TWI361171B - - Google Patents

Description

1361171 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a clay film and a method of manufacturing the same. Further, the present invention relates to an electronic paper, a substrate, and a gas film which are at least partially composed of a clay film. [Prior Art] 5. In many chemical industries, various productions under high temperature conditions are used. Process. For the g-tube joints and the like of the production lines, for example, a method of preventing leakage of a liquid or a gas by a gasket or welding or the like is employed. Heretofore, a gasket excellent in flexibility has been produced, for example, using an organic high molecular material or asbestos. However, in the case of using an organic polymer material, Teflon (registered trademark) is the highest in terms of heat resistance, and 'spoon is 250 C. If it is at a relatively hot temperature, metal lining must be used. pad. However, compared with the case of using an organic polymer material, the use of a metal spacer is not preferable, and there is a problem that the impact on the surface facing the (four) is strong. Moreover, asbestos-containing materials have excellent heat resistance and chemical resistance, but the problem is that asbestos is highly toxic to humans, and the industry expects to develop other materials as soon as possible instead. On the other hand, in recent years, the manufacturing technology of a flat panel display (hereinafter referred to as FPD) represented by a liquid crystal display has been progressing rapidly, and a thin display which cannot be realized by the previous Brown tube has become a reality. In the case of the current FPD, substantially all of the components are formed on the glass substrate, and there is no practical FPD using a substrate other than the glass substrate. The reason for this is as follows: the glass substrate has high heat resistance, and is suitable for forming a display φ. , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , It is possible to suppress the stress applied to the drive or the variation of the characteristics of the component to the stress of the component, so that the wiring is easy to take out the light; further, the resistance is transparent in the visible light domain, and the oxygen or water vapor from the outside enters: =, which can be used as a stop to vacuum or the like. And the bismuth material can be kept as high as necessary. :: The glazing substrate does not have softness and is easily broken... produces heavy weight = problem with deformation or difficulty in operation. Further, the glass substrate T '., and the method are used in a flexible display such as a bendable electronic cymbal which is intended to be used for the purpose of transportation. In the case of falling, the component 衮j; is easy to know for the household, because the glass substrate also has the above-mentioned defects; suitable for mobile applications. From this point of view, the industry 4 looks the same as glass', The production of the substrate, the transparency, the gas barrier, etc., can be put into practical use, and the film can be put into practical use.

= system: the electricity: the circuit board of the parts, the high density I of the parts installation, is gradually increasing. Moreover, due to the increase in the number of rotating and shaped electrical products represented by mobile phone terminals, the demand for flexibility is also increasing. Therefore, the need for a flexible circuit substrate or a copper backing layer is also increasing. As the flexible circuit board, a substrate formed of a resin such as polyethylene terephthalate, polycarbonate, or polyimide, or an epoxy glass substrate is used. However, when manufacturing a printed circuit board using a conductive ink such as a conductive material to form a circuit wiring by printing or coating, it is U7849-99] 〇 14.d (1361171 obtains a wiring having a sufficiently high conductivity, and is coated. After the conductive ink, it is generally required to be fired at a high temperature of 300 ° C or higher. However, for a flexible circuit board using a substrate formed of the resin as described above, the heat resistance of the resin is low. The coefficient of linear expansion is generally large, so that the above-mentioned high-temperature firing cannot be performed, but it needs to be performed at a relatively low temperature. However, since the sintering of the conductive ink is not performed sufficiently at a low temperature, it is not compatible with the metal foil or Compared with the wiring obtained by vacuum evaporation, there is generally a problem of poor electrical conductivity. Although the polyimide resin has high heat resistance, it is difficult to be used for RFID such as RFID (RadiQ f]requeney identification because of its high price. In the case where the cost is the most important, such as radio frequency identification, the industry expects an inexpensive flexible printed circuit board that is insulating and has high heat resistance and flame retardancy. In addition, there are a large number of clays in nature, which are minerals that are cheap, harmless to the human body, and difficult to burn. Moreover, most of the "green" colors that are recognized in natural clay are mostly due to organic matter or iron. It is produced by impurities. However, it is also possible to obtain a colorless clay which does not contain such impurities by chemical synthesis. Clay minerals can be roughly classified into crystalline minerals and amorphous minerals, and all of the crystalline fractions mean "leafy" The citrate, which has a leaf shape, is basically a layered structure. That is, in general, a mineral called a layered citrate belongs to the category of minerals defined as clay. Most clay systems It is composed of a lamellar layered inorganic compound in which the thickness of the laminated layer 1 to 3 is about 0.2 nm centering on oxygen (〇), bismuth (si), and aluminum (A1). The dimension of the tetrahedral thin layer or the octahedral thin layer to the long sleeve of about nm5 nm is about several tens of nm to 5 μm, and the aspect is relatively large. H7849-991014.doc 1361171 Hereinafter, the layered 矽 is described in further detail. Acid salt four Of thin layers or octahedral sheet. Tetrahedral sheet line is formed in the following manner, in

Four Si 配 are coordinated on the Si to form a Si〇4 tetrahedron, and the tetrahedrons share three of them and are connected into a hexagonal network. Depending on the case, Al can be formed by substituting A1 for Si. In addition to this, a tetrahedron can also be produced using iron (Fe) or the like. On the other hand, the octahedral thin layer is formed by coordinating six hydroxyl groups (〇H) or yttrium on A1, and may be formed of magnesium (Mg) or Fe instead of A1. Further, since Si in the tetrahedral thin layer is replaced by A1 or the like, or the octahedral thin layer is replaced by ruthenium or the like, the charge of the thin layer is excessive or insufficient, and the thin layer is often charged with a permanent charge. It is also possible to manually control and introduce elements other than the above in the tetrahedral or octahedral thin layer, thereby attempting to change various physical properties such as magnetic properties or optical properties. Various layered inorganic compounds are produced by such a thin layer or by laminating and laminating the thin layers. In the present invention, the early layer obtained by combining the thin layers is defined as clay crystals. For example, as a crystal composed of a clay having only a tetrahedral thin layer as an early layer, a series of minerals (for example, Magady stone) generally called a layered polyphthalic acid can be cited. On the other hand, it is known that a clay mineral called hydrotalcite is formed by having an anion such as a carbonate ion between a positively charged octahedral thin layer and an octahedral thin layer. A tetragonal thin layer and an octahedral thin layer are combined in a ratio of 1:1 to form a clay mineral of the clay layer of the early layer of (4). It is generally known as Zhongmuling Stone and Kaolinite. . Relative to this 'tetrahedral thin layer and octahedral thin household formed by 2: layer (ie, tetrahedral thin layer - Η, '. σ,, 'product octahedral 溥 layer - tetrahedral thin layer) There are 117849-991014.doc 1361171 as clay minerals in the early layer of clay, there are shale, talc, total de-staining clay, insect to stone, 11 # i 1 - mother clay minerals. In particular, it belongs to the smectite paste (for example, 'montmorillonite, saponite, montmorillonite, slippery stone, etc.), it can be said that 'in the case of the generality of inorganic cations between layers, it can be uniformly Disperse in a highly polar solvent such as water or alcohol (especially in water), and can be dispersed in a polar solvent (for example, refer to the material referred to as the layer 1 for the use of the clay as described above). — Ancient w, hi r slaves have added a small amount of scorpion in the tree month (generally, about 5 wt% of the material has been extensively studied, so that it does not..., the composite material is added to the clay for a small amount. The improvement of the strength or flame retardancy of the nanocomposite ^ ^ 疋 ', or the improvement of the gas barrier effect is less than the proportion of the clay in the nano composite, so it is essentially gas barrier or The flame retardancy is not a gentleman, (4) the big ^. For example, the gas barrier property and the second = there is a case where the transmittance of the gas becomes a fraction or more by the addition of clay, and there is almost no such thing as ', '? Increase the gas barrier property - the number of digits, and move the gas by increasing the gas as the gas passes through Or synthetic mica:; ': yellow coloring and biting caused by natural montmorillonite soil with larger crystal size: in case of natural montmorillonite scattering, it is difficult to obtain; the larger size of the mother leads to The degree of light is small, colorless, and the 'haze' in the second indicator (when the amount of turbidity is small, it is difficult, the addition of clay, and the large-scale smear of gas, other than gas barrier 117849-991014.doc 136,1171 =, for example, dimensional stability under heat resistance or temperature change, and it is difficult to sufficiently exhibit the essential characteristics of clay having high heat resistance and excellent dimensional stability. In order to improve gas barrier properties, transparency is improved to suppress light scattering. It is more important to form a nanocomposite which makes the crystal layer of the clay dense and highly aligned. Thereby, dimensional stability is also considered to be improved. Previously, for example, a dispersion of clay was known on a glass plate. By expanding, standing, and drying, the film is uniformly aligned with the particles, and the film of the χ line diffraction method is gradually adjusted by the formation of the film (see Non-Patent Document 3). - Brockett method Langmuir_B1〇dgett Meth〇d) is made of a clay film (for example, 'Refer to Non-Patent Document 4). However, when this method is used, a clay film is formed on the surface of a substrate made of a material such as glass, and is not a clay having the strength of an independent film. Further, various methods for adjusting a functional clay film, etc. have been reported. For example, a method in which a water-based dispersion of a hydrotalcite-based interlayer compound is formed into a film and dried to form a transparent clay film (refer to the patent document) 1) a method for producing a layered clay mineral film which has a combined structure of a fixed layered clay mineral by reacting a layered clay mineral with a phosphoric acid or a phosphoric acid group, and performing a heat treatment for promoting the reaction (refer to the patent document) 2) An aqueous composition for coating treatment containing a smectite-based clay mineral and a complex of a divalent or higher metal (see Patent Document 3), etc., and the above-mentioned items are representative, and there are a large number of examples. However, all of the film-like clay forms in these prior documents are formed on a support, and do not have a clay alignment film which can be used as a mechanical strength of the independent film and a high degree of alignment of the clay particles. Further, as a film using a transparent clay, there is an example in which a synthetic saponite or a synthetic 117849-99l014.doc 1361171 aqueous dispersion of montmorillonite is applied onto a film to form a phase difference film of a liquid crystal display. For the transparent film, by utilizing the large difference between the inner direction of the thin layer of the clay crystal of the synthetic f stone or the smectite smectite and the refractive index of the thickness direction of the thin layer, the transparent film can be provided with respect to the progress of the light. Phase difference. In such a transparent film, there is also a part obtained by partially peeling off the clay film formed on the support (refer to the patent document. However, in the point film obtained by the self-supporting body disclosed in Patent Document 4, It is only assumed that the amount of clay contained in the clay film which can be used as the mechanical strength of the independent film is about 47 wt% 'more than half of it is composed of additives such as polymers. Therefore, it is difficult to call it clay-based. The film may not be sufficient to suppress gas barrier properties. Further, if a thick film is formed by increasing the amount of clay, the phase difference between the in-plane direction and the thickness direction of the film becomes too large, and the phase for the liquid crystal display is lost. The suitability of the film is poor. Therefore, it is necessary to reduce the proportion of clay when making a thick film with self-standing properties. Further, it is also developed to contain transparent polyimine and hydrophobic clay, high degree and water resistance. a transparent clay film. The hydrophobic clay system allows: the exchange of inorganic ions in the t-smectite hydrophilic clay in the water to organic salt, etc., so that the dispersibility in the organic solvent is improved. The hydrophobic clay (refer to Patent Document 5). The clay film is different from the clay film disclosed in Patent Document 4, and does not dissolve even when it comes into contact with water. However, Patent Document 5 discloses that the clay is contained. When the amount is less than 2% by weight, the clay partially aggregates in the production step. As a result, the haze is increased and it is difficult to be called a transparent state (haze value is 50% or more), and the decrease in toughness is also remarkable. # ' It is the same as the previous one with the addition of clay 117849-99I014.doc • 12-1361171 nanocomposite, which is difficult to call a film that greatly improves gas barrier properties or dimensional stability by using clay as the main body. Under such circumstances, the inventors of the present invention have made various attempts at a method for producing a clay alignment film which is dense and highly aligned with a crystal layer of clay, and it can be seen that in the process, 'clay particles have been aligned and can be used as an independent The clay film having the strength of the film can be obtained by the following method. That is, there is a method of adjusting the spot soil dispersion to obtain a dispersion of the homogenate, and horizontally disposing the dispersion to make the clay particles The deposition is carried out by various solid-liquid separation methods (for example, 'centrifugal separation, enthalpy, vacuum drying, vacuum drying, or heating and evaporation) to separate the liquid as a dispersion solvent to form a film, and then self-support Body peeling (refer to Patent Document 6). It can be seen that the softness or strength of the clay film can be improved not only by clay but also by using a clay-containing liquid in which a small amount of additive is added to the clay dispersion (refer to the patent literature). 7); or a clay film can be produced in a short time by using a clay material which improves the solid ratio of the clay-containing liquid (refer to Patent Document 8), and further, by using a synthetic clay or the like by using Jiaer into the straw a clay film which is mainly composed of clay and which is not colored and which is transparent in the visible light region. Furthermore, it can be confirmed that the clay is a soil film which is densely and highly aligned with the soil of ± _. Compared with the previous proportion of clay, the common characteristics are as follows: (1) It is right-handed + is (factory, has heat resistance, (2) has high gas barrier properties against inorganic gases such as oxygen or hydrogen, (3) There is no pinhole in the film, (4) has flexibility, (7) has good resistance, (4) has a low coefficient of linear expansion, (7) has flame retardancy and insulation, and can be ashamed. For the material constituting the pad described above, or for the component for display as described above, the edgeability

