% relative humidity for 24 hours to remove the moisture of the gel clay film to obtain a dried clay film. The dry clay film was subjected to a cross-cut tape peeling test according to JIS D0202. As a result, peeling from the glass surface was confirmed, and the adhesion was not good. It was confirmed that the adhesion was lower than when polyacrylate was used.

(Comparative Example 3)
(1) Production of hydrogen ion exchange membrane As clay, 80 parts by weight of synthetic smectite (Smecton SA, manufactured by Kunimine Kogyo Co., Ltd.) is added to distilled water, and this is placed in a plastic sealed container and rotated by Teflon (registered trademark). The mixture was put together with a child and shaken vigorously at 25 ° C. for 1 hour to obtain a uniform dispersion having a solid-liquid ratio of about 2 percent.

  Further, 20 parts by weight of sodium polyacrylate (degree of polymerization 22000-70000, manufactured by Wako Pure Chemical Industries, Ltd.) is added to distilled water, and this is put in a plastic sealed container together with a Teflon (registered trademark) rotor, The mixture was shaken vigorously at 25 ° C. for 1 hour to obtain a uniform paste having a solid-liquid ratio of about 0.2 weight percent.

  These two liquids were mixed, mixed with a homogenizer for 1 hour, and then the paste was deaerated with a vacuum deaerator. Next, this paste was applied on the FEP sheet. A stainless steel gravel was used for applying the paste. A spacer film was used as a guide to mold a uniform thickness paste film. Here, the thickness of the paste was 5 mm.

  The FEP sheet was dried in a forced convection oven kept at 60 ° C. and a relative humidity of 10 percent to obtain a transparent and uniform film. After standing for a whole day and night, the produced clay film was peeled from the FEP sheet to obtain a self-supporting film having a thickness of about 51 μm and excellent in flexibility without distortion.

  The obtained transparent free-standing film was immersed in concentrated nitric acid at 25 ° C. (63 weight percent, manufactured by Wako Pure Chemical Industries, Ltd.) for 6 hours, then taken out, washed with distilled water three times, and immersed in distilled water for 30 minutes. As a result, a gel-like transparent clay film was obtained. Moreover, the water | moisture content of the gel-like transparent clay film | membrane was removed by natural drying on the FEP sheet | seat, and the dry clay self-supporting film | membrane was obtained.

(2) Adhesiveness of hydrogen ion exchange membrane The obtained gel-like clay membrane was gently placed on a slide glass so that no bubbles would enter. It was air-dried or placed on a hot plate heated to 40 ° C., or left standing overnight in an oven at 40 ° C. and 10% relative humidity to remove moisture from the gel clay film to obtain a dry clay film. The dry clay film was subjected to a cross-cut tape peeling test according to JIS D0202. As a result, peeling from the glass surface was confirmed, and the adhesion was not good. It was confirmed that the adhesion was lower than when polyacrylate was used.

(Comparative Example 4)
(1) Preparation of potassium ion exchange untreated membrane As clay, 80 parts by weight of synthetic smectite (stevensite) is added to distilled water, and this is put into a plastic sealed container together with a Teflon (registered trademark) rotor, The mixture was shaken vigorously at 25 ° C. for 1 hour to obtain a uniform dispersion having a solid-liquid ratio of about 2 percent.

  Further, 20 parts by weight of sodium polyacrylate (degree of polymerization 22000-70000, manufactured by Wako Pure Chemical Industries, Ltd.) is added to distilled water, and this is put in a plastic sealed container together with a Teflon (registered trademark) rotor, The mixture was shaken vigorously at 25 ° C. for 1 hour to obtain a uniform paste having a solid-liquid ratio of about 0.2 weight percent.

  These two liquids were mixed, mixed with a homogenizer for 1 hour, and then the paste was deaerated with a vacuum deaerator. Next, this paste was applied on the FEP sheet. A stainless steel gravel was used for applying the paste. A spacer film was used as a guide to mold a uniform thickness paste film. Here, the thickness of the paste was 5 mm.

