JP2017105991A - Heat-resistant gas barrier film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-resistant gas barrier film comprising lignin and clay mineral and having heat resistance of 200°C or more and high water vapor permeability for a long time.SOLUTION: The present invention provides a heat-resistant gas barrier film comprising modified lignin, modified with polyethylene glycol, and clay mineral.SELECTED DRAWING: None

Description

  The present invention relates to a heat-resistant gas barrier film and a method for producing the same.

  With the spread of digital home appliances such as mobile phones and tablet terminals in recent years, development of flexible devices that are excellent in storability, portability, and lightweight has been promoted. Such a device is usually configured by manufacturing an electronic device with a wiring material or the like on a highly flexible thin film substrate. The performance required for the substrate for the electronic device is required to have heat resistance to a high temperature process of about 300 ° C. or higher, gas shielding property to water vapor and oxygen, dimensional stability to heating / cooling in the manufacturing process, and the like. As for substrate materials, organic resins have been studied due to their good flexibility, but the heat resistance of many resins is about 200 ° C, and at present, they are limited to polyimide resins having heat resistance of 300 ° C or higher. There was a problem. Furthermore, the polyimide resin has poor water vapor barrier properties and dimensional stability, and its use as a device has been limited.

In order to compensate for the disadvantages of such organic resins, attempts have been made to improve heat resistance, dimensional stability, etc. by compounding with inorganic compounds. Silica, layered clay minerals, and the like are used as inorganic compounds, and a technique for combining layered clay minerals with organic resins has been disclosed (Patent Document 1). By using a layered clay mineral excellent in film formability, a thin film material having flexibility and having heat resistance, gas shielding properties, dimensional stability, incombustibility, and the like is provided. In this technology, it plays a role as a binder for layered clay minerals, the main component of which is an organic resin. However, when heat resistance is intended, it is necessary to use a resin with high heat resistance, Of these, use of polyimide resin or epoxy resin is indispensable. Further, lignin can also be used as a biological resin. Therefore, the technique using the lignin origin epoxy resin composition (patent document 2) using lignin is indicated. However, the moisture permeability of the film obtained is about 2.0 g / m ² / day when the film thickness is about 20 μm, and it cannot be said that the film has a high moisture permeability.

Japanese Patent No. 5099412 Japanese Patent No. 4304251

  Under such circumstances, in view of the above-mentioned conventional technology, the present inventors have a mechanical strength that can be used as a self-supporting film, are water resistant, and can be used under high temperature conditions exceeding 200 ° C. Mechanical strength that can be used as a self-supporting film by using modified lignin and, if necessary, a cross-linking agent in the process of accumulating earnest research with the goal of developing a gas barrier film mainly composed of clay minerals. It was found that a film material having high moisture permeability, smoothness, and electrical insulation can be obtained while having thermal stability.

  This invention makes it a subject to provide the film | membrane which has the heat resistance of 200 degreeC or more and high water-vapor permeability over a long time about the heat-resistant gas barrier film which consists of a lignin and a clay mineral.

In order to solve the above problems, the present invention provides the following inventions.
(1) A heat-resistant gas barrier film comprising a modified lignin modified with polyethylene glycol and a clay mineral.
(2) The heat resistant gas barrier film according to (1), wherein the clay mineral is lithium, proton or ammonium ion exchange bentonite.
(3) The heat-resistant gas barrier film according to (2), wherein the clay mineral is lithium, proton or ammonium ion exchange bentonite that has been heat-treated at a temperature of 230 ° C. or higher.
(4) The heat-resistant gas barrier film according to (1), wherein the modified lignin is a modified lignin modified with polyethylene glycol having a carboxyl group added.
(5) The heat-resistant gas barrier film according to any one of the above (1) to (4), wherein the weight ratio of the modified lignin to the clay mineral is in the range of 20 parts by weight to 80 parts by weight to 40 parts by weight to 60 parts by weight. .
(6) The heat-resistant gas barrier film according to any one of (1) to (5), wherein the modified lignin contains a crosslinking agent.
(7) The heat-resistant gas barrier film according to (6), wherein the crosslinking agent is an isocyanate compound, pyromellitic anhydride, an oxazoline group-containing resin, or a polycarbodiimide resin.
(8) The heat-resistant gas barrier film as described in (6) or (7) above, wherein the weight ratio of the modified lignin and the crosslinking agent is in the range of 90 parts by weight to 10 parts by weight to 50 parts by weight to 50 parts by weight.
(9) The heat resistant gas barrier film according to any one of the above (1) to (8), which has heat resistance capable of maintaining a form at 200 ° C. for 2 hours.
(10) The heat resistant gas barrier film according to any one of the above (1) to (9), which has a gas barrier property of less than ² g / m ² / day as a water vapor barrier property.
(11) The heat-resistant gas barrier film according to any one of (1) to (10), wherein the film thickness is 3 to 100 μm.
(12) A modified lignin modified with polyethylene glycol and a clay mineral are mixed with a solvent as a dispersion medium to obtain a uniform dispersion, and this dispersion is applied to a support, and then the solvent is evaporated. A method for producing a heat-resistant gas barrier film, characterized in that a heat-resistant gas barrier film is obtained by heating to obtain a film-like solid content and heating.
(13) The method for producing a heat-resistant gas barrier film according to the above (12), wherein the clay mineral is lithium, proton or ammonium ion exchange bentonite.
(14) The method for producing a heat-resistant gas barrier film according to (12), wherein the modified lignin is a modified lignin modified with polyethylene glycol having a carboxyl group added.
(15) The method for producing a heat-resistant gas barrier film according to any one of (12) to (14), wherein the dispersion further contains a crosslinking agent.
(16) The method for producing a heat-resistant gas barrier film according to any one of the above (12) to (15), wherein the heating of the film-form solid is performed in the range of 150 to 800 ° C.

  According to the present invention, it is possible to provide a flexible film material having heat resistance of 200 ° C. or higher, thermal dimensional stability, high gas shielding properties, and electrical insulation. For example, the film material of the present invention is not only used as a flexible substrate for an electronic device, but also has a special effect that it can be used for incombustibility of packaging materials and wood.

  The heat-resistant gas barrier film of the present invention is a material having a high moisture permeability, the main component of which is a clay mineral, preferably a clay mineral and a modified lignin treated with water resistance, or a clay mineral and a modified lignin, and a crosslinking agent. The weight ratio of clay to the total solid is 60% or more; mechanical strength that can be used as a self-supporting film and sufficient smoothness.

  In the present invention, a clay mineral, modified lignin, and if necessary, a small amount of a crosslinking agent are mixed in a solvent to obtain a uniform dispersion containing no lumps. It is applied to the substrate, and the solvent as a dispersion medium is removed by drying and heating to form a film-like solid content. If necessary, it is peeled off from the support by drying, heating and cooling, and then heated. To do. As a result, a modified lignin-clay film in which clay crystals are oriented and excellent in flexibility, moisture permeability, and heat resistance is obtained.

  That is, the heat-resistant gas barrier film of the present invention comprises a modified lignin modified with polyethylene glycol and a clay mineral.

  The clay mineral may be natural or synthetic, preferably, for example, bentonite, mica, vermiculite, montmorillonite, beidellite, saponite, hectorite, stevensite, magadiite, ilarite, kanemite, illite, sericite. More than one species, more preferably, any of natural or synthetic products thereof or a mixture thereof is exemplified.

  These clay minerals are more suitably used by exchanging the interlayer ions with lithium ions, protons or ammonium ions.

  Furthermore, the clay mineral obtained by lithiating the interlayer ions of the clay mineral is heat-treated to move the lithium between the layers into the clay octahedron layer, thereby reducing water content by reducing the ionic components between the layers. Is preferred. As the clay mineral to be used, bentonite, montmorillonite, beidellite and stevensite are preferable. This improvement in water resistance is noticeable when the lithium ion content of the ionic substance between layers is 50% or more. The temperature condition is usually preferably 200 ° C. or higher, more preferably 300 ° C. or higher, and most preferably 350 ° C. or higher. Exceeding 800 ° C is not preferable because clay deteriorates. The heat treatment time is 20 minutes or more and 24 hours or less. When the temperature is low, the treatment tends to be required for a longer time.