S 117849-991014.doc 1361171 In the use of electronic materials such as circuit boards. However, using the previous method, when the additive is added to the clay dispersion and mixed, there is a case where the clay is agglomerated by the addition. Or the 'clay dispersion has a sharp rise and the additive is not uniformly distributed in the clay dispersion'. There is also a non-uniform agglomerate in the clay dispersion or agglomeration of the clay to form a particulate precipitate, resulting in the obtained clay. The film is not smeared and spreads evenly. In addition, when the additive has a low solubility or dispersibility in dispersing and dissolving the clay, the additive is also not sufficiently dispersed. This produces a situation similar to the above. As a result, there is a problem in the case of a transparent clay film, that is, a region having a low transparency has a clay or an additive in which particles are aggregated into a particle, and light scattering and haze increase. Even if the additive is added to improve the physical properties of the clay film, the type or amount of the additive is limited. It is also known that if the clay crystal layer is dense and highly aligned by increasing the proportion of clay in the clay film, it becomes difficult to extract the gas component remaining in the clay film from the clay film. In other words, in the case where the clay contains bubbles (voids) derived from the gas component mixed with the clay-containing liquid, there is a problem that the bubble rapidly expands upon rapid heating and a circular protrusion is formed on the surface of the clay film to destroy the clay film. 'The gap existing in the transparent clay film becomes a cause of light scattering inside, and the clay film becomes hazy and haze becomes large. Since the gas component remaining in the clay film is derived from the gas component contained in the clay containing liquid, it is considered that it is important to sufficiently form the film on the support after the silk component contains the gas component in the liquid. The clay film was obtained by drying the 117849-991014.doc -14· 136,1171. Especially in the case of making a clay film with a large proportion of clay, that is, when the proportion of clay in the clay dispersion is large, since the viscosity or flow loss-reducing property derived from clay is remarkably exhibited, the clay dispersion is The flow is reduced and it is too difficult to remove these gas components. Therefore, the industry has an important method to reduce the amount of gas contained in the clay to reduce the amount of clay in the clay. Further, in general, the method of shaking by a dispersing device or the like is used as a method of dispersing clay particles in a solvent. However, in particular, when the solid concentration is high, it is necessary to shake for a long time by means of a dispersing device. X, the concentration of the clay dispersion limited by the liquid limit of the clay generally has an upper limit, so that it is difficult to make the solid concentration of the point soil dispersion higher than the value set by the liquid limit. Further, in the case of the transparent # soil film composed of clay and additives, if the long-term door is placed on the air towel, the haze increases, and the clay film becomes cloudy and the transparency is lowered. The increase in the haze of the haze is caused by an increase in the surface convex time of the clay film. In order to improve the transparency of the clay film in order to reduce the haze, it is also carried out by grinding the surface to smooth it, or to form a clay different from the composition of the clay, such as a transparent tree. (4) Research 'However, smoothing is required It is carried out under the meter-level precision, and the strength and durability of the clay film are problematic, so physical grinding is difficult. Further, in the case where the heat-resistant temperature of the above-mentioned application layer is low, the heat resistance of the clay crucible is greatly lowered, and the linear expansion coefficient corresponding to the temperature change is different from that of the clay film, so that the film is embossed or caused by stress. Problems such as defects in the clay film. So, as with resin

S 117849-99I014.doc •15- 1361171 There are many problems in the method of forming a layer different from clay. Further, in the case where a clay film is produced by a simple and general method, that is, a heating evaporation method, a solvent is removed, and as the solvent evaporates, the volumetric shrinkage occurs in the process of solidifying and gradually drying the clay. The crucible is subjected to the stress generated by the above volume contraction. Therefore, when the strength of the clay film cannot withstand the stress, there is a problem that the clay film is broken during the drying process. Therefore, an object of the present invention is to solve the problems of the prior art as described above, and to provide a clay film having a clay and an additive uniformly dispersed, having difficulty in generating cracks or cracks, and having a strength which can be used as an independent film. Production method. In addition, it is a problem to provide a transparent clay film which has a high light transmittance and a small haze, and which is difficult to cause an increase in haze over time even if it is placed in the atmosphere, and a method for producing the same. Further, the subject matter is to provide an electronic paper, a substrate, and a gas barrier film having such a clay film. [Patent Document 1] 曰 专利 6 6 平 平 平 9 9 9 9 平 平 平 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 254 [Patent Document 4] Japanese Patent Publication No. 3060744 [Patent Document 5] Japanese Patent Laid-Open Publication No. 200679 No. No. No. No. No. No. No. No. No. No. No. No. No. No. Patent Document 7] Japanese Patent Laid-Open Publication No. Hei. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. .doc •16· 1361171 The True Color and Charm of the Earth--, Japan, Sankyo Publishing, p. 6 (2000) [Non-Patent Document 2], in the article, "The development of the mouth of polymer-based nanocomposites" Sakamoto, Frontier Publishing, p. 25~90 (2004) [Non-Patent Document 3] Shiraishi Akira, "Clay Mineralogy - Foundation of Clay Science-", Japan, Asakura Bookstore, p. 57 (1988) [Non-Patent Literature 4] Mezetai History' "Clay Science", Sakamoto, Vol. 42, 'No. 4, 218~222 (2003) SUMMARY OF THE INVENTION In order to solve the above problems, the present invention includes the following configuration. That is, the method for producing a clay film of the present invention is characterized by comprising the steps of: a clay-containing liquid adjusting step of separately preparing a clay dispersion for dispersing a clay in a solvent, and an additive containing the additive dispersed or dissolved in a solvent; a liquid, mixing the above-mentioned clay dispersion with the additive-containing liquid, and obtaining a clay-containing liquid by making the ratio of the above-mentioned clay and the additive-added amount of the additive (4) to 30% by weight or less; In the drying step, the clay-containing liquid is placed on the surface of the support, and the solvent is removed and dried. In the method for producing a clay crucible according to the present invention, it is preferred to include a degassing step of reducing the gas contained in the clay-containing liquid. Further, a peeling step of peeling off the dry product obtained through the above drying step from the support may be included. Further, in the above-described clay-containing liquid adjusting step, it is preferred to mix in a high-gray hanging degree. The clay dispersion liquid and the additive-containing liquid are used to obtain the above-mentioned point-containing liquid. 117849-991014.doc 丄州1171 Further, it is better to make the temperature of the clay-containing liquid higher than normal temperature and put it under a reduced pressure environment to reduce the gas contained in the clay-containing liquid. The result is that the temperature of the clay-containing liquid is higher than normal temperature and is mixed in a reduced environment, thereby reducing the gas contained in the clay-containing liquid. Further, in the method for producing a mulch film according to the present invention, the support is also flexible, and in this case, it is preferred that the support is dried in a state in which the support is detachable from the support. The above-mentioned dried support may be a resin film. Further, the peeling facilitation treatment may be performed. The water-repellent processing support body may be further advanced. The method for producing the clay film of the present invention may further include a surface of the dried material obtained by the re-drying step and the known step. In the above, the liquid etched by the above-mentioned clay is dispensed into a liquid which dissolves or disperses the above-mentioned additives. At this time, the liquid may be attached to the surface of the dried product by immersing it in the liquid, or the liquid may be attached to the surface of the dried product by (4) attaching the liquid. In the above re-drying step, the surface of the dried disc which is partially swollen at least in the vicinity of the surface due to the distribution of the liquid on the surface may be caused by the contact of the sliding member to smooth the surface, and then the liquid is re-slurried. Γ = = part: may also have flexibility and can be deformed. In this case, it is preferable to dry the liquid in the above-mentioned dried product and the above-mentioned flat. . State of contact. In the method for producing a film, it is preferred that the above-mentioned 4 series are hydrophilic clay which has high affinity for water and is easily dispersed in water. J17849-991014.doc -18- 1361171 Further, the above clay may also be a hydrophobic clay which has high affinity to the right 媸.6, machine and mixture and is easily dispersed in the organic bath. - In the case of a hydrophobic clay, the comparison is:: The inorganic ions exchanged by the water-based clay are exchanged for organically separated from the dream forest: the hydrophilic and dispersible hydrophobic clay in the organic 'valley The above organic ions include at least one of a recording ion, a town ion, and a beer salium ion. A further preferred crucible is by exchanging the constituents of the clay (4) into other clays of hydrophobic substituents. In the method of producing a clay film of the present invention, the film may also be transparent. Further, the clay film of the present invention is characterized in that it is produced by a method for producing a clay film as described above, and a layered clay film is laminated in the thickness direction. Further, it is preferable that 4 (TC to 25 (the average linear expansion coefficient of rc is 2 G ppm or less. Further, it is preferable that the average linear expansion coefficient of the thief to bribe is 1 〇 ppm or less. Further, preferably The tensile strength is 1 GMPa or more. Further, the haze is preferably 5 Å/〇 or less. Further, the clay film of the present invention preferably has a haze of 5% or less and a total of $100 transmittance. The light transmittance in the wavelength range of 85% or more and in the range of _(10) or less is 85% or more and 95% or less. For the haze, the haze is preferably 2% or less, more preferably fog. The degree is less than 1%. Further, it is preferable that the haze change in time is 2% or more and 2% or less in an environment of 24 ° C, i gas pressure, and humidity of 45%. Further, the clay of the present invention The film 'preferably has a film thickness greater than 15 μm.