  The FEP sheet was dried in a forced convection oven maintained at 60 ° C. and a relative humidity of 10% to obtain a transparent and uniform film. After standing for a whole day and night, the produced clay film was peeled from the FEP sheet to obtain a self-supporting film having a thickness of about 51 μm and excellent in flexibility without distortion.

  The obtained transparent self-supporting film was immersed in distilled water for 30 minutes to obtain a gel-like transparent clay film. Moreover, the water | moisture content of the gel-like transparent clay film | membrane was removed by natural drying on the FEP sheet | seat, and the dry clay self-supporting film | membrane was obtained.

(2) Adhesiveness of untreated potassium ion exchange membrane The obtained gel-like clay membrane was gently placed on a slide glass so that no bubbles would enter. It was naturally dried or placed on a hot plate heated to 40 ° C., or left still in an oven at 40 ° C. and 10% relative humidity for 24 hours to remove the moisture of the gel clay film to obtain a dried clay film. The dry clay film was subjected to a cross-cut tape peeling test according to JIS D0202. As a result, peeling from the glass surface was confirmed, and the adhesion was not good. It was confirmed that the adhesion was low compared to the case where potassium ion exchange was not performed.

(Comparative Example 5)
(1) Preparation of clay thin film containing no additives As clay, synthetic smectite (Smecton SA, manufactured by Kunimine Kogyo Co., Ltd.) is added to distilled water, and this is put into a plastic sealed container and rotated by Teflon (registered trademark). The mixture was put together with a child and shaken vigorously at 25 ° C. for 1 hour to obtain a uniform dispersion having a solid-liquid ratio of about 2 percent.

  This dispersion was deaerated with a vacuum deaerator. Next, this paste was applied on the FEP sheet. A stainless steel gravel was used for applying the paste. A spacer film was used as a guide to mold a uniform thickness paste film. Here, the thickness of the paste was 5 mm.

  The FEP sheet was dried at room temperature to obtain a transparent and uniform film. However, this film could not be peeled off from the FEP sheet, and a self-supporting film could not be obtained.

  Saturated potassium chloride solution was poured into the film adhered on the FEP sheet to perform potassium treatment. However, in several hours, the shape of the film adhered on the FEP collapsed, and a potassiumated film could not be obtained. It was found that it was extremely difficult to obtain a self-supporting film in the film to which no additive was added, compared to the film in which the additive was added, and it was not possible to perform potassium treatment.

(Comparative Example 6)
(1) Preparation of clay thin film containing no additive As clay, synthetic smectite (Stevensite) is added to distilled water, and this is put into a plastic sealed container together with a Teflon (registered trademark) rotor, and 25 ° C. The mixture was shaken vigorously for 1 hour to obtain a uniform dispersion having a solid-liquid ratio of about 2 percent.

  This dispersion was deaerated with a vacuum deaerator. Next, this paste was applied on the FEP sheet. A stainless steel gravel was used for applying the paste. A spacer film was used as a guide to mold a uniform thickness paste film. Here, the thickness of the paste was 5 mm.

  The FEP sheet was dried at room temperature to obtain a transparent and uniform film. However, this film could not be peeled off from the FEP sheet, and a self-supporting film could not be obtained.

  Saturated potassium chloride solution was poured into the film adhered on the FEP sheet to perform potassium treatment. However, in several hours, the shape of the film adhered on the FEP collapsed, and a potassiumated film could not be obtained. It was found that the film without the additive was remarkably inferior to the film with the added film and could not be subjected to potassium treatment.

(Comparative Example 7)
Film formation and potassium treatment only with additives (1) Preparation of polyvinyl alcohol film Polyvinyl alcohol (# 500, manufactured by Kanto Chemical Co., Inc.) was added to distilled water to prepare a 9.9 weight percent solution. This solution was deaerated with a vacuum deaerator and then developed on a polypropylene balance dish and allowed to air dry overnight at room temperature to obtain a self-supporting film of only additive. The obtained film was immersed in a saturated potassium chloride solution for 50 hours. Subsequently, it was rinsed 3 times with distilled water and immersed in distilled water for 30 minutes. As a result, it was not possible to obtain a self-supporting membrane which was redissolved and treated with potassium.