  Regarding the heat treatment, the film-like solid separated from the support may be heat-treated, but it is more preferable to heat-treat the lithiated clay mineral raw material before preparing the membrane. . The temperature conditions may be the above conditions, but 400 ° C. and 2 hours are particularly preferably used.

  In place of the lithium exchange bentonite, proton or ammonium ion exchange bentonite can be used. In addition, talc may be added. Addition of talc improves heat dissipation and electrical insulation.

  Moreover, the clay mineral after heat processing (henceforth water-resistant clay) is used more preferably by setting it as the dispersion liquid of a solvent. In this case, after mixing the clay mineral and the solvent, it is preferable to further disperse with a stirrer or the like. The concentration of solids in the resulting clay mineral dispersion is 5 to 40 weight percent, preferably 10 to 20 weight percent. If the clay mineral concentration is too thin, there is a problem that it takes too long to dry. Moreover, when the density | concentration of a clay mineral is too deep, since a clay mineral does not disperse | distribute favorably, there exists a problem that a lump is easy to generate | occur | produce and a uniform film | membrane cannot be formed. In addition, when the concentration of the clay mineral is too high, there is a problem that cracks due to shrinkage, surface roughness, film thickness non-uniformity, etc. occur during drying.

  As the solvent, water and an organic solvent, a mixed solution of ammonia or a mixed solution of water and an amine compound are preferable, and acetonitrile and dimethylformamide are preferably used as the organic solvent used in the former. As the amine compound used in the latter, triethanolamine is preferably used. The stirrer is not particularly limited as long as it can disperse as vigorously as possible, but a method using a stirrer equipped with a stirring blade, a shaker stirrer, a homogenizer or the like is preferable.

  As the modified lignin used in the present invention, one in which a polyethylene glycol chain is bonded to the lignin skeleton is used. The methods for linking polyethylene glycol chains to lignin include derivatization methods using polyethylene glycol having an epoxy group, methods of dissolving polyethylene glycol in black liquor containing lignin and processing, acid addition solvents using polyethylene glycol as a medium Examples of the decomposition method include, but in the present invention, modified lignin obtained by an acid solvolysis method is preferably used. Here, the molecular weight of polyethylene glycol used in the reaction is preferably 200 to 600. Plant biomass used as a raw material for producing modified lignin is not particularly limited, but coniferous materials such as cedar and cypress, hardwood materials such as hippopotamus and mizunara, or herbaceous biomass such as rice straw, bagasse and bamboo Is used. Acid solvolysis is preferably performed by adding about 5 times by weight of polyethylene glycol and 0.1 to 0.9% sulfuric acid to polyethylene glycol and about 60 to 90 minutes at about 140 ° C. Performed with warming. The reaction product is preferably diluted with a 0.1 to 0.2 M thin caustic soda solution, then insoluble pulp components are removed by filtration, and the filtrate is acidified with sulfuric acid or the like to form a precipitate. A substance obtained by removing the precipitate by filtration or centrifugation is used as the modified lignin.

  In addition, a modified lignin having a polar group added as the modified lignin is also preferably used. As the polar group, a carboxyl group, an amino group, or a hydroxyl group is preferably used, and a carboxyl group is more preferably used. As the modified lignin, modified lignin modified with polyethylene glycol is preferably used.

  Moreover, as a crosslinking agent used by this invention, an isocyanate compound and pyromellitic acid anhydride are used. In addition, commercially available resin-based cross-linking agents are used. For example, diisocyanic acid-4,4′-diphenylmethane, oxazoline group-containing resin “Epocross” (registered trademark), and a cross-linking agent for an aqueous resin that is a kind of polycarbodiimide resin “ Carbodilite "(registered trademark) or the like is preferably used. The cross-linking agent is used as necessary, but the weight ratio of the cross-linking agent to the total solid when used is less than 20 weight percent, preferably 3 to 15 weight percent. By using a cross-linking agent, high moisture permeability can be maintained for a longer period.

  In addition, in order to maintain the strength of the heat-resistant gas barrier film of the present invention, a heat-resistant resin may be added. Examples of the heat resistant resin include polyimide, polyetheretherketone, polyphenylene sulfide and the like.

  The heat-resistant gas barrier film of the present invention is a modified lignin modified with polyethylene glycol optionally having a polar group and a clay mineral, or in addition to these, a crosslinking agent is further mixed with a solvent as a dispersion medium, After obtaining a uniform dispersion, the dispersion is applied to a support, and then the solvent is evaporated and removed to obtain a film-like solid content. If necessary, the support is dried, heated, cooled, or the like. It can be obtained by peeling from the film and further heating.

  As a method of mixing clay mineral, modified lignin, and crosslinking agent, a method of adding an aqueous dispersion of clay mineral to a solution containing modified lignin and a crosslinking agent, or a dispersion of water-resistant clay is modified lignin and a crosslinking agent. The method etc. which are added to the solution containing are illustrated.

  The weight ratio of modified lignin and clay mineral is preferably in the range of 20 parts by weight to 80 parts by weight to 40 parts by weight to 60 parts by weight. Also, the weight ratio of modified lignin to crosslinking agent is preferably in the range of 90 parts by weight to 10 parts by weight to 50 parts by weight to 50 parts by weight.

  Furthermore, when adding heat resistant resin and talc, the weight ratio of modified lignin and clay mineral is maintained within the above range, while the weight ratio of talc is 10 to 30 parts by weight. Is preferably added in the range of 10 to 50 parts by weight.

  A solution containing the modified lignin and the crosslinking agent is weighed, and in addition to the clay mineral or the water-resistant clay dispersion, a mixed solution containing the clay mineral or the water-resistant clay, the modified lignin and the crosslinking agent is prepared. In this case, as a solvent for mixing the modified lignin and the crosslinking agent, an organic solvent miscible with the solvent in which the clay mineral is dispersed can be used. For example, N-methyl-2-pyrrolidone, acetonitrile, dimethylformamide, Examples include dimethylacetamide and dioxane. Further, a mixed solvent of water and an amine compound can be used as a solvent for mixing the modified lignin and the crosslinking agent. The concentration of the amine compound is from 0.1 mol / L to 0.0001 mol / L, preferably from 0.01 to 0.001 mol / L, more preferably from 0.006 to 0.002 mol / L. A triethanolamine is illustrated as an amine compound. When these solvents are used, the clay mineral, the modified lignin, and the crosslinking agent are mixed without separation. The weight ratio with respect to the total solid in the mixed solution is less than 30%, preferably 3% to 20%.

  Furthermore, it is preferable to forcibly stir the mixed liquid composed of the clay mineral, the modified lignin and the additive to produce a uniform dispersion. The method for obtaining a uniform dispersion is not particularly limited as long as it can stir as vigorously as possible, but there is a method using a stirrer equipped with a stirring blade, a shaking stirrer, a homogenizer, etc. In order to eliminate small lumps, a method using a homogenizer at the final stage of dispersion is preferred. When lumps remain in the dispersion, it can be made a uniform dispersion by filtering the dispersion with a filter. Next, the dispersion is degassed as necessary. Examples of the deaeration process include evacuation, heating, and centrifugation, but a method including evacuation is more preferable. The steps of dispersing, filtering and defoaming may be repeated once or a plurality of times.

  Next, a dispersion liquid is apply | coated to the support surface by fixed thickness. Next, the solvent that is the dispersion medium is slowly evaporated, and the remainder is formed into a film. As the support, fluororesin, polyethylene terephthalate resin, glass and the like are preferably used. The film-like solid thus formed is preferably dried by, for example, any one of vacuum drying, freeze vacuum drying and heat evaporation, or a combination of these methods.

  Furthermore, the obtained membranous solid is heated. In this case, the temperature condition is usually preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and most preferably 250 ° C. or higher. Exceeding 800 ° C is not preferable because clay deteriorates. The heat treatment time is 20 minutes or more and 24 hours or less. When the temperature is low, the treatment tends to be required for a longer time.