Further, the electronic paper of the present invention is characterized in that at least a part thereof is obtained by using the earth-leaf film obtained by the method for producing the earth-leaf film of the present invention as described above, or as described above. The clay film of the present invention is constructed. Further, the flexible substrate of the present invention is characterized in that at least a portion thereof is composed of a clay film obtained by using the method for producing a clay film of the present invention as described above or a clay film of the present invention as described above. Further, the flexible printed circuit board of the present invention is characterized in that the pot is composed of at least a ruthenium film which is obtained by using the method for producing a clay film of the present invention as described above, or the smear film of the present invention as described above. The substrate of the present invention is characterized in that an electronic component having a non-issue==conductor or an amorphous inorganic semiconductor is mounted, and at least a part of the resistive substrate is used by using the manufacturing method of the present invention as described above. The obtained clay film or the clay film as described above is composed. The gas barrier film of the light source is characterized in that it protects the electronic component having the non-crystalline amorphous inorganic semiconductor from the gas barrier, and at least a part thereof is used by using the invention as described above = The clay film obtained by the method for producing a film or the clay film as described above is used. [Embodiment] The clay film of the agent = the film composed of the point soil and the additive, but the total amount of the added additive _ must be more than 〇wt% r, more preferably more than 0 wt% and 40 Below wt%. In order to obtain better properties as a clay film, it is better that the additive H7849-9910l4.doc • 20-13 (the ratio of 51171 exceeds 〇wt% and is less than 3〇wt%) and further preferably more than 〇Wt/ ° and less than 30 wt%, particularly preferably more than 0 wt ° / and below 15 Wt / ° 'best is more than 〇 wt% and 10 wt ° /. Below. The proportion of right additives is larger , because of the increase in the amount of additives between the unit layers of the clay and the large opening between the crystal layers of the clay, and the influence of the alignment of the soil crucibles, resulting in a decrease in transparency T and additives. The heat resistance of the hot knife is lowered, and the gas barrier properties of the gas permeation of the additive are decreased, and the dimensional change of the clay film due to the temperature change is increased, and there is little difference from the previous nano composite material depending on the physical properties. U-shaped. Knowing that the ratio of the additive is less than wt% (especially if it is less than 3 )) can be obtained with different characteristics of the previous nanocomposite with a lower ratio of clay (for example, low linear expansion coefficient and high resistance) Gas). In general, clay film Only the clay or the clay-containing liquid containing the clay and the additive is distributed on the surface of the support, and then dried, thereby obtaining the effect of the additive in the clay film, depending on the function or use to be expressed. However, in general, it is difficult to obtain the strength of the use as a separate film by clay, and it is more or less required to have the function of imparting strength. When the average aspect ratio of clay crystals is relatively large, for example, When using a natural montmorillonite having an average aspect ratio of 3 〇〇 or more, 'a clay film having strength which can be used as a stand-alone film can be obtained even without an additive, however, the obtained clay film is more brittle' Preferably, the additive is used. Even in the present invention, the most important effect of the additive is to increase the strength of the clay film. Therefore, if an additive having an effect of increasing strength is added (for example, polymerization)