(2) Preparation of methyl vinyl ether maleic anhydride film Methyl vinyl ether maleic anhydride (manufactured by Daicel Chemical Industries, Ltd.) was added to distilled water to prepare a 20 weight percent solution. This solution was deaerated with a vacuum deaerator and then developed on a polypropylene balance dish and allowed to air dry overnight at room temperature to obtain a self-supporting film of only additive. When the obtained membrane was immersed in a saturated potassium chloride solution, its shape collapsed and dissolved, and a self-supporting membrane treated with potassium could not be obtained.

(3) Production of sodium carboxymethylcellulose membrane Sodium carboxymethylcellulose (MP Biomedicals) was added to distilled water to prepare a 10 weight percent solution. This solution was deaerated with a vacuum deaerator and then developed on a polypropylene balance dish and allowed to air dry overnight at room temperature to obtain a self-supporting film of only additive. When the obtained membrane was immersed in a saturated potassium chloride solution, its shape collapsed and dissolved, and a self-supporting membrane treated with potassium could not be obtained.

(4) Preparation of carboxymethylcellulose ammonium membrane Carboxymethylcellulose ammonium (manufactured by Daicel Chemical Industries, Ltd.) was added to distilled water to prepare a 14 weight percent solution. This solution was deaerated with a vacuum deaerator and then developed on a polypropylene balance dish and allowed to air dry overnight at room temperature to obtain a self-supporting film of only additive. When the obtained membrane was immersed in a saturated potassium chloride solution, its shape collapsed and dissolved, and a self-supporting membrane treated with potassium could not be obtained.

(5) Preparation of hydroxyethyl cellulose membrane Hydroxyethyl cellulose (manufactured by Wako Pure Chemical Industries, Ltd.) was added to distilled water to prepare a 5 weight percent solution. This solution was deaerated with a vacuum deaerator and then developed on a polypropylene balance dish and allowed to air dry overnight at room temperature to obtain a self-supporting film of only additive. When the obtained membrane was immersed in a saturated potassium chloride solution, its shape collapsed and dissolved, and a self-supporting membrane treated with potassium could not be obtained.

(6) Production of polyacrylic acid film Polyacrylic acid (average molecular weight 250,000, manufactured by Wako Pure Chemical Industries, Ltd.) was added to distilled water to prepare a 5 weight percent solution. This solution was deaerated with a vacuum deaerator and then developed on a polypropylene balance dish and allowed to air dry overnight at room temperature to obtain a self-supporting film of only additive. When the obtained membrane was immersed in a saturated potassium chloride solution, its shape collapsed and dissolved, and a self-supporting membrane treated with potassium could not be obtained.

(7) Preparation of sodium polyacrylate film Sodium polyacrylate (polymerization degree: 22000-70000, manufactured by Wako Pure Chemical Industries, Ltd.) was added to distilled water to prepare a 2 weight percent solution. This solution was deaerated with a vacuum deaerator and then developed on a polypropylene balance dish and allowed to air dry overnight at room temperature to obtain a self-supporting film of only additive. When the obtained membrane was immersed in a saturated potassium chloride solution, its shape collapsed and dissolved, and a self-supporting membrane treated with potassium could not be obtained.

(Comparative Example 8)
(1) Film formation of transparent material Film formation was performed according to Example 8 of JP2007-63118A. The obtained film was used for an adhesion test or the like without being subjected to potassium treatment.

(2) Adhesion test When the above film was placed on glass and lightly pressed, this film peeled off from the glass, and a cross-cut tape peel test could not be performed in accordance with JIS D0202. Moreover, water was used as an adhesive layer, and the above membrane was gently placed on the slide glass so that no bubbles would enter. It was air-dried or placed on a hot plate heated to 40 ° C., or left in an oven at 40 ° C. and 10% relative humidity overnight.