  Regarding the thickness of the film of the present invention, a film having an arbitrary thickness can be obtained by increasing or decreasing the solid weight used in the dispersion. Regarding the thickness, there is a problem that the flexibility is reduced by increasing the thickness of the film, and since it becomes difficult to highly orient the water-resistant clay particles as described later, the thickness should be 0.2 mm or less. Is desirable.

  In the present invention, the highly oriented lamination of water-resistant clay particles means that unit structures of water-resistant clay particles (thickness of about 1 nanometer to 1.5 nanometers) are stacked so that the orientation of the layer faces is the same. It means to have a high periodicity in the direction perpendicular to. In order to obtain such an orientation of water-resistant clay particles, a thin and uniform dispersion containing water-resistant clay particles, modified lignin and a crosslinking agent is applied to the support, and the liquid as the dispersion medium is slowly evaporated. It is important that the water-resistant clay particles are molded into a densely laminated film.

The obtained film has a thickness of 3 to 100 μm, preferably 10 to 30 μm, moisture permeability is preferably less than 2 g / m ² / day, and the area is increased to 100 × 40 cm or more. It has high heat resistance and surface flatness is 1 μm or less. That is, the heat-resistant gas barrier film of the present invention has heat resistance capable of maintaining its form when heated at 200 ° C. for 2 hours, and has thermal dimensional stability with a linear expansion coefficient of less than 20 ppm / K from room temperature to 300 ° C. It has an electrical insulating property of 1 × 10 ¹⁴ Ω · cm or more in volume resistivity, 1 × 10 ¹⁵ Ω or more in surface resistivity, and a gas barrier property of moisture permeability of less than ² g / m ² / day as a water vapor barrier property. Can be maintained for a long time.

  As a method for measuring the linear expansion coefficient, a method of measuring with a thermomechanical analyzer is known. Data obtained by the thermomechanical analyzer is a dimensional change amount of the sample, and a compression method, a needle insertion method, a tension method, or the like is used, but any method may be used. Moreover, as a method for measuring volume resistivity or surface resistivity, resistivity measurement using a four-probe method or a four-terminal method is known, but any method may be used.

As a method for measuring moisture permeability, a moisture sensor method (Lyssy method), a cup method (JIS Z0208-1976), and an infrared sensor method (mocon method) are known. Among these methods, the cup method is a method in which a moisture permeable agent / calcium chloride (anhydrous) is enclosed in a moisture permeable cup, and weighing operation is repeated at regular intervals, and the increase in the mass of the cup is evaluated as the amount of permeated water vapor. It has the advantage of being able to measure moisture permeability around 1 g / m ² / day with a simple operation. In addition, methods for measuring dry gas barrier properties include the pressure method (JIS K7126-1, JIS Z1707), the differential pressure method, the oxygen electrolysis sensor method (JIS K7126-2 appendix A), the gas chromatographic method. (JIS K7126-2 Annex B), atmospheric pressure ionization mass spectrometer API-MS method, and differential pressure mass spectrometry. Differential pressure mass spectrometry can measure the barrier properties of various gases including hydrogen and helium, and the measurement lower limit is as low as 10 ^-3 cc / m ² / day atm, which is advantageous for high barrier measurements. It has the advantage of being able to calibrate in a way that ensures traceability.

  The heat-resistant gas barrier film, which is a lignin-clay film of the present invention, can be used as a self-supporting film in which the lamination of clay particles is highly oriented and separated from the support, has excellent flexibility, and does not have pinholes. It is possible to maintain gas / liquid barrier properties. The heat-resistant gas barrier film of the present invention can be easily cut into an arbitrary size and shape such as a circle, a square, and a rectangle with, for example, scissors and a cutter.

  Moreover, since the heat-resistant gas barrier film of the present invention is mainly composed of an electrically insulating clay mineral, it can be widely used as an electrically insulating film.

  Therefore, the heat-resistant gas barrier film of the present invention is excellent in flexibility under a high temperature condition of 200 ° C., preferably 300 ° C. or more, excellent in thermal dimensional stability from room temperature to 300 ° C., and has a water vapor barrier property. As an excellent self-supporting film, it can be used widely, and can be used as a flexible packaging material, sealing material, insulating material, etc. that are chemically stable and can maintain water resistance.

  Furthermore, the heat-resistant gas barrier film of the present invention includes, for example, a substrate film for LCD (liquid crystal display), a substrate film for organic EL, a substrate film for electronic paper, a sealing film for electronic devices, a film for PDP (plasma display), and a LED. Films, optical communication members, various functional film substrate films, IC tag films, other flexible films for electronic devices, fuel cell sealing films, solar cell films, food packaging films, beverage packaging films, pharmaceuticals It can be used as a packaging film, a daily necessities packaging film, an industrial product packaging film, and other various product packaging films.

  Since the heat-resistant gas barrier film of the present invention is excellent in flexibility and workability, it is considered possible to apply a roll-to-roll process.

  The heat-resistant gas barrier film can be used as a multilayer film by being attached to another member. That is, it is possible to improve gas barrier properties, water vapor barrier properties, and mechanical strength by multilayering a lignin-clay composite film with a film made of another material. As an example of such multilayering, for example, a film obtained by laminating a polyethylene film, a polyethylene terephthalate film, a fluororesin film or the like as a lignin-clay film and a plastic film with an adhesive is exemplified. Examples of the multilayer film include those obtained by multilayering the lignin-clay film of the present invention with metal foil, plastic film, paper and the like. Examples of the plastic film include polyethylene, polypropylene, polyethylene terephthalate, polyamide, fluororesin, acrylic resin, and polyimide. Examples of the material to be surface-coated include metals, metal oxides, ceramics, plastics, plastic foam materials, wood, gypsum board, and rubber. The surface coating of the lignin-clay film of the present invention can improve corrosion resistance, weather resistance, water vapor barrier properties, water resistance, heat resistance, chemical resistance, flame resistance, and the like.

Next, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
Example 1
As the modified lignin, one obtained by an acid hydrolysis method using a polyethylene glycol having a molecular weight of 200 as a solvent was used.

  Lithium exchange type purified bentonite (“Kunipia M”: Kunimine Kogyo Co., Ltd.) was heated at 400 ° C. for 2 hours. Then, it was dispersed in an aqueous solution of acetonitrile and ammonia. At this time, the dispersion concentration was 20%. Further, the dispersion was mixed for 5 hours with a universal mixer to obtain a redispersion liquid of “Kunipia M”.

  Distilled water (40 g) was added to the re-dispersed liquid (40 g) of “Kunipia M” and mixed with a rotating and rotating mixer. At this time, the mixing conditions were 2000 rpm and 20 minutes in the mixing mode of the apparatus. The resulting dispersion was allowed to stand overnight. After allowing to stand, the mixture was further mixed using a rotation / revolution mixer. The mixing conditions at this time were 2000 rpm and 10 minutes in the mixing mode. After mixing, N-methyl-2-pyrrolidone (108 g) was added and mixed with a homogenizer. The mixing condition at this time was 6000 rpm. After mixing, 20% NMP dispersion (10 g) of modified lignin was added and mixed with a homogenizer. The mixing condition at this time was 4000 rpm. After mixing, the mixture was cooled to 20 ° C. or lower with ice water, and further mixed with a rotation and revolution mixer. The mixing conditions at this time were 2000 rpm for 5 minutes. The obtained dispersion was passed through a sieve having an opening of 53 μm and mixed with a rotating and rotating mixer. At this time, the mixing conditions were 2000 rpm and 2 minutes in the mixing mode. Then, it further mixed with the rotation revolution mixer. The mixing conditions at this time were 2200 rpm for 10 minutes in the defoaming mode. The mixture was allowed to stand for 15 minutes, and further mixed with a rotation and revolution mixer. At this time, the mixing condition was 2200 rpm for 10 minutes in the defoaming mode. The finally obtained dispersion was placed on a PET (polyethylene terephthalate) sheet and stretched using a casting knife. At this time, the clearance of the casting knife was 0.7 mm. The stretched dispersion was dried at room temperature. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 300 ° C. for 2 hours. By this heat treatment, a modified lignin clay composite film having a film thickness of about 20 μm was obtained. The ratio of modified lignin to Kunipia M in the composite membrane was modified lignin: “Kunipia M” = 20 parts by weight: 80 parts by weight.