S H7849-99l0u.doc -21 - the ratio of the substance or the polymerizable monomer), and the strength of the S clay film will also be improved. As in the previous Nailai composite, when the proportion of the additive is larger (more than 5 Gwt%), even if the orientation of the crystallization of the soil, the insertion of the additive (the target substance intercalated between the layers of the crystallization of the point soil), and the clay ab are not partially considered The degree of progress or dispersion of the layer peeling, the removal of the gas component in the clay-containing liquid, and the like, and the strength of the additive, etc., can be inferred to have a strength and a fixed degree of peeling from the support. Transparency. However, in the case of a clay film having a large proportion of clay, especially when the proportion of clay is 70 wt% or more, if the previously known method is used, the clay or the additive may not be sufficiently dispersed in the clay. In the liquid, the gas component mixed in the clay-containing liquid cannot be sufficiently removed, so that the obtained clay film becomes uneven. As a result, there is a case where the mechanical strength or the slackability of the clay film becomes insufficient. X, the aggregation due to the addition of the additive or the increase in the solid concentration in the clay dispersion is insufficient for the transparent clay film to be insufficient in transparency. In such a case, in order to further improve the transparency, it is generally considered to carry out countermeasures such as applying a layer different from the clay such as a surface flat π layer, but there may be an increase in manufacturing steps or due to the provision of the above-mentioned paying layer. And the problem of lowering heat resistance. Further, even if such countermeasures are carried out, the deterioration of physical properties caused by the uneven structure generated inside the clay film cannot be avoided. Therefore, the inventors of the present invention have intensively studied to solve the above problems, and have found a method for producing a clay film which can obtain a clay film in which clay and an additive are uniformly dispersed. The method for producing a clay film of the present invention is 117849-991014.doc -22-characterized by the following steps: (a) clay containing liquid adjusting step, respectively, the clothes are dispersed in the solvent a clay dispersion liquid, and an additive containing liquid for dispersing or/or dissolving the additive in the mixture, mixing the above clay dispersion with the V addition agent to have a liquid 'and making the above additive in the clay and the above-mentioned additive O *^lj -λ· I ja_ 〇° The proportion of lysium exceeds 0 wt% and is less than 50% by weight, UJt obtains 1U of liquid; and (b) drying step, the clay containing liquid is disposed on the support After the surface, the above solvent is removed and dried. The viscosity can be obtained by appropriately selecting the type of clay or additive, and in the present invention, the total light transmittance is 70/. Above °, the haze is 5% or less, and the light transmittance in the wavelength range of 400 nm or more and 800 nm or less is 75% or more and 95% or less. However, the transparency is the minimum, and the total light transmittance is preferably. More than 80%, more preferably more than 85%, further better is 88% The haze value is preferably 3% or less, more preferably 2% or less, and even more preferably less than 1 /〇. Further, the light transmittance in the wavelength range of 400 nm or more and 800 nm or less' Preferably, 80% or more and 95% are T, more preferably 85% or more and 95% or less. Furthermore, the total light transmittance and haze described herein are made of plastic transparent as specified in Japanese Industrial Specifications. Test method for total light transmittance of materials JIS K 7361, optical test method for plastics JIS κ 71〇5, method for obtaining haze of plastic transparent materials; 18 κ 7136 as a benchmark. Previously, manufactured by this When the clay film obtained by the method for producing a clay film of the invention is used, even when the ratio of the clay is 7 〇 wt% or more, the additive is directly added to the clay dispersion in which the clay is dispersed in the solvent, and 117849-991014. Doc -23- ^01171 Modulate clay containing liquid. However, if this method is used, the higher the solid concentration of the clay in the bein clay dispersion, the higher the viscosity of the clay dispersion, and the flow decarburization becomes significant. The fluidity of the clay dispersion is obvious When it is lowered, it is difficult to uniformly disperse or dissolve the additive in the clay-containing liquid. In particular, it is more difficult to have an additive (for example, polyacrylate) which acts to thicken the clay-containing liquid by the addition. Therefore, in the method of the present invention, the clay dispersion liquid in which the clay is dispersed in the agent and the additive liquid in which the additive is dispersed or dissolved in the solvent are separately prepared, and then the mixture is mixed to prepare the clay content & It is an additive which exhibits a viscosity-increasing effect in a dissolution process or a dispersion process in a solvent, or an additive which is low in dispersibility or solubility in a solvent for dispersing a clay, and can be uniformly dispersed in a clay-containing liquid. in. Therefore, the kind or amount of additives that can be used is hardly limited. Further, by mixing the clay and the additive sufficiently in a state of being dispersed or dissolved, it is possible to suppress the aggregation of the clay to form a non-uniform cake due to the action of the additive. In the method, it is preferred that the clay and the additive are dispersed or dissolved in a solvent at a temperature higher than a normal temperature, and the viscous dispersion is added and the illusion is added. Thus, the additive can be dispersed or dissolved more uniformly and at a high concentration. Further, it is preferable that the clay-containing liquid is obtained by constituting a clay dispersion and an additive-containing liquid at a temperature higher than a normal temperature. Thus, the clay can be more uniformly dispersed and the additive can be more uniformly dispersed or dissolved, and a clay-containing liquid having a higher solid concentration can be prepared. A method for preparing a clay dispersion and an additive-containing liquid by dispersing or dissolving a clay and an additive in a solvent at a temperature higher than a normal temperature in a solvent of 117849-991014.doc •24-1361171, and adding a clay or an additive to the solvent, Using a heater, blowing hot air, heating in water, etc., heating, stirring, shaking, and mixing and mixing, using the above method, mixing, shaking, and mixing; A method in which the dispersing device, the homogenizer, and the like supply energy to cause the additive-containing liquid to self-heat while stirring and shaking. In the present invention, the mixed clay dispersion and the additive liquid may be mixed at room temperature. However, in terms of producing a uniform clay-containing liquid, in terms of improving the solid concentration of the clay-containing liquid, Mixing clay dispersions and additives containing liquids at a temperature higher than normal temperature to adjust; clay is better for liquids. As such a method, a mixed clay dispersion liquid and an additive-containing liquid are used, and the mixture is heated by a heater, a hot air, and heated in water, and then stirred and shaken to be mixed; A method in which the mixture is stirred and shaken, and the mixture is stirred, and the mixture is stirred and shaken by using an ultrasonic dispersing device, a homogenizer, or the like to supply energy. Further, the clay contained in the clay dispersion may be used as a seed or a mixture of two or more different clays. Similarly, the additives contained in the additive-containing liquid may be used in the form of a mixture of two or more different types of clay. Further, a clay-containing liquid can be produced by using two or more different types of clays such as clay types, and a clay-containing liquid can be produced by using two or more additive-containing liquids of the additive type. Or, also ^ 117849-991014.doc -25- 1361171 Do not mix a plurality of clay dispersions and a plurality of additives containing liquid to prepare a clay-containing liquid. Thus, by adjusting the liquid at a temperature higher than normal temperature to obtain a clay-containing liquid in which the clay and the additive are more uniformly dispersed, the generation of aggregates can be suppressed, and the clay crystal film formation step is evenly inserted between the clay crystal layers. The additive (intercalation) enables the production of a clay film having sufficient mechanical strength and flexibility to impart sufficient transparency to the transparent clay film. Further, by mixing the clay and the additive with the solvent at a temperature higher than the normal temperature, the solid concentration of the clay-containing liquid can be increased. If the solid concentration of the clay-containing liquid is increased, it becomes easy to shorten the drying time or to manufacture a thicker clay film. Further, the low-viscosity clay-containing liquid can be disposed only on the horizontal surface of the surface of the support at right angles to the direction of gravity, and if it is disposed on the inclined surface, it will flow down. However, if the solid concentration of the clay-containing liquid is increased, it becomes In the form of a slurry, it may be disposed on an inclined surface. Further, the fluidity is lowered, so that it is not necessary to prevent the clay from preventing the clay-containing liquid from flowing out of the support. The liquid containing the liquid flows out of the support (for example, no frame is required). In the present invention, the clay dispersion liquid, the additive-containing liquid, and the mixture in which the clay contains the liquid are prepared, and the container which is rotated while revolving around the axis can be used. In the method of producing a clay film containing clay and an additive, at least one of the preparation of the clay dispersion, the additive-containing liquid, and the clay-containing liquid is carried out using the above container, and the clay-containing liquid is prepared. The mixing method used to prepare the clay dispersion, the additive-containing liquid, and the clay-containing liquid can be used - any one that can sufficiently disperse the soil and the additive. However, the method of using the above container can be used not only by the force H7S49-99J014.doc •26- 13*61171 The stirring and degassing ability can be dispersed or dissolved in a short time, and it can also be stirred in a gel state exceeding the liquid limit, so it can be excellently used. A clay containing liquid having a higher solid concentration is obtained. In particular, when the inside of the container is in a reduced pressure state such as a vacuum, and then the clay containing liquid is stirred under a reduced pressure environment, vacuum degassing can be performed while mixing. Therefore, the degassing of the clay-containing liquid which is difficult to reduce the gas component which is mixed due to the high solid concentration and high viscosity can be sufficiently and efficiently performed. Further, a plurality of the above methods are combined to prepare a clay film. In the clay film produced by the production method of the present invention, when the ratio of the additive is 30 wt% or less, if bubbles (voids) are mixed, the bubbles may be expanded to break the clay film during heating and drying, or may be transparent. Problems such as a decrease in transparency due to scattering of light or the like in the film. Further, in general, the higher the solid concentration in the clay-containing liquid, the higher the viscosity, and the more the viscosity reduction becomes stronger. Therefore, if the mixing is stopped, the tendency to lose fluidity becomes stronger. As a result, it becomes difficult to remove the gas component mixed into the clay-containing liquid. In a clay-containing liquid in which a solid concentration of a practical drying speed can be obtained, it is difficult to reduce the gas component in which the X is poured into the clay-containing liquid by a particularly strong one.中 In the clay film with a higher enthalpy of clay, the clay crystals are densely packed: the resistance is improved, and as a result, it becomes difficult to remove the bubbles remaining inside the earth film. Therefore, it is extremely important to sufficiently remove the clay containing the gas components contained in the two, and it is an essential step for the clay film of the ratio of the earth to earth. Furthermore, the clay film with a higher proportion of point soil can be used as a separate film. 117849-991014.doc

S -27- 1361171 Intensity requires a certain thickness of film. The thickness of the clay film is preferably thicker than 1 〇 _, more preferably thicker than 15 (four), and further preferred is thicker than particularly preferably thicker than 30 μm, and most preferably thicker than 5 〇 (four). The difference between the film thickness and the film thickness at which Km is not required to be self-supporting, and can be effectively used for coating a film in most cases. However, if the film thickness of the clay film is increased as described above in order to increase the strength, the gas component mixed in the clay-containing liquid is more difficult to remove from the inside of the clay film at the time of film formation, and is likely to remain inside the clay film. This indicates that the thicker the film thickness, the more the defects caused by bubbles or the like remaining inside the clay film, resulting in, for example, a decrease in transparency due to scattering of light or breakage of the clay film during heating.

In order to make the desired clay thicker, it is generally considered to increase the concentration of the clay-containing clay and to thicken the liquid film containing the liquid on the support. In the case of using the former method, as the solid concentration of the clay increases, the clay-containing liquid (4) rises, and the flow viscosity-reducing property also becomes conspicuous, and the fluidity of the clay-containing liquid is lowered. Therefore, using a certain It is important that these methods fully implement the removal of the mixed Z-scores. Further, in the case of the latter method, if the thickness of the liquid helium disposed on the support is increased, the amount of the gas component to be mixed is also increased. Therefore, it is important to sufficiently remove the gas which has been mixed by using some methods. As a method of sufficiently removing the gas component contained in the clay-containing liquid, the method of separating the gas component from the clay-containing liquid by centrifugation is also preferable, but it is particularly preferable to place the clay-containing liquid in a reduced pressure environment. Thus, a method of vacuum degassing is carried out by 117849-991014.doc -28-1361171. At this time, if the viscosity of the clay-containing liquid is higher than the normal temperature and the viscosity is lowered, even if the clay having a high solid concentration contains liquid, the gas can be degassed satisfactorily. That is, it is preferred that the clay-containing liquid is heated to a temperature higher than normal temperature and placed under a reduced pressure environment to remove the bubbles contained in the clay-containing liquid before the clay-containing liquid is distributed on the surface of the support. In this case, when the clay-containing liquid is stirred in a reduced-pressure environment, not only the gas remaining in the clay-containing liquid is moved in the vicinity of the liquid surface, but also easily discharged from the clay-containing liquid, and the performance of the flow-reducing property can be suppressed. By suppressing the increase in the viscosity of the clay-containing liquid, the degassing effect is further improved. Further, if degassing is carried out at a relatively high temperature, as described above, the viscosity is lowered, so that degassing can be favorably performed. However, since the solvent of the clay-containing liquid is easily evaporated during degassing, it is especially a solvent. The concentration of solids in the vicinity of the liquid surface being evaporated tends to rise, and as a result, precipitation of solid matter is likely to occur. Further, by degassing while stirring, the local solid concentration is not increased in the clay-containing liquid, and the viscosity is prevented from increasing by the viscosity reduction property, which can be preferably performed at a higher temperature. Degas. The degassing operation as described above may be performed by heating the clay containing liquid by using a heater, blowing hot air, opening/hoting, or the like, or by using the above-mentioned side heating enthalpy, or by using an ultrasonic dispersion device. The homogenizer supplies energy and causes the clay-containing liquid to heat itself. In addition, when the clay containing liquid is stirred under the decompression brother, both the stirring wing and the stirring wing can be estimated. In the case of using the month's article, one side of the axis revolves around the side and the side rotates, and the clay containing liquid can be distributed on the support body as described above.