  A cross-cut tape peeling test was performed on the dried clay film adhered on the slide glass in accordance with JIS D0202. As a result, peeling of the dried clay film from the glass surface occurred, and it was confirmed that the adhesion to the glass surface was lower than when no potassium treatment was performed.

  As described in detail above, the present invention relates to a gel-like clay film and a dry clay free-standing film produced therefrom, and according to the present invention, even when heat treatment at 230 ° C. or higher is performed, the film substrate is thermally decomposed. It is possible to obtain a protective layer that does not deteriorate and is nonflammable and transparent. The gel-like clay film and the dried clay free-standing film of the present invention are very easy to construct, can be coated without an adhesive layer, and can easily provide a heat-resistant layer on the surface of the protected material. It has the characteristics that a nonflammable layer can be easily applied to the surface, and a scratch-resistant layer can be applied to the surface of the material to be protected. INDUSTRIAL APPLICABILITY The present invention is useful, for example, as providing a new clay free-standing film that can be used as a surface protection for glass for gauges, a surface protection for heat-resistant glass, an improved protective film for scratch resistance on the glass surface, and a metal surface protective material It is.

It is a TG-DTA chart figure of the synthetic clay film | membrane (saponite) containing 20 weight% of an additive. It is the photograph of the corrosion test of the silver plate which stuck the dry clay film. It is a TG-DTA chart figure of the synthetic clay film | membrane (Stevensite) containing 20 weight% of an additive.

Claims (16)

  It is a hydrogel clay film with mechanical strength and flexibility that can be used as a self-supporting film, in which clay is the main component among components other than water, and it contains a water-soluble polymer as an additive. Of the interlayer ions, the proportion of potassium ions is at least 70 percent with respect to the sum of the clay interlayer ions, and the water-soluble polymer is any of sodium carboxymethylcellulose, polyacrylic acid, and sodium polyacrylate, and is transparent. And a gel-like clay film characterized by being a gel-like clay self-supporting film having a property of adhering to the surface of an object.   The gelled clay film according to claim 1, wherein the clay is mainly composed of smectite.   The gel-like clay film according to claim 1, wherein the weight of water relative to the dry weight of the free-standing film ranges from 50 percent to 150 percent. Water-soluble polymer, polyacrylic acid, or a sodium carboxymethylcellulose, gelatinous clay film of claim 1. The gel clay film according to any one of claims 1 to 4, wherein the abundance ratio of the clay and the additive is in a range of 80/20 to 95/5 in terms of a clay / additive ratio (mass ratio) .   The gel-like clay film according to any one of claims 1 to 5, which is a gel-like clay film attached to the surface of an object as a material to be protected and has a property of sticking to the surface of the object.   The gelled clay film according to claim 6, wherein the object is glass or metal. A dry clay film from which moisture of the gel-like clay film according to claim 6 or 7 is removed, wherein the thickness of the dry clay film is 0.01 mm or more and 0.1 mm or less, and the total light transmittance is A dry clay film characterized in that it is at least 90 percent.   The dry clay film according to claim 8, wherein the thickness is 0.01 millimeter or more and 0.1 millimeter or less.   The dry clay film according to claim 8, wherein the dry clay film has adhesion that prevents the dry clay film from peeling off from the surface of the protected material in a tape peeling test (JIS D0202) of the dry clay film attached to the surface of the object as the protected material.   The dry clay film according to claim 8, wherein the total light transmittance is 90% or more and 95% or less.   The dry clay film according to claim 8, wherein the total light transmittance after heat treatment at 350 ° C. for 24 hours under normal air conditions is 80% or more and 90% or less.   The dry clay film according to claim 8, wherein the total light transmittance after performing a hydrothermal treatment at 230 ° C for 24 hours is 80% or more and 90% or less.   The dry clay film according to claim 8, which is nonflammable.   An adhesive member comprising the gel-like clay film or the dried clay film according to any one of claims 1 to 14.   The sticking member according to claim 15, wherein the member is a coating material, a heat insulating material, a heat resistant material, or a flame retardant / incombustible material.