The obtained film retained the form before heating, and was a film having flexibility and handling properties. Further, the water vapor permeability of the modified lignin clay composite membrane was measured by the cup method. The permeability at a measurement time of 24 hours was 0.88 g / m ² / day. When the measurement was further performed after 48 hours, 71 hours, 168 hours, and 408 hours, the permeability was 1.1, 1.2, 1.6, and 3.3 g / m ² / day.

  The obtained film was subjected to thermogravimetric analysis. As a result, the weight loss by heating to 200 ° C. was 1.4 parts by weight, and the weight loss from 200 ° C. to 300 ° C. was 0.2 parts by weight. The decrease to 200 ° C was attributed to the desorption of adhering water. There was little weight loss in the range from 200 ° C to 300 ° C, and weight loss due to decomposition of membrane components was not observed.

In addition, the permeability of hydrogen and helium was evaluated by differential pressure mass spectrometry of the modified lignin clay composite membrane. After the membrane was placed in the sample chamber, it was evacuated and heated and degassed at 80 ° C. for 5 hours or more. Thereafter, the temperature of the modified lignin clay composite film was kept constant at 40 ° C., the detection side was evacuated by a turbo molecular pump to 10 ⁻⁶ Pa or less, and the exposure gas was filled with 0.1 atm of the exposure side. From the exposed side to the detecting side, the permeated test gas was measured with a quadrupole mass spectrometer. The gas permeability was quantified by calibrating the mass spectrometer “in situ” using a calibrated quantitative gas introduction element. The hydrogen and helium permeability of the modified lignin clay composite membrane measured by differential pressure mass spectrometry was 0.69 cc / m ² / day and 0.91 cc / m ² / day.

In addition, the average roughness obtained by the atomic force microscope was 280 nm and had sufficient smoothness. Moreover, the linear expansion coefficient obtained by the thermomechanical analyzer was 7 ppm / K in the range from room temperature to 300 ° C.
Comparative Example 1
A commercially available lignin (Tokyo Chemical Industry Co., Ltd., lignin (dealkaline)) was used to obtain a lignin clay composite film having a thickness of about 20 μm under the same conditions as in Example 1. The water vapor permeability of the obtained membrane was 1.1 g / m ² / day at a measurement time of 24 hours. When the measurement was further performed after 48 hours, 168 hours, and 214 hours, the permeability was 1.6, 23, and 36 g / m ² / day. The water vapor permeability of the commercially available lignin clay composite membrane was inferior to that of the modified lignin clay composite membrane, and the time degradation was significant.

Further, the permeability of hydrogen and helium measured by differential pressure mass spectrometry was 0.87 cc / m ² / day and 0.94 cc / m ² / day. The permeability of hydrogen and helium was inferior to the modified lignin clay composite membrane.
Example 2
Under the same conditions as in Example 1, clay composite membranes were prepared in which the ratio of modified lignin to “Kunipia M” was 30 parts by weight: 70 parts by weight and 40 parts by weight: 60 parts by weight, respectively. The film thickness was about 30 μm. When the water vapor permeability of the obtained membrane was measured, the moisture permeability after 30 hours by weight, 70 parts by weight of the clay composite membrane at 25 hours, 1027 hours, and 1862 hours was 0.99, 1.1, and 2.0 g / m ² / day. there were. The moisture permeability of the clay composite film of 40 parts by weight: 60 parts by weight was 1.7, 2.5, and 3.7 g / m ² / day after 309 hours, 1029 hours, and 1768 hours.
Example 3
A dispersion similar to that in Example 1 was prepared, stretched on a PET sheet under the same conditions, and dried at room temperature. After separating the film from the PET sheet, it was heated in an electric furnace at 230 ° C. for 10 hours. By this heat treatment, a modified lignin clay composite film having a film thickness of about 20 μm was obtained.

The water vapor permeability (JIS Z0208-1976) measured by the cup method of the modified lignin clay composite membrane was 1.8 g / m ² / day at a measurement time of 24 hours.
Example 4
As the modified lignin, the same one obtained by the acid hydrolysis method using polyethylene glycol having a molecular weight of 200 as a solvent was used.

  Lithium-exchanged purified bentonite (“Kunipia M”) was heated at 400 ° C. for 2 hours. Then, it was dispersed in an aqueous solution of acetonitrile and ammonia. At this time, the dispersion concentration was 20%. Further, the dispersion was mixed for 5 hours with a universal mixer to obtain a redispersion liquid of “Kunipia M”.

  A 20% acetonitrile aqueous solution (61 g) was added to the re-dispersed liquid of “Kunipia M” (35 g), and the mixture was mixed by a rotation and revolution mixer. After mixing, 15 g of 20% modified lignin dispersion (3.0 g of lignin, 7.2 g of acetonitrile, 4.8 g of water) was added, and the mixture was mixed using a rotation and revolution mixer. After mixing, the mixture was cooled to 20 ° C. or lower with ice water, and further mixed with a rotation and revolution mixer. The finally obtained dispersion was placed on a PET sheet and stretched using a casting knife. At this time, the clearance of the casting knife was 0.4 mm. The stretched dispersion was dried at room temperature. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. By this heat treatment, a modified lignin clay composite film having a film thickness of about 20 μm was obtained. The ratio of modified lignin to Kunipia M in the composite membrane was modified lignin: Kunipia M = 30 parts by weight: 70 parts by weight.

The obtained film retained the form before heating, and was a film having flexibility and handling properties. Further, the water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 22 hours was 1.7 g / m ² / day. When the measurement was further performed after 94 hours, 500 hours, 1027 hours, and 1842 hours, the permeability was 2.4, 4.0, 4.4, and 5.6 g / m ² / day.
Example 5
Under the same conditions as in Example 4, clay composite membranes were prepared in which the ratio of modified lignin and “Kunipia M” was 25 parts by weight: 75 parts by weight, 40 parts by weight: 60 parts by weight, and 50 parts by weight: 50 parts by weight, respectively. did. The film thickness was about 20 μm. When the water vapor permeability of the obtained membrane was measured, the moisture permeability after 25 hours by weight: 75 parts by weight of the clay composite membrane was 23, 497 hours, 1002 hours, and 2010 hours was 3.0, 5.2, 5.8, 6.7 g / m ² / day. The moisture permeability after 40 parts by weight: 60 parts by weight of the clay composite membrane after 21 hours, 1005 hours, 1961 hours is 1.5, 1.6, 2.7 g / m ² / day, and 50 parts by weight: 50 parts by weight. The moisture permeability of the clay composite film after 21 hours, 496 hours, 1000 hours, and 1505 hours was 2.1, 3.3, 3.6, and 3.8 g / m ² / day.
Example 6
Lithium-exchanged purified bentonite (“Kunipia M”) was heated at 400 ° C. for 2 hours. Then, it was dispersed in an aqueous solution of acetonitrile and ammonia. At this time, the dispersion concentration was 20%. Further, the dispersion was mixed for 5 hours with a universal mixer to obtain a redispersion liquid of “Kunipia M”.

  A 20% acetonitrile aqueous solution (63.4 g) was added to the re-dispersed liquid of “Kunipia M” (28 g), and the mixture was mixed using a rotation and revolution mixer. After mixing, 12 g of a 20% modified lignin dispersion (2.4 g of lignin, 5.76 g of acetonitrile, 3.84 g of water) was added, and the mixture was mixed using a rotation and revolution mixer. After mixing, 2.4 g of an oxazoline group-containing resin “Epocross” (registered trademark) WS-700 (Nippon Shokubai Co., Ltd., hereinafter referred to as “Epocross”) was added as a cross-linking agent, and the mixture was mixed in a revolving mixer. After mixing, the mixture was cooled to 20 ° C. or lower with ice water, and further mixed with a rotation and revolution mixer. The finally obtained dispersion was placed on a PET sheet and stretched using a casting knife. At this time, the clearance of the casting knife was 0.4 mm. The stretched dispersion was dried at room temperature. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. By this heat treatment, a modified lignin clay composite film having a film thickness of about 20 μm was obtained. The ratio of the modified lignin, “Epocross” and “Kunipia M” in the composite membrane was modified lignin: “Epocross”: “Kunipia M” = 28 parts by weight: 7 parts by weight: 65 parts by weight.