S 117849-991014.doc • 29-1361171 describes the degassing operation. In this case, by dispersing the clay-containing liquid on the support, it becomes a thin liquid film, and degassing in a state in which the clay-containing liquid enters the degassing box or the like in a state of a thick liquid film. In the case of operation, the gas composition can be reduced more effectively than '. In the case of producing a clay-containing liquid in the present invention, it is preferred that the solid concentration of the clay-containing liquid is 0.5 wt% or more and 2 wt% or less. By increasing the solidity/agronomy, the time required for drying can be shortened, so that the solid concentration is preferably 0.5 Wt%. Further, by setting the solid concentration to 2 Å or less, a clay-containing liquid in which clay and additives are well dispersed can be obtained. In addition, the viscosity of the soil-containing liquid is suppressed to a specific value or less, and the performance of the flow-reducing property can be suppressed. Therefore, the gas component mixed in the clay-containing liquid can be easily removed. As a result, the orientation and uniformity of the clay crystals in the obtained clay film are improved, thereby improving the transparency of the clay film, gas barrier properties, dimensional stability, and the like. In order to obtain such effects sufficiently, the solid concentration of the clay-containing liquid is preferably 1 wt% or more and 15 wt% or less, and more preferably 丄 wt% or more and 12 wt% or less. In the present invention, the gas component contained in the clay-containing liquid may be reduced in a reduced pressure environment (fourth), and then the solvent may be reduced by a treatment such as heating to obtain a slurry having a further improved solid concentration. The clay is contained in this situation, and the solid concentration of the clay-containing liquid can be further increased as compared with the preferred range described above. Thereby, the gas component contained in the clay can be removed and the drying time can be shortened, so that the effect of improving the mass productivity of the clay film can be obtained. " Further 'by increasing the viscosity, depending on the situation, significantly showing the rogue 7849-9910l4.d, • 30· 136.1171 dynamic viscosity reduction, can reduce the liquidity, therefore, 4* Μ you said The limitations of the support. That is, since the slurry-like Μ Μ + # β is less maneuverable, the clay-containing liquid applied to the support does not smash the sputum- 曰Μ, so that it is not necessary to use, for example, a 4-wall type Out of the makeup point 4* person Dan & blade again conforms. Further, each of the slurry-like soils has an advantage that it can be applied to an inclined surface. Furthermore, the clay contains a liquid nail to add a tackifier and the like. It can also be used to achieve the above-mentioned "as a method of reducing the solvent of the soil containing liquid order, but it is more limited to the evaporation method, but it is particularly limited to $", and can be used for centrifugation, transition, and enthalpy. The well-known solid-liquid separation technology is known. + Potassium concentration of the above-mentioned US solid concentration:;; carried out under reduced pressure, especially if the thickness of the clay-containing liquid is 2, while the action of the clay is carried out by the action of the sputum, etc. - when the concentration is increased, the solvent is It is more effective to increase the amount of evaporation so that it can be concentrated in a short time. Concentration is carried out in the environment of the heart of the heart and the environment is reduced, so it is better to degas the gas at the same time. However, if the clay-containing liquid is concentrated, then as described above, the pain in the 3 liquid is difficult to remove. The residue contained in the clay contains the knives. Therefore, it is important that the clay contains liquid in the liquid. The ingredients are fully reduced. And.. At the same time, when the situation is pushed, Cao contraction and degassing, the important #(10) is to order the suffocation. The desired 疋' needs to be removed before the concentration is completed. After the clay-containing surface is obtained, the solvent is slowly removed. (4) The thickness of the coating is not particularly limited. However, it is preferable that, for example, the film is removed. The method is dry and dry, and the bead is vacuum dried, separated, filtered, and is directly in an inert gas atmosphere, and added 117849-991014.doc s 117 117 1171 thermal evaporation method. Alternatively, a plurality of the methods may be combined. In these methods, for example, a heating tray is used, for example, a flat tray is used as a support, and a point-containing liquid is applied thereto. ^The material of the holding body is not particularly limited. However, it is necessary to withstand the temperature of heating. For example, T is a film made of polyethylene terephthalate (PET) or polypropylene. The film is made of a resin, glass or 11 crystal. circle. Further, a substrate made of brass, steel, non-recorded steel, or metal may be listed. Regarding the support body, it is generally preferred that the thermal conductivity is higher. Furthermore, when the clay-containing liquid has a high viscosity or a strong flow-reducing viscosity, the coated clay: when the liquid does not flow out, does not require a structure such as a tray to prevent the fluid from flowing out of the tank. A flat support made of the above materials. The volume shrinkage occurs during the solidification and drying of the clay-containing liquid as the solvent evaporates, and the stress generated by the above volume shrinkage is used in cooperation with the obtained clay film. Therefore, the strength of the clay film cannot be carried out; in the case of the stress, the clay film is broken during the drying process, and it is difficult to produce a large-area clay film in the shape of the moon, so that there is a problem that the usable use is limited. In such a case, in order to absorb the stress generated by shrinkage of the volume, a support having flexibility and being easily deformed is preferably used. In this way, the clay film itself can be deformed together with the support during the drying process, or the support can be actively edge-shaped to form a shape capable of alleviating the stress generated by the volume shrinkage. It relieves the stress remaining in the earth's membrane and thus inhibits the cracking of the clay film. The support body is not particularly limited as long as it has flexibility and is easily deformed. 117849-991014.doc •32· However, if the peeling property of the clay film after drying is taken into consideration, the clay film is continuously produced in the form of a roll, and the clay compound is produced. For the influence of the manufacturing cost of the system of 4 Torr, it is preferable to use a film made of an inexpensive resin such as PET. It is preferred that the portion of the surface of the support which is in contact with the clay film is subjected to a peeling facilitation treatment or a water repellent treatment in order to easily peel the clay film from the support. Or, it is preferable to form a support by using a polypropylene having a high water repellency, a polytetraethylene or a thief. Examples of the ease of peeling treatment include ultraviolet irradiation treatment, electron beam irradiation treatment, ion beam irradiation treatment, corona discharge treatment, electric power treatment (for example, remote electropolymerization treatment, flame electropolymerization treatment), and physical treatment. (For example, mechanical processing to machine the surface as the contact area changes). Further, the treatment may be carried out by applying a resin such as an fluorenone resin to reduce the adhesion, or applying a physical stimulus such as light or heat to cause a change in softness or Young's modulus or foaming. (4) Treatment of sexual payment. Alternatively, a plurality of the methods may be combined. Further, as the water repellent treatment, the same effect as the above-described peeling facilitation treatment can be obtained. However, as a preferable example, a method of applying a fluororesin or titanium dioxide can be mentioned. The support surface is preferably as smooth as possible. In the case where it is not smooth, the surface of the clay film is transferred with the raw sugar on the surface of the support, so that the surface smoothness of the clay film is lowered. Further, the light is scattered on the transparent film, which causes the haze to increase. In a clay film containing hydrophilic clay, the stress generated in the clay film is larger after drying and shrinking due to drying shrinkage, but is placed after drying.

S 117849-99l014.doc -33- 1361171 A moment, the internal stress is reduced. For example, a transparent film containing a hydrophilic clay is often curled by internal stress after being dried, but if it is left for about minutes, the internal stress is released and becomes a flat film. Therefore, until the internal stress is reduced, the generated stress is dissipated by deforming the support, and the clay film is peeled off from the support after the internal stress is released, whereby the internal stress can be made less, without cracking or rolling. Shrinking clay film. As a reason for reducing the internal stress after being left for a while after drying, it is generally considered that the softness is improved by the absorption of moisture in the air. Therefore, the dry and straight clay film is kept in a controlled environment for a while, and the internal stress of the clay film containing the hydrophilic clay can be effectively removed. As described above, by using the deformable support, the damage of the clay film caused by the stress caused by the volume shrinkage during the production of the clay crucible can be suppressed. Therefore, even if it is a clay film of a large surface, it can be used in a high yield, and therefore, it can be preferably used for a film which requires a large area such as a display, etc. Further, according to the present invention, In the case where the support made of a film having a roll shape is subjected to continuous production of a roll, a continuous clay film can be easily obtained, and thus it is easy to produce a long strip of clay film (for example, clay poem). In the case of removing the solvent of the soil containing liquid by the heating evaporation method, a forced air type oven or the like can also be used. Furthermore, at 3〇.黏土 Under the temperature conditions below i2〇t, the clay film can be obtained after drying for 1 minute or more and 7 hours or less. Regarding the temperature condition, it is better that the machine is more than (4) and further preferably 50°C or more. Wide iv τ / OCU. Further, as for the drying time, it is more preferably 20 minutes or more and 3 hours to τ ^ , J 呀 or less, and further preferably 2 〇 minutes to 117849-991014.doc • 34· for 2 hours or less. However, the most suitable drying time varies depending on the solid concentration of the liquid contained in the earth film, the heat ratio of the four soils due to water, and the drying cost, type, and the like.疋Organic solvent, especially good machine solvent with lower stagnation point as solvent, use # & _ ^, use _ 〇 with hydrophobic clay as the group of clay, obliquely shorten the drying time phase. When the material is being irritated, if the stagnation point of the solvent is too low, the solvent will volatilize and the solid will rise when the clay liquid is adjusted, and the risk of ignition is also increased. Therefore, the ship and the ship are safe. (4), it is preferred to appropriately select the type of solvent. According to the clay material of the present invention, the clay film used as the independent film can produce a clay film having a (4) strength and a small coefficient of linear expansion. . 1. In the case of a non-colored point soil such as synthetic point soil, the spectral characteristics are flat, no coloring, and t is the first or the fog sound is m. The clay film having a transmittance X: is visually confirmed in a wide range. However, in the previous clay film, if the right place is placed in the atmosphere, the surface roughness will increase with time. The hydrophilic synthesis is straight, and the human i, especially saponite or synthetic hectorite, is used as the viscous salt. As an additive, the use of water as the "A" "~ use of propylene as a solvent for the clay-containing liquid, a; seeing more prominent. The unevenness of the surface of the clay film, not only the = surface of the soil film to other films to form electrons When the components are equal in time, the haze is increased due to the increase in the unevenness. 'The earth film becomes cloudy and the transparency is lowered'. Therefore, it is an important issue to be solved. The clay film obtained by the dry clay-free liquid described so far is solved in the following manner (hereinafter, also referred to as drying once)