The obtained film retained the form before heating, and was a film having flexibility and handling properties. Further, the water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 21 hours was 1.5 g / m ² / day. When the measurement was further performed after 497 hours, 1001 hours, and 2010 hours, the permeability was 3.3, 3.6, and 4.9 g / m ² / day.
Example 7
Under the same conditions as in Example 6, the ratio of modified lignin, “Epocross” and “Kunipia M”, the ratio of modified lignin: “Epocross”: “Kunipia M” = 26 parts by weight: 13 parts by weight: 61 parts by weight It was made with. The water vapor permeability of the obtained film was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 21 hours was 1.1 g / m ² / day. When the measurement was further performed after 497 hours, 1001 hours, and 2010 hours, the transmittances were 1.84, 1.94, and 2.52 g / m ² / day.

Example 8
About the film | membrane obtained in Example 6 and Example 7, after isolate | separating a film | membrane from a PET sheet | seat, the film | membrane heated for 48 hours at 200 degreeC with the electric furnace was produced. The water vapor permeability of the obtained film was measured by the cup method (JIS Z0208-1976). Modified lignin: “Epocross”: “Kunipia M” = 26 parts by weight: 13 parts by weight: 61 parts by weight The permeability of the clay composite membrane was measured after 20 hours, 519 hours, and 1839 hours. The permeability was 2.5, 5.1, 6.1 g / m ² / day. Moreover, when the permeability of the clay composite membrane of 28 parts by weight: 7 parts by weight: 65 parts by weight was measured after 21 hours, 496 hours, and 1576 hours, the permeability was 2.7, 5.6, 7.4 g / m ² / day.

Example 9
The same modified lignin and “Kunipia M” dispersion as in Example 4 were used. A 20% acetonitrile aqueous solution (54.7 g) was added to the re-dispersed liquid of “Kunipia M” (28 g), and the mixture was mixed by a rotation and revolution mixer. After mixing, 10.8 g of a 20% modified lignin dispersion (2.16 g of lignin, 5.18 g of acetonitrile, 3.46 g of water) was added, and the mixture was mixed using a rotation and revolution mixer. After mixing, 0.6 g of a polycarbodiimide resin “Carbodilite” (registered trademark) V-02 (Nisshinbo Chemical Co., Ltd., hereinafter referred to as “Carbodilite”) as a cross-linking agent was mixed in a revolving mixer. After mixing, the mixture was cooled to 20 ° C. or lower with ice water, and further mixed with a rotation and revolution mixer. The finally obtained dispersion was placed on a PET sheet and stretched using a casting knife. At this time, the clearance of the casting knife was 0.4 mm. The stretched dispersion was dried at room temperature. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. By this heat treatment, a modified lignin clay composite film having a film thickness of about 20 μm was obtained. The ratio of the modified lignin, “carbodilite” and “Kunipia M” in the composite membrane was modified lignin: “carbodilite”: “Kunipia M” = 27 parts by weight: 3 parts by weight: 70 parts by weight.

The obtained film retained the form before heating, and was a film having flexibility and handling properties. Further, the water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 21 hours was 1.8 g / m ² / day. When the measurement was further performed after 1024 hours and after 2129 hours, the transmittances were 1.7 and 2.6 g / m ² / day.
Example 10
Under the same conditions as in Example 6, the ratio of modified lignin, “Carbodilite” and “Kunipia M”, the ratio of modified lignin: “Carbodilite”: “Kunipia M” = 24 parts by weight: 6 parts by weight: 70 parts by weight It was made with. The water vapor permeability of the obtained film was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 21 hours was 1.7 g / m ² / day. When the measurement was further performed after 1024 hours and after 2129 hours, the permeability was 1.7 and 2.5 g / m ² / day.

Example 11
About the film | membrane obtained in Example 9 and Example 10, after isolate | separating a film | membrane from a PET sheet | seat, the film | membrane heated for 48 hours at 200 degreeC with the electric furnace was produced. The water vapor permeability of the obtained film was measured by the cup method (JIS Z0208-1976). Modified lignin: “Carbodilite”: “Kunipia M” = 27 parts by weight: 3 parts by weight: 70 parts by weight The permeability of the clay composite membrane was measured after 28 hours, 478 hours, and 1175 hours. The permeability was 3.7, 9.1, 12 g / m ² / day. Further, the permeability of 24 parts by weight: 6 parts by weight: 70 parts by weight of the clay composite film was measured after 28 hours, 478 hours, and 1175 hours. The permeability was 6.3, 12, 15 g / m ² / day.

Example 12
Distilled water (40 g) was added to a 20% redispersion liquid (40 g) of “Kunipia M” and mixed with a rotating and rotating mixer. The resulting dispersion was allowed to stand overnight. After allowing to stand, the mixture was further mixed using a rotation / revolution mixer. After mixing, N-methyl-2-pyrrolidone (108 g) was added and mixed with a homogenizer. After mixing, 10 g of a dispersion of modified lignin and diisocyanate-4,4′-diphenylmethane (2 g of modified lignin, 1 g of diisocyanate-4,4′-diphenylmethane, 12 g of NMP) was added and mixed with a homogenizer. After mixing, the mixture was cooled to 20 ° C. or lower with ice water, and further mixed with a rotation and revolution mixer. The obtained dispersion was passed through a sieve having an opening of 53 μm and mixed with a rotating and rotating mixer. The mixture was allowed to stand for 15 minutes, and further mixed with a rotation and revolution mixer. The finally obtained dispersion was placed on a PET sheet and stretched using a casting knife. At this time, the clearance of the casting knife was 0.7 mm. The stretched dispersion was dried at room temperature. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 300 ° C. for 2 hours. By this heat treatment, a modified lignin clay composite film having a film thickness of about 30 μm was obtained. The ratio of the modified lignin and “Kunipia M” in the composite film was modified lignin: diisocyanate-4,4′-diphenylmethane: “Kunipia M” = 18 parts by weight: 9 parts by weight: 73 parts by weight.

The obtained film retained the form before heating, and was a film having flexibility and handling properties. Further, the water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 24 hours was 2.8 g / m ² / day. When the measurement was further measured after 2015 hours, their permeability was 2.8 g / m ² / day.
Example 13
Na-type purified bentonite (“Kunipia-F”) (100 g) was added to a 0.5 M aqueous ammonium acetate solution (1700 g), and the mixture was stirred for 1 hour to carry out an ion exchange reaction. After stirring, the reaction solution was filtered. The obtained filter cake was washed with 60% IPA-40% water mixed solution (1.5 kg) to obtain an ammonium type bentonite cake. Further, distilled water was added so that the solid content concentration was 20% and kneaded to obtain an ammonium-type bentonite dispersion.

  Distilled water (175 g) was added to a dispersion (60 g) of ammonium ion-exchanged bentonite and mixed with a homogenizer. After mixing, 15 g of 20% modified lignin dispersion (prepared by mixing 3 g of lignin, 4.48 g of triethanolamine, and 7.52 g of water, adjusting the concentration of triethanolamine to 0.004 mol / L) In addition, they were mixed with a homogenizer. After mixing, the mixture was cooled with ice water until the liquid temperature became 20 ° C. or lower, and mixed with a rotation and revolution mixer. Thereafter, the dispersion was passed through a sieve having an opening of 53 μm, and further mixed by a rotation and revolution mixer. The finally obtained dispersion was placed on a PET sheet and stretched using a casting knife. The stretched dispersion was dried at room temperature. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 200 ° C. for 24 hours. By this heat treatment, a modified lignin clay composite film having a film thickness of about 26 μm was obtained. The ratio of modified lignin and ammonium exchanged bentonite in the composite membrane was modified lignin: ammonium exchanged bentonite = 20 parts by weight: 80 parts by weight.

The obtained film retained the form before heating, and was a film having flexibility and handling properties. Further, the water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The transmittance at a measurement time of 64 hours was 0.35 g / m ² / day. When the measurement was further measured after 1250 hours, their permeability was 0.43 g / m ² / day.

Further, the surface resistivity and deposition resistivity of the obtained film were 2.23 × 10 ¹⁵ Ω and 4.76 × 10 ¹⁴ Ωcm, respectively.
Example 14
A dispersion was prepared under the same conditions as in Example 13. The finally obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. The ratio in the composite membrane was modified lignin: ammonium exchange type bentonite = 30 parts by weight: 70 parts by weight. By this heat treatment, a modified lignin clay composite film having a film thickness of about 32 μm was obtained. The ratio in the composite membrane was modified lignin: ammonium exchange type bentonite = 30 parts by weight: 70 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 21 hours was 0.28 g / m ² / day. Further, when measured after 2345 hours, the transmittance was 0.55 g / m ² / day.

Further, the surface resistivity and the deposition resistivity of the obtained film were 4.05 × 10 ¹⁵ Ω and 3.13 × 10 ¹⁴ Ωcm, respectively.
Example 15
A dispersion was prepared under the same conditions as in Example 13. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 200 ° C. for 48 hours. By this heat treatment, a modified lignin clay composite film having a film thickness of about 32 μm was obtained. The ratio in the composite membrane was modified lignin: ammonium exchange type bentonite = 30 parts by weight: 70 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 186 hours was 0.27 g / m ² / day. Further, when measured after 5274 hours, the permeability was 0.27 g / m ² / day.

Further, the surface resistivity and the deposition resistivity of the obtained film were 1.74 × 10 ¹⁵ Ω and 4.72 × 10 ¹⁴ Ωcm, respectively.
Example 16
A dispersion was prepared under the same conditions as in Example 13. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 200 ° C. for 24 hours. By this heat treatment, a modified lignin clay composite film having a film thickness of about 35 μm was obtained. The ratio in the composite membrane was modified lignin: ammonium exchange type bentonite = 30 parts by weight: 70 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The transmittance at a measurement time of 66 hours was 0.12 g / m ² / day. Further, when measured after 4506 hours, the permeability was 0.41 g / m ² / day.

Example 17
A dispersion was prepared under the same conditions as in Example 13. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 180 ° C. for 96 hours. By this heat treatment, a modified lignin clay composite film having a film thickness of about 31 μm was obtained. The ratio in the composite membrane was modified lignin: ammonium exchange type bentonite = 30 parts by weight: 70 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The transmittance at a measurement time of 93 hours was 0.15 g / m ² / day. Further, when measured after 928 hours, the transmittance was 0.19 g / m ² / day.

Example 18
A dispersion was prepared under the same conditions as in Example 13. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 180 ° C. for 72 hours. By this heat treatment, a modified lignin clay composite film having a film thickness of 29 μm was obtained. The ratio in the composite membrane was modified lignin: ammonium exchange type bentonite = 30 parts by weight: 70 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The transmittance at a measurement time of 47 hours was 0.30 g / m ² / day. Further, when measured after 556 hours, the permeability was 0.47 g / m ² / day.

Example 19
A dispersion was prepared under the same conditions as in Example 13. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 160 ° C. for 96 hours. By this heat treatment, a modified lignin clay composite film having a film thickness of 31 μm was obtained. The ratio in the composite membrane was modified lignin: ammonium exchange type bentonite = 30 parts by weight: 70 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The transmittance at a measurement time of 90 hours was 0.41 g / m ² / day. Further, when measured after 424 hours, the transmittance was 0.54 g / m ² / day.

Example 20
A dispersion was prepared under the same conditions as in Example 13. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 200 ° C. for 48 hours. A modified lignin clay composite film having a film thickness of 44 μm was obtained. The ratio in the composite membrane was modified lignin: ammonium exchanged bentonite = 40 parts by weight: 60 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The transmittance at a measurement time of 499 hours was 0.58 g / m ² / day. When the measurement was further measured after 2164 hours, their permeability was 0.90 g / m ² / day.

Further, the surface resistivity and volume resistivity of the obtained film were 3.64 × 10 ¹⁵ Ω and 5.99 × 10 ¹⁴ Ωcm, respectively.
Example 21
A dispersion was prepared under the same conditions as in Example 13. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 220 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 25 μm was obtained. The ratio in the composite membrane was modified lignin: ammonium exchanged bentonite = 40 parts by weight: 60 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 41 hours was 0.67 g / m ² / day. When the measurement was further measured after 2164 hours, their permeability was 0.90 g / m ² / day.

Example 22
A dispersion was prepared under the same conditions as in Example 13. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 200 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 45 μm was obtained. The ratio in the composite membrane was modified lignin: ammonium exchange type bentonite = 50 parts by weight: 50 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 41 hours was 1 g / m ² / day. When the measurement was further measured after 2164 hours, their permeability was 1 g / m ² / day.

Further, the surface resistivity and volume resistivity of the obtained film were 3.81 × 10 ¹⁵ Ω and 6.37 × 10 ¹⁴ Ωcm, respectively.
Example 23
Distilled water (140.8 g) was added to a dispersion (52.5 g) of ammonium ion-exchanged bentonite and mixed with a homogenizer. After mixing, 15 g of 20% modified lignin dispersion (prepared by mixing 3 g of lignin, 4.48 g of triethanolamine, and 7.52 g of water, adjusting the concentration of triethanolamine to 0.004 mol / L) In addition, they were mixed with a homogenizer. After mixing, 6.02 g of “Epocross” (concentration 24.9%) was added as a cross-linking agent and mixed with a homogenizer. The mixture was cooled with ice water until the liquid temperature became 20 ° C. or lower, and mixed with a rotating / revolving mixer. Thereafter, the dispersion was passed through a sieve having an opening of 53 μm, and further mixed by a rotation and revolution mixer. The finally obtained dispersion was placed on a PET sheet and stretched using a casting knife. The stretched dispersion was dried at room temperature. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 200 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 36 μm was obtained. The ratio of the modified lignin to the ammonium exchange bentonite and “epocros” in the composite membrane was modified lignin: ammonium exchange bentonite: “epochros” = 20 parts by weight: 70 parts by weight: 10 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 47 hours was 0.66 g / m ² / day. Measurements were taken after another 2922 hours, and their permeability was 0.85 g / m ² / day.

Further, the surface resistivity and volume resistivity of the obtained film were 1.77 × 10 ¹⁵ Ω and 5.34 × 10 ¹⁴ Ωcm, respectively. In addition, the linear expansion coefficient obtained by the thermomechanical analyzer was 10 ppm / K in the range from room temperature to 300 ° C., and the average roughness obtained by the atomic force microscope was 49 nm.
Example 24
50 g of modified lignin, 10.93 g of phthalic anhydride, and 8.82 g of pyridine were dissolved in 337 mL of tetrahydrofuran and stirred overnight under a nitrogen atmosphere. Then, after drying under reduced pressure with an evaporator, further vacuum drying was performed to remove tetrahydrofuran. The obtained powder was well ground in a mortar, transferred to a beaker, and dispersed in 100 mL of distilled water. Thereafter, the mixture was vigorously stirred for 1 hour, separated by filtration, and the solid content was dried under reduced pressure and vacuum to obtain carboxyl group-added modified lignin (hereinafter referred to as C-modified lignin).

A dispersion was prepared under the same conditions as in Example 13 using C-modified lignin and ammonium ion-exchanged bentonite. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 200 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 27 μm was obtained. The ratio in the composite membrane was C-modified lignin: ammonium exchanged bentonite = 30 parts by weight: 70 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 23 hours was 1.59 g / m ² / day. When the measurement was further carried out after 665 hours, their permeability was 2.63 g / m ² / day.