S I17849-99J014.doc -35- 1361171 Membrane), a liquid which swells the clay or a liquid which dissolves or disperses the additive, and then re-drys. Further, even if such a problem does not occur, the surface of the clay film can be smoothed by such a method, so that the haze can be lowered. The method of drying the film surface liquid (liquid for swelling the clay or liquid for dissolving or dispersing the additive) obtained after the liquid is contained in the dry clay is not particularly limited, however, for example, it is possible to use a primary dry film to be immersed in In the above liquid method, a method of spraying the above liquid on the surface of a dry film as a spray may also be used. Alternatively, a method of placing a dry film once in a high-concentration vapor gas atmosphere of the above liquid may be used. At this time, if the time during which the primary drying film is in contact with the liquid is too long, a part or all of the primary drying film may be redispersed in the liquid, or the dried film may absorb the liquid to be excessively swollen. Therefore, it is preferred that the time during which the primary dried film is in contact with the liquid is as short as several seconds or more, and even if it is made longer, it is preferably within several minutes. Further, if the liquid is dispensed by spraying the surface of the primary dried film onto the surface of the flowing liquid, the surface of the dried film is immersed once = dry, and the film is dispensed, the haze of the film can be effectively suppressed. There are more big situations. On the surface of the sub-dry film, the film is allowed to remain in the -drying =! The sub-dry film is changed from the horizontal state to the inclined state, so that the above liquid flow can be lowered. The second two: The sub-dry film is kept in a tilted state from the horizontal state and the enthalpy of the distribution is applied to the mesh wire used for papermaking, etc. 117849.991014.doc • 36 - 136.1171 The dried film is placed and the liquid is dispensed. Thus, the excess liquid can easily flow from the surface of the primary dried film, so that it is possible to suppress partial or total dispersion of the primary dried film in the liquid or excessive swelling. The liquid _ ' is not particularly limited as long as it can swell the clay, and the -money additive is dissolved or placed, and is selected according to the type of the clay and the additive. In particular, for a clay film having a hydrophilic clay which is swollen in water or an additive which is dissolved in water, water is preferred. When the liquid is distributed on the surface of the dry film and the whole grain of the film easily absorbs the liquid and changes to a gel state, the volume of the primary dried film increases as the volume is condensed. As a result, there is a case where a clay film having wrinkles or the like is formed. In such a case, the clay film is stretched, so that the pleats are elongated and the clay film is flattened, whereby the soil film after drying is more than 4 months. As a method of extending the clay film, a method of pressing a light or the like on the earth film, or a method of stretching the two axes of the stretched clay film may be mentioned. The extension of the clay crucible can be carried out on a smooth surface member, on a mesh wire used for papermaking, or in a state in which it is not in contact with the smoothing portion support. After the drying, the additive is precipitated on the surface of the clay film, and (4) the additive is caused by the increase in haze. If the liquid is disposed on the surface of a dry film as described above, it can be precipitated by the liquid removal. A human additive to achieve the effects of the present invention. Further, in the primary dried film in which the liquid is dispensed as described above, or in addition, the liquid is absorbed, and the entire surface of the primary dried film or the vicinity of the surface of the secondary dried film which is in contact with the liquid is swollen.

_9·"10 丨4d〇C -37. S 1361171=In this state, 'not only due to the surface swelling of the sub-dry film, the surface = large, the smoothness is improved' and the surface of the once dried film becomes gelatinously softened, It is easy to cause deformation due to external force. Therefore, if the surface of the under-dried film is temporarily brought into contact with a smooth surface having a smooth surface, the surface of the once-dried film follows the surface of the smoothed member and is deformed to make a dry film. The surface is smoothed to improve the smoothness of the surface of the obtained earth film. For example, a primary dry film in which the above liquid is disposed is disposed on a smooth glass substrate or a resin film, whereby a clay film having a smooth surface can be obtained. Further, the same glass substrate or resin thinner is disposed on the upper side thereof, and the clay film is smeared by the smooth member, whereby the two clay films can be smoothed. The smoothing member used for smoothing is not particularly limited as long as the surface is smooth, and a resin substrate such as a glass substrate, a tantalum substrate, or a polyethylene terephthalate (PET) film can be used. Further, in order to easily peel off the clay film after smoothing, the surface of the smoothing member may be subjected to a peeling facilitation treatment or a water repellent treatment, which is used in the production of the primary dry film described above. The processing of the support is the same. Further, when the primary dried film is brought into contact with the smoothing member to be smoothed, an external force can be actively applied. For example, the dry film may be disposed on a smooth resin film, and the surface of the rotating surface may be smoothed to smooth the secondary drying film, and an external force such as pressure may be applied to press the primary drying film on the smoothing member. And smooth. At this time, the newspaper or the pressurizing device may be directly in contact with the secondary drying film, and when it is intended to prevent the primary drying film from adhering to the roller or the pressing device, etc., it may be implemented as required. 117849-991014.doc •38 - A smooth film obtained by peeling off a smooth resin film or the like, and an external error is applied, and the primary dry film to which the liquid is dispensed is dried again, whereby the clay film which can achieve the effect of the present invention as described above can be obtained. Drying can be carried out in any part, cow =, or in contact with the member, however, in order to finally obtain a smooth surface clay film, it is preferable to use the smoothing member for smoothing the surface of the clay film surface. get on. The method of re-drying has no particular limitation. However, it is preferred to carry out, for example, centrifugation, separation, enthalpy, vacuum drying, vacuum drying, placing in an inert gas atmosphere, and heating and evaporation. Alternatively, a plurality of the methods may be combined. Or, it can be placed only in the atmosphere. At this time, in order to prevent foreign matter from adhering to the surface of the clay film, the surface (four) property is lowered. It is preferable to re-dry the foreign matter in a dry gas atmosphere in a clean oven or a clean room in a J/ clean room. When it is dried again, volume shrinkage also occurs in the clay film, so that the stress generated by the above volume shrinkage acts on the earth film. Especially in the case where the entire film has been swollen, the stress generated by the above volume shrinkage has a strong effect. Therefore, when the strength of the re-dried clay film on the smoothing member is not able to withstand the stress, there is a case where the clay film is also broken during the dry T process when the film is produced. In order to avoid this, it is preferable that the flat member has flexibility, and after the smoothing member is re-dried, the flat (four) member (four) clay film is used. It is preferable to use a resin film as the above-mentioned smoothing member having eight softnesses. According to the method for producing a clay film of the present invention, it is possible to produce a clay layer with a southerly orientation and a layer, and the additive is evenly inserted between the clay layers.

S 117849-991014.doc *39- Excellent clay, mixed with gas caused by the absence of clay film from the evening & M h. As a result, the obtained clay film has a mechanical strength which can be used as an independent film and has a small coefficient of linear expansion by a dense laminated structure. In addition, when a non-colored clay such as synthetic 2 soil is used, it is possible to produce a point film β which can have a flat spectral characteristic and a colorless color, and can visually confirm the unevenness of transmittance or haze over a wide range. It is difficult to define the mechanical strength of the independent film. However, the tensile strength of the clay film is preferably 1 () Mpa or more, more preferably 15 Mpa or more, further preferably 2 GMP or more, and most preferably 25 Mpa. the above. If it is 10 MPa or more, it can be said that it has a strength that can be handled by hand, and if it is 25 MPa or more, it can be said to have sufficient strength. In the clay film obtained by the production method of the present invention, the gas component contained in the clay-containing liquid can be sufficiently removed, so that bubbles (voids) and the like inside are extremely small. Therefore, although it depends on the heat resistance of the additive, it is a clay film excellent in thermal stability as described below, for example, even if it is rapidly heated (for example, at a rate of increase in the degree of brewing per c )), it is heated to 3 〇〇 <>c and after a period of time, the surface of the film is not observed on the surface, and it can not be seen on the surface. It can be used under high temperature conditions of 30 °C. Further, the 'transparent clay film' is in the entire visible light field. Has a higher permeability: 'haze less color and no coloration, and 'there is less unevenness in the surface with transparency. °#The removal of the gas components contained in the soil containing liquid is especially large." The reduction in the degree of haze is also a very important issue when it is used in optical applications such as displays. In this month, 'the introduction of the gas component in the clay-containing liquid is reduced by 117849-991014.doc -40 · 136.1171 A small number of steps, even in the case where the clay film is thick (for example, thicker than 15 claws), the haze (turbidity) of the film formation can be made 5% or less. , preferably 3% or less, more preferably 2% or less, further More preferably, it is less than 1 ° /.. 'The haze of 24 ° C, 1 atmosphere, and 45% humidity can be changed to 2% or less. The haze change over time, better. It is 1% or less, more preferably 0.5% or less. Further, it is possible to produce a light having a total light transmittance of 85% or more in a wavelength range of 4 〇〇 nm or more and 8 〇〇 nm or less of an ultraviolet visible spectrometer. A clay film having a transmittance of 85% or more and 95% or less. If the haze exceeds 5%, the transparency is low, and a problem that the desired optical characteristics are not obtained may occur, and a glass substrate having a smooth surface and a low haze may be produced. Or the haze of the optical film material or the like is generally about 5%, especially when the transparency is about 0.2%, and the surface of the clay film obtained by using it or the like is used as a support or a smooth member. The haze of the clay film obtained by the base or the smoothing member is generally (4) or less, and even if it is better, it is about 2%. Further, if the haze changes over time by more than 2%, It may result in a decrease in the transparency of the clay film over time and the desired optical properties. Good condition. Further, the upper limit of the light transmittance of the system is determined by the refractive index of the film