Further, the surface resistivity and volume resistivity of the obtained film were 1.94 × 10 ¹⁵ Ω and 5.89 × 10 ¹⁴ Ωcm, respectively.
Example 25
A dispersion was prepared under the same conditions as in Example 23 using C-modified lignin, ammonium-exchanged bentonite, and “Epocross”. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 27 μm was obtained. The ratio of C-modified lignin and ammonium exchanged bentonite, “Epocross” in the composite membrane was C-modified lignin: ammonium exchanged bentonite: “Epocross” = 20 parts by weight: 70 parts by weight: 10 parts by weight. It was. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 21 hours was 0.28 g / m ² / day. When the measurement was further measured after 2345 hours, their permeability was 0.55 g / m ² / day.

Example 26
A dispersion was prepared under the same conditions as in Example 23 using C-modified lignin, ammonium-exchanged bentonite, and “Epocross”. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 200 ° C. for 48 hours. A modified lignin clay composite film having a film thickness of 28 μm was obtained. The ratio of C-modified lignin and ammonium exchanged bentonite, “Epocross” in the composite membrane was C-modified lignin: ammonium exchanged bentonite: “Epocross” = 20 parts by weight: 70 parts by weight: 10 parts by weight. It was. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 88 hours was 1.68 g / m ² / day. When the measurement was further measured after 1431 hours, their permeability was 1.81 g / m ² / day.

Further, the surface resistivity and volume resistivity of the obtained film were 3.24 × 10 ¹⁵ Ω and 7.31 × 10 ¹⁴ Ωcm, respectively.
Example 27
A dispersion was prepared using C-modified lignin, ammonium-exchanged bentonite, and “carbodilite” under the same conditions as in Example 23. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 200 ° C. for 48 hours. A modified lignin clay composite film having a film thickness of 24 μm was obtained. The ratio of C-modified lignin to ammonium-exchanged bentonite and “carbodilite” in the composite membrane was C-modified lignin: ammonium-exchanged bentonite: “carbodilite” = 20 parts by weight: 70 parts by weight: 10 parts by weight. It was. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 24 hours was 0.71 g / m ² / day. When the measurement was further measured after 2660 hours, their permeability was 1.31 g / m ² / day.

Further, the surface resistivity and volume resistivity of the obtained film were 2.38 × 10 ¹⁵ Ω and 6.17 × 10 ¹⁴ Ωcm, respectively.
Example 28
A dispersion was prepared using C-modified lignin, ammonium-exchanged bentonite, and “carbodilite” under the same conditions as in Example 23. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 200 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 23 μm was obtained. The ratio of C-modified lignin to ammonium-exchanged bentonite and “carbodilite” in the composite membrane was C-modified lignin: ammonium-exchanged bentonite: “carbodilite” = 20 parts by weight: 70 parts by weight: 10 parts by weight. It was. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 23 hours was 0.89 g / m ² / day. The measurements were taken after another 569 hours and their permeability was 1.07 g / m ² / day.

Example 29
A dispersion was prepared under the same conditions as in Example 13 using lithium-exchanged bentonite (“Kunipia M”) and modified lignin. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 200 ° C. for 48 hours. A modified lignin clay composite film having a film thickness of 28 μm was obtained. The ratio of the modified lignin and “Kunipia M” in the composite membrane was modified lignin: “Kunipia M” = 20 parts by weight: 80 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 24 hours was 0.46 g / m ² / day. When the measurement was further measured after 2684 hours, their permeability was 1.49 g / m ² / day.

Example 30
A dispersion was prepared under the same conditions as in Example 13 using lithium-exchanged bentonite (“Kunipia M”) and modified lignin. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 200 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 25 μm was obtained. The ratio of modified lignin to Kunipia M in the composite membrane was modified lignin: Kunipia M = 20 parts by weight: 80 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 23 hours was 1.51 g / m ² / day. When the measurement was further measured after 2202 hours, their permeability was 1.78 g / m ² / day.

Example 31
A dispersion was prepared under the same conditions as in Example 13 using lithium-exchanged bentonite (“Kunipia M”) and modified lignin. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 28 μm was obtained. The ratio of modified lignin and “Kunipia M” in the composite membrane was modified lignin: “Kunipia M” = 30 parts by weight: 70 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 113 hours was 0.05 g / m ² / day. When the measurement was further measured after 5202 hours, their permeability was 0.52 g / m ² / day.

Example 32
Distilled water (199 g) was added to a 20% aqueous dispersion (45 g) of “Kunipia M” and mixed with a homogenizer. After mixing, modified lignin (6 g) was added and mixed with a homogenizer. After mixing, the mixture was cooled with ice water until the liquid temperature became 20 ° C. or lower, and mixed with a rotation and revolution mixer. Thereafter, the dispersion was passed through a sieve having an opening of 53 μm, and further mixed by a rotation and revolution mixer. The finally obtained dispersion was placed on a PET sheet and stretched using a casting knife. The stretched dispersion was dried at room temperature. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 36 hours. A modified lignin clay composite film having a film thickness of 28 μm was obtained. The ratio of modified lignin and “Kunipia M” in the composite membrane was modified lignin: “Kunipia M” = 40 parts by weight: 60 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The transmittance at a measurement time of 70 hours was 0.22 g / m ² / day. When the measurement was further measured after 3119 hours, their permeability was 2.34 g / m ² / day.

Example 33
A dispersion was prepared using “Kunipia M”, C-modified lignin, and “Epocross” under the same conditions as in Example 23. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 26 μm was obtained. The ratio of C-modified lignin and ammonium exchange bentonite, “Epocross” in the composite membrane was C-modified lignin: “Kunipia M”: “Epocross” = 20 parts by weight: 70 parts by weight: 10 parts by weight. It was. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 24 hours was 0.14 g / m ² / day. When the measurement was further measured after 5729 hours, their permeability was 0.16 g / m ² / day.

Example 34
A dispersion was prepared using “Kunipia M”, C-modified lignin, and “Epocross” under the same conditions as in Example 23. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 200 ° C. for 48 hours. A modified lignin clay composite film having a film thickness of 38 μm was obtained. The ratio in the composite film was C-modified lignin: “Kunipia M”: “Epocross” = 20 parts by weight: 70 parts by weight: 10 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 48 hours was 1.66 g / m ² / day. When the measurement was further performed after 5296 hours, their permeability was 0.64 g / m ² / day.

Example 35
A dispersion was prepared using “Kunipia M”, C-modified lignin and “carbodilite” under the same conditions as in Example 23. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 28 μm was obtained. The ratio in the composite film was C-modified lignin: “Kunipia M”: “carbodilite” = 20 parts by weight: 70 parts by weight: 10 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 71 hours was 0.51 g / m ² / day. When the measurement was further performed after 5296 hours, their permeability was 0.64 g / m ² / day.

Example 36
A dispersion was prepared under the same conditions as in Example 13 using the re-dispersion of “Kunipia M” described in Example 9 and modified lignin. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 29 μm was obtained. The ratio of the modified lignin and “Kunipia M” in the composite membrane was modified lignin: “Kunipia M” = 20 parts by weight: 80 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 91 hours was 0.18 g / m ² / day. When the measurement was further carried out after 5296 hours, their permeability was 0.57 g / m ² / day.

Example 37
A dispersion was prepared under the same conditions as in Example 13 using the re-dispersion of “Kunipia M” described in Example 9 and modified lignin. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 37 μm was obtained. The ratio of modified lignin and “Kunipia M” in the composite membrane was modified lignin: “Kunipia M” = 30 parts by weight: 70 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 24 hours was 0.67 g / m ² / day. The measurements were taken after a further 5489 hours and their permeability was 0.49 g / m ² / day.

Example 38
A dispersion was prepared under the same conditions as in Example 13 using the re-dispersion of “Kunipia M” described in Example 9 and modified lignin. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 31 μm was obtained. The ratio of modified lignin and “Kunipia M” in the composite membrane was modified lignin: “Kunipia M” = 40 parts by weight: 60 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 91 hours was 0.16 g / m ² / day. When the measurement was further measured after 5296 hours, their permeability was 0.50 g / m ² / day.

Example 39
A dispersion was prepared under the same conditions as in Example 13 using the re-dispersion of “Kunipia M” described in Example 9 and modified lignin. At that time, the triethanolamine concentration in the added 20% modified lignin dispersion was 0.0005 mol / L. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 39 μm was obtained. The ratio of modified lignin and “Kunipia M” in the composite membrane was modified lignin: “Kunipia M” = 30 parts by weight: 70 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 113 hours was 0.33 g / m ² / day. When the measurement was further measured after 2586 hours, their permeability was 0.51 g / m ² / day.

Example 40
A dispersion was prepared under the same conditions as in Example 13 using the re-dispersion of “Kunipia M” described in Example 9 and modified lignin. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 220 ° C. for 48 hours. A modified lignin clay composite film having a film thickness of 42 μm was obtained. The ratio of modified lignin and “Kunipia M” in the composite membrane was modified lignin: “Kunipia M” = 30 parts by weight: 70 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The transmittance at a measurement time of 89 hours was 0.09 g / m ² / day. When the measurement was further measured after 2609 hours, their permeability was 0.19 g / m ² / day.

Example 41
A dispersion was prepared under the same conditions as in Example 23 using the re-dispersion of “Kunipia M” described in Example 9, modified lignin, and “Epocross”. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 25 μm was obtained. The ratio in the composite membrane was modified lignin: “Kunipia M”: “Epocross” = 20 parts by weight: 70 parts by weight: 10 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 91 hours was 0.08 g / m ² / day. When the measurement was further measured after 5296 hours, their permeability was 0.45 g / m ² / day.

Example 42
A dispersion was prepared using bentonite (“Kunipia F”) and the C-modified lignin used in Example 24 under the same conditions as in Example 13. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 36 hours. A modified lignin clay composite film having a film thickness of 24 μm was obtained. The ratio in the composite film was C-modified lignin: “Kunipia F” = 20 parts by weight: 80 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 25 hours was 0.99 g / m ² / day. The measurements were taken 2302 hours later and their permeability was 1.16 g / m ² / day.

Example 43
A dispersion was prepared using bentonite (“Kunipia F”) and the C-modified lignin used in Example 24 under the same conditions as in Example 13. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 36 hours. A modified lignin clay composite film having a film thickness of 26 μm was obtained. The ratio in the composite film was C-modified lignin: “Kunipia F” = 30 parts by weight: 70 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 66 hours was 0.74 g / m ² / day. When the measurement was further measured after 4194 hours, their permeability was 0.88 g / m ² / day.

Example 44
A dispersion was prepared using “Kunipia F”, C-modified lignin, and “carbodilite” under the same conditions as in Example 24. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 36 hours. A modified lignin clay composite film having a film thickness of 30 μm was obtained. The ratio in the composite film was C-modified lignin: “Kunipia F”: “carbodilite” = 20 parts by weight: 70 parts by weight: 10 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The transmittance at a measurement time of 95 hours was 1.16 g / m ² / day. When the measurement was further measured after 2113 hours, their permeability was 1.56 g / m ² / day.

Example 45
A dispersion was prepared using “Kunipia F”, C-modified lignin, and “carbodilite” under the same conditions as in Example 24. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 36 hours. A modified lignin clay composite film having a film thickness of 23 μm was obtained. The ratio in the composite film was C-modified lignin: “Kunipia F”: “carbodilite” = 27 parts by weight: 70 parts by weight: 3 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 24 hours was 0.40 g / m ² / day. When the measurement was further measured after 2296 hours, their permeability was 0.66 g / m ² / day.

Example 46
A dispersion was prepared using “Kunipia F”, C-modified lignin, and “carbodilite” under the same conditions as in Example 24. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 24 hours. A modified lignin clay composite film having a film thickness of 26 μm was obtained. The ratio in the composite film was C-modified lignin: “Kunipia F”: “carbodilite” = 27 parts by weight: 70 parts by weight: 3 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The transmittance at a measurement time of 24 hours was 0.85 g / m ² / day. When the measurement was further measured after 3691 hours, their permeability was 1.70 g / m ² / day.

Example 47
A dispersion was prepared using “Kunipia F”, C-modified lignin, and “Epocross” under the same conditions as in Example 24. The obtained dispersion was placed on a PET sheet and stretched using a casting knife. After drying, the membrane was separated from the PET sheet and heated in an electric furnace at 250 ° C. for 30 hours. A modified lignin clay composite film having a film thickness of 24 μm was obtained. The ratio in the composite film was C-modified lignin: “Kunipia F”: “carbodilite” = 27 parts by weight: 70 parts by weight: 3 parts by weight. The water vapor permeability of the modified lignin clay composite membrane was measured by the cup method (JIS Z0208-1976). The permeability at a measurement time of 24 hours was 1.13 g / m ² / day. When the measurement was further measured 3259 hours later, their permeability was 1.83 g / m ² / day.

  According to the present invention, a flexible film material having a heat resistance of 200 ° C. or higher and a high gas shielding property can be provided. For example, the film material of the present invention is not only used as a flexible substrate for an electronic device, but also has a special effect that it can be used for incombustibility of packaging materials and wood.

Claims (16)

  A heat-resistant gas barrier film comprising a modified lignin modified with polyethylene glycol and a clay mineral.   The heat resistant gas barrier film according to claim 1, wherein the clay mineral is lithium, proton or ammonium ion exchange bentonite.   The heat-resistant gas barrier film according to claim 2, wherein the clay mineral is lithium, proton or ammonium ion exchange bentonite that has been heat-treated at a temperature of 230 ° C or higher.   The heat-resistant gas barrier film according to claim 1, wherein the modified lignin is a modified lignin modified with polyethylene glycol having a carboxyl group added thereto.   The heat-resistant gas barrier film according to any one of claims 1 to 4, wherein the weight ratio of the modified lignin and the clay mineral is in the range of 20 parts by weight to 80 parts by weight to 40 parts by weight to 60 parts by weight.   The heat-resistant gas barrier film according to any one of claims 1 to 5, wherein the modified lignin contains a crosslinking agent.   The heat-resistant gas barrier film according to claim 6, wherein the crosslinking agent is an isocyanate compound, pyromellitic anhydride, an oxazoline group-containing resin, or a polycarbodiimide resin.   The heat-resistant gas barrier film according to claim 6 or 7, wherein the weight ratio of the modified lignin and the crosslinking agent is in the range of 90 parts by weight to 10 parts by weight to 50 parts by weight to 50 parts by weight.   The heat-resistant gas barrier film according to any one of claims 1 to 8, which has heat resistance capable of maintaining a form upon heating at 200 ° C for 2 hours. The heat-resistant gas barrier film according to any one of claims 1 to 9, which has a gas barrier property of moisture permeability of less than ² g / m ² / day as a water vapor barrier property.   The film thickness of a film is 3-100 micrometers, The heat-resistant gas barrier film of any one of Claims 1-10.   The modified lignin and clay mineral modified with polyethylene glycol are mixed with a solvent as a dispersion medium to obtain a uniform dispersion, and then this dispersion is applied to a support, and then the solvent is evaporated and removed. A method for producing a heat-resistant gas barrier film, comprising obtaining a film-shaped solid and heating to obtain a heat-resistant gas barrier film.   The method for producing a heat-resistant gas barrier film according to claim 12, wherein the clay mineral is lithium, proton or ammonium ion exchange bentonite.   The method for producing a heat-resistant gas barrier film according to claim 12, wherein the modified lignin is a modified lignin modified with polyethylene glycol having a carboxyl group added thereto.   The method for producing a heat-resistant gas barrier film according to any one of claims 12 to 14, wherein the dispersion further contains a crosslinking agent.   The method for producing a heat-resistant gas barrier film according to any one of claims 12 to 15, wherein the heating of the film-form solid is performed in a range of 150 to 800 ° C.