In the version of TO, the refractive index of clay is mostly about 1>5 left 纟. Therefore, it is generally considered that even if an additive having a lower refractive index is added, the parallel light of the clay film is strongly produced by the method for producing a clay film of the present invention. The light transmittance is also limited to about 95%. Of course, for example, the anti-reflection film, the light-reflecting film using the light H t and the low refractive index first dry β layer, or the film having the anti-glare treatment of S. 117849-9910I4.doc 1361171 may be laminated. - Steps increase the transmission rate. According to the manufacturing method of the clay film of the seventh and seventh month, the average linear expansion (four) near the thief can be obtained by the effect of the proportion of the additive being small, the viscosity of the crystal layer being highly aligned, and the additive being evenly intercalated between the layers (four). For clay films with a value below 20 Ppm. The coefficient of linear expansion is better. The following is better than 10 ppm, and even more preferably less than 7 ppm, more preferably less than 5 ppm, and most preferably less than 3 ppm. Such a small coefficient of linear expansion is in the case of a prior film containing a resin, or in a previous nanocomposite in which the clay is mainly composed of a resin and the crystal layer of the clay is dense and highly aligned without being laminated. The minimum value obtained is especially the value that is extremely difficult to obtain for a transparent film. Most of the 70 pieces of electrons are composed of inorganic substances having a small coefficient of linear expansion, etc., so it can be said that the clay film of the present invention has a characteristic that is extremely suitable for use as a soil plate for mounting a rafter element of a scorpion, and will be so When the clay film is used as a gasket or the like, since the unevenness of the surface is small, an effect of further suppressing leakage of gas or the like can be obtained. After the clay film is produced, as a method of confirming that the clay and the additive are uniformly dispersed and sufficiently removing the mixed gas, whether or not the clay film having a highly aligned clay crystal layer is obtained is effectively used, and the X-ray winding is analyzed using a rifling diffraction device. The spectrum was observed and the state of the layer was observed directly using a transmission electron microscope (TEM). Compared with the prior art, the dispersion of the clay crystals formed on a support such as a glass substrate or the dispersion or peeling of the clay crystals in the nanocomposite containing clay can be measured extensively by twisting. Two states, etc. are studied and evaluated...in general, 'based on crystallization by clay _ 117849-991014.doc •42- 136.1171 The first diffraction of the surface is generated by the main peak in the x-ray diffraction spectrum (most at low The strength and position of the bottom surface reflection peak of the 2nd side, and the improvement of the base of the diffraction spectrum of the 低 line in the low 20 area, etc., can be known as the laminated state of the clay crystal (the average interval of the layers) and the dispersion state. The average layer spacing in the clay film in which the additive ratio is less than 30% by weight is converted to 10 nm or less from the position of the above-mentioned main peak in the right X-ray diffraction spectrum. The average interlayer distance is preferably 7 nm or less, more preferably 5 nm or less, further preferably 4 nm or less, particularly preferably 疋3.5 nm or less, and most preferably 2 nm or less. Further, when the average interlayer distance is 1.5 nm or less, it is possible to express extremely high gas barrier properties below the measurement limit of the measuring device. Regarding the preferred average interlayer distance, if converted to the tip position of the primary diffraction peak (the value of 2 )) as described above, the measurement is performed using the wavelength of the general copper (4), that is, 1'54 ,, For a clay film containing a smectite clay or a synthetic mica clay having a thickness j of about 1 nm, which is a crystal 曰 of a piece of clay, '2 Θ corresponds to a region below G8 and below 9 。. Furthermore, the minimum value of the average interlayer distance is equivalent to the average interlayer distance of the clay-only compound. However, since the clay film of the present invention is added to the average intercalation layer, the average interlayer distance is larger than the group containing only clay. two:. As a method for confirming this, the standard is whether or not the peak tip position of the above-mentioned main peak of the X-ray diffracted light 2 is closer to the lower side than the composition containing only clay, and the cap is broadened. In addition, whether the peak width of the lit peak is in the lower middle, whether the average inter-layer distance is within the above-mentioned pregnancy, or the image obtained from the photograph of the TEM from the mountain is straight H7849-99l014.doc -43- 1361171 The length of the distance between the measurement layers is determined by this. Further, the clay film obtained by the method for producing a clay film of the present invention has a high barrier property to inorganic gases such as hydrogen, oxygen, and nitrogen, and is largely different depending on the type of clay and additives used. The film of the additive _ below. The transmittance at the second time f only contains the film of the additive used, and it is better that <(10) or less, and then ====(10)(8) or less. There is also a gas barrier property below the measurement limit of the conventional gas permeability device (for example, a device of M〇c〇n Co., Ltd.) according to the composition of the clay film. Further, since the clay film of the present invention can be used for the leachite film, it can be used as an independent film, so that it is on the way. For example, it exhibits heat resistance and gas barrier properties, such as softness = raw = silkiness, and an active matrix drive circuit which can be directly formed on a clay film as a base plate of a replaceable electronic paper at a high temperature. In this way, it is also possible to use a method in which the heat-resistant glass is used to transfer the film to the driving circuit after the film is formed on the film, thereby reducing the manufacturing cost of the electronic paper. In the case of the bottom plate of the electronic paper, it is generally not required to be transparent. However, if the earth film is transparent, it can be used as a substrate or a gas barrier film on the side of the front side of the paper. Further, the type of the electronic paper to which the clay film of the present invention is applied is not particularly limited. However, for example, an electrophoretic-driven or electronic powder fluid type electronic paper may be cited. In addition, # may exhibit an insulating property' The film is widely used as a flexible substrate for an electric circuit. In the case of a substrate used as an electric circuit, 117849-991014.doc * 44 - 1361171%, more preferably, for the purpose of preventing breakage of wiring or the like, The surface of the substrate has a small unevenness or a coefficient of linear expansion, so that the clay film of the present invention is preferable. In particular, a flexible printed circuit board t' for forming a conductor portion on a substrate by coating or printing a conductive ink can exhibit clay. The heat resistance of the film and the low coefficient of linear expansion are used to burn the conductive ink at a higher temperature, so that the electrical resistivity of the conductor portion formed by coating or printing can be further reduced. As such a flexible substrate and soft printing For better use of the circuit board, an RFIDk-signed substrate, a copper-stacked laminate, etc. can be cited. Further, if it is a transparent clay film, it can also be applied to a solar cell or the like that requires light to pass through. Or an organic semiconductor represented by a thiophene, which is easily deteriorated by oxygen or moisture, and an amorphous inorganic semiconductor is not affected by an organic semiconductor, but is also affected by oxygen or moisture. Therefore, it is used. In the element, it is necessary to sufficiently prevent the intrusion of oxygen and water vapor. ▲ Since the clay film of the present invention has high gas barrier property, it can be preferably used as an organic semiconductor or semiconductor which is sensitive to deterioration caused by oxygen or the like. A substrate for an electronic component of a crystalline inorganic semiconductor, a gas barrier film of an organic semiconductor or an amorphous inorganic semiconductor, and a softness can be maintained even at a high temperature due to the clay crucible. Therefore, the electronic component can be made flexible. In addition, when the clay film of the present invention is used for the electronic paper, the flexible substrate, the flexible printed circuit board, and the electronic component including the organic semiconductor or the amorphous inorganic semiconductor, The clay film can be used as it is, and a film having other functions can be applied to the clay film as needed (for example, a hydrostatic barrier film mainly containing an inorganic material, a reinforcing material containing a resin material, etc., to prevent damage, etc.)

S 117849-99I0l4.doc -45- 1361171 Use a protective layer, a smoothing layer that smoothes the surface, etc. In addition, the above-mentioned water vapor barrier film may be provided with a resin material, a strong material, a protective layer for preventing damage, and a flat surface such as a ruthenium layer having a function different from clay. Dispensing the liquid on the surface of the clay film and making it _ 're-drying to improve the + slip property of the # soil film portion. For example, it can also be attached to the surface of the soil film. The film containing the clay and the resin film is immersed in the liquid or attached to the surface of the soil to swell, and then swelled, and then re-dried. When..., for most laminates, there are clay films and clays with different functions. In the composite film of the film, the improvement of the above method can be carried out as long as at least the outermost layer of the composite film surface is a point film. The clay film of the present invention and the method for producing the same will be further described in detail. The type of clay to be used is not particularly limited, and may be a day... or a point clay may be a synthetic clay. Example #, preferably mica, warp, montmorillonite, iron montmorillonite, beidellite, soap Stone, hectorite, slip saponite, Green stone, Magadia [hydrotalcite, kaolinite, and kaolin. Especially in the case of transparent clay film, synthetic clay is preferred. As synthetic clay, it is better to synthesize soapstone, synthetic clock. Montmorillonite, synthetic slippery mica, synthetic hydrotalcite, synthetic kaolinite, etc., in terms of dispersibility, etc., furthermore belongs to the clay of the smectite group. It is preferred to be a natural montmorillonite or a mica clay which is relatively large in cross-section of the clay crystal layer. Further, in terms of gas barrier properties, it is also a 'high aspect ratio synthetic smectite clay. Synthetic cloud U7849-9910l4.doc -46- U61171 Mother, hydrotalcite. Also, the following hydrophobic point soil can be used, that is, the use of recorded salt, scales, imidazole rust salt, carboxylic acid, etc. The salt of the sculpt is yokeed and treated to improve the dispersibility of the organic solvent. The treatment is to exchange the inorganic ions of the hydrophilic clay into organic ions. Further, the underlying clay can also be used. That is, by using chemical reactions to convert most clay mines物物二二: The treatment of the octahedral thin layer of the octahedral layer described above as a constituent of the layer structure is converted to other hydrophobic displacement groups (for example, by dehydration bonding with any decane coupling agent) The replacement of a hydroxyl group with another organic group is carried out to improve the water resistance or to control the dispersibility thereof in an organic solvent: in particular, the ease of handling and dispersibility of the above treatment are carried out. The organic montmorillonite which is hydrophobized by the montmorillonite clay is used as the above-mentioned treatment. As the ammonium salt in the salt containing organic ions, it may be mentioned that it contains a hospital base, a base group, a polyoxyethylene group, and an oxyethylene group. a salt of a base, an oxypropyl group, a salt of a dimethyl stearyl ammonium salt, a dimethyl stearyl ammonium salt, etc., and a heat resistance of a salt of a scale or a salt. It is difficult to decompose or color, even if it is high temperature. Therefore, a clay film which is excellent in heat resistance can be obtained by using a hydrophobic clay which has been treated with a scale salt or a salt of salt. Since the affinity between the hydrophobic clay and the water is lowered, the obtained clay film has low affinity with water, and as a result, the water resistance is excellent. Further, the clay of the present invention comprises both of the hydrophilic clay and the hydrophobic clay. In the hydrophobic clay, the organic ion obtained by combining the tetrahedral thin layer or the octahedral thin layer surface as described above is defined as one part of the clay 117849-9910l 4.doc • 47·5. The presence of organic ions in hydrophobic clays has the disadvantage of reducing the gas barrier properties due to a slight increase in the interlayer distance of the clay crystals, but it is strongly bonded to the tetrahedral thin layer or the octahedral thin layer surface. Therefore, generally, the material of the HI dimensional stability of the clay is relatively small, and it is more like the water-resistant effect of the hydrophilic and dangerous clay. In addition, it can be obtained by exchanging inorganic ions such as an alkali metal existing between the hydrophilic clay layers into organic ions. Therefore, if a hydrophobic clay which is sufficiently ion-exchanged is used, a clay film which hardly contains a metal test can be obtained in principle. Therefore, it is generally considered that it can be preferably used in the use of electronic components for repelling alkali metals. The type of the additive to be used in the present invention is not particularly limited. However, the main effect of the additive is to increase the flexibility and strength of the clay film, and to relieve the stress caused by shrinkage of the body when removing the solvent of the clay-containing liquid (to ensure the surface) The smoothness and the uniformity of the inside of the clay film), in general, it is preferred that the additive itself has flexibility, elasticity or fluidity. The form of the additive itself need not be a solid, and may be in the form of a liquid, a sol or a gel as long as it is uniformly dissolved or dispersed in a solvent. In the case of producing a transparent clay film, it is preferred that the additive be transparent or less colored. As such a substance, it is particularly preferable that the polymer mainly contains carbon or ruthenium in the main chain. Of course, it is also a monomer having a polymerizability which is converted into a polymer by polymerization with other monomers or polymers in a clay film. Further, it may contain organic ions that interact with the clay. Such additives are specifically indicated. In the case of dissolving or dispersing clay 117849-9910Rdoc -48- 13 (51171 $ when the granule is water, the light 疋' additive is also hydrophilic and has higher dispersibility or solubility in ^. For example, The good thing is that caprolactam, dextrin, starch, fiber are exaggerated 斟 yesterday ^ iron, 隹 糸 糸 曰 纤维素, cellulose fiber, gelatin, agar, wheat flour, gluten, 嶎 嶎Known eucalyptus, polyurethane resin, cyclic fluorene resin, fluororesin, propylene glycol resin, methyl acrylate resin, phenylpandip diamine resin, polyester resin, poly-imine resin, Polyethylene tree" 曰 ♦ ethyl alcohol, polyacrylamide, polyethylene oxide, protein, ribonucleic acid, ribonucleic acid, polycrystalline soil, phenol, benzoic acid. Latex or emulsion can also be used. The water-dispersible material. Furthermore, the low-dispersibility or solubility of the water is higher, so the water resistance is generally insoluble in the addition of salt, other reactive monomers, polymers, or oligomers. However, the use of latex or emulsion to improve the water resistance of the film. : Using a hydrophobic clay such as organic smectite as a point soil, using a solvent other than water or a mixture of water and an elixir, and a mixed solvent of a hydrophilic bath as a solution == use is hydrophilic and In the case of the dispersibility in the water or the additive of the car, in this case, if it is an additive with low solubility, then the sorrow of the sorrow of the knife is U or the fruit of the fruit. #土膜是形成性性, 八... Fruit, a clay film with high water resistance can be obtained. Additives of acid = ^, for example, benzophene resin, propylene glycol = family = _ acid _ resin 'Alipid Polycarbonate Brewing Tree XS Lanthanum Resin, Aliphatic Polyester Resin, Hydrocarbon Resin, Ring Charm @ & Months fat private polyene women's secret fat, polyamine resin, polyphenylene bond Tether tree

H7849-991〇14.doc S • 49. 1361171 A thermoplastic resin such as a thermoplastic polyimine resin, a polyacetal resin, a polysulfonated resin, or an amorphous fluorine resin. Epoxy resin, thermosetting modified polyphenylene ether resin, thermosetting polyimine resin, urea resin, allyl resin, enamel resin, benzoquinone, and phenol; A thermosetting resin such as a polyester resin, a bismaleimine diazine resin, an alkyd resin, a furan resin, a melamine resin, a polyamino phthalate resin, or an aniline resin. Further, a photocurable resin may be used, and examples thereof include an epoxy resin containing a latent photocationic polymerization initiator. Further, in the case where the photocurable resin is cured, it is also possible to heat the light while irradiating the light. In addition, the present invention can also be used together with a thermosetting resin and a photocurable resin, and a curing agent can be used in combination with a curing agent. Then, as long as it is generally cured by a thermosetting resin and a photocurable resin. , there is no special limit. Specific examples of the curing agent include a polyfunctional amine, a polyamine, a fatty acid, and a benzene resin. Specific examples of the curing catalyst include odorazole and the like. These hardeners and hardening catalysts may be used singly or in combination of (10) or more. Further, the above resins may be used singly or in combination of two or more. The above is mainly a resin containing a carbon atom in the main chain, but the main chain does not necessarily have to contain a carbon atom, for example, a resin which contains a stone atom in the main chain, or a resin mainly containing a stone and oxygen in the main chain (for example) , Shixi Ketone). Further, as the additive, a salt containing an organic ion such as a salt, a scale salt or a ten-salt salt used in the treatment of the clay described above may be used. Therefore, the combination of the salt and the clay is high, so it can be preferably used as an additive. especially

117849-991014.doc •50· 1361171 /, an additive containing more than two of the above organic salt parts in one knife, which improves the clay film by cross-linking the layers of clay crystals to improve the interlayer bonding force of the clay crystals Water resistance and gas barrier properties. Examples of the additive containing two or more organic salt sites include, for example, a unit containing two or more organic salt sites, and a chain containing a stone atom or a chain containing a stone atom and a milk atom (for example, Molecular or ketonic acid, etc.) linked molecules. Further, it can be exemplified by a fraction of a portion containing a salt of the above-mentioned organic salt portion, a vinyl group or an epoxy resin having a polymerizable portion. Furthermore, the 'additives are not limited to those that contribute to the strength improvement of the clay film. For example, in the case of the desire to pay and the flame retardancy, the addition of a helmet-like flame retardant such as antimony trioxide is required. A plasticizer such as dimethyl phthalate may also be added when the shape of the king is used. However, in the case of the w-transparent clay film, it is preferred that the above additives are less transparent or less colored. Further, the type of the solvent used in the present invention is not particularly limited, and water or an organic solvent may be used instead. Further, the force J has a small amount of water such as an organic substance such as N-monomethylformamide, ethanol or methanol, or a salt. The purpose of adding the organic matter, the salt, and the like is to change the dispersibility of the soil in the clay-containing liquid, to change the viscosity of the clay-containing liquid, and to improve the uniformity of the clay film. In order to sufficiently disperse the hydrophobic clay, it is effective to add a highly polar solvent such as methanol. In particular, when the main solvent is a solvent having a relatively small polarity such as toluene, it is preferred to add a highly polar solvent such as methanol in a main solvent. Adding a highly polar solvent such as methanol, and a better 疋 main solvent in β. 1

S 117849-991014.doc -51 - 1361171 Above 20 wt%, more preferably 〇 5 m% or more i5 correction %. Add a small amount of sterol to the dispersion of the aqueous clay, and the sterol will invade the layers of the clay crystals of the condensed hydrophobic clay to enlarge the interval of the layers. If sufficient time and shear force are applied, It can be dispersed near the unit layer of the crystal of the clay. Since the dispersion of the clay crystals is extremely promoted, and there is almost no clay agglomerate, most of the clay is peeled off until the vicinity of the unit layer, thereby obtaining a clay-containing liquid which is extremely uniformly mixed with an additive and a binder. Further, by adding methanol or the like in this way, the clay-containing liquid is promoted to produce a clay film, and in particular, the effect of greatly reducing the haze can be achieved in the transparent clay film. Further, in the case where the treated hydrophobic transfer soil is applied by using f, an aromatic hydrocarbon (for example, toluene, xylene), a screaming type (example ^, yoke, tetrahydrofuran), a ketone can be used as a solvent. Classes (eg, propyl-, methyl ethyl ketone), aliphatic hydrocarbons (eg, N-octane) 'alcohols (eg, methanol, ethanol, isopropanol), dentate hydrocarbons (eg, chloroform, dichloro A, B, B, B, or Ν, Ν dimethyl carbamide, N-methylpyrrolidone, dioctyl phthalate, dimercapto sulfoxide, methyl cellosolve, etc. The type of organic solvent in which the hydrophobic clay is dispersible depends on the type of the organic functional group on the surface of the crystalline clay which exhibits hydrophobicity, so it is necessary to select the appropriate one. Also, attention should be paid to the final clay containing liquid. Selection of the solubility and dispersibility of the additive (4) Preferably, the organic solvent of the dispersibility of the clay and the solubility and dispersibility of the additive are selected, however, the solvent and additive liquid of the clay dispersion is 117849- 99l〇l4.d〇c •52- 1361171 solvent is not necessary In the same kind, the clay and the additive are not particularly limited as long as they are mixed to obtain a clay-containing liquid. The present invention will be further described in detail with reference to examples. [Example 1] Synthetic stone (Sumecton SA, manufactured by Kunimine Industries Co., Ltd.) is used as a clay, and sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) is used as an additive. 10.2 g of clay and 594 ml of pure water together with a spinner are placed in the plastic. In a sealed container, shake vigorously at 25 ° C for 2 hours to obtain a uniform clay dispersion. In addition, 18 g of sodium polyacrylate and 594 Μ pure water together with the rotor were placed in a plastic sealed container. After shaking vigorously for 2 hours at 25 °, the mixture was stirred for a minute at a rotation speed of ΐθθθθ ΓΡΠ1 using a homogenizer to obtain a uniform additive-containing liquid. At this time, the additive-containing liquid was heated and the temperature was raised to about 6 Torr. (3, Liquid The viscosity gradually decreases. Then, the clay dispersion and the additive-containing liquid are placed together with the spinner in a plastic compact. In the container, shake vigorously for 2 hours at 25°, and then use a homogenizer to stir at a rotation speed of 10,000 rpm for 2 minutes to obtain a uniform clay-containing liquid. At this time, the clay contains liquid heat and the temperature rises to, The viscosity of the 90 C clay-containing liquid gradually decreases. Further, about 9 〇. The clay-containing liquid is placed in a vacuum degassing device and degassed for 20 minutes under a declination condition of 0.08 MPa or less. The clay containing liquid is applied to a flat portion of the surface of the polypropylene tray. In the coating process of the clay containing liquid, a stainless steel knife is used. 7849-9910 】 4.doc -53· 1361171 with a guide rail, the partition member Used as a guide, thereby forming a clay film containing a uniform thickness. The tray was placed in a forced air oven and heated to a temperature of 6 Torr for about 6 hours to dry. The clay film formed by peeling off the tray was obtained as a uniform clay film having a thickness of about 22 μm. The obtained clay film has mechanical strength which can be used as a stand-alone film. Further, the transparency was high, and the exchangeability was excellent, and the flexibility of the clay film was confirmed to be bent into a cylindrical shape having a radius of 6 mm. However, cracks and the like were not generated, and no defects were caused. In addition, in order to confirm the transparency of the clay film, the transmittance of the wavelength range of 2 〇〇 nm or more and 800 nm or less is measured by the ultraviolet visible spectrophotometer "UV-3101PC" manufactured by Shimadzu Corporation. A transmittance of 85% or more in the range of 2 to 800 nm (see Fig. 1), and coloring cannot be confirmed. Further, the entire film of the clay film was measured using a turbidity meter "NDH2000" manufactured by Nippon Denshoku Industries Co., Ltd. The light transmittance was 91.7%, and the haze (turbidity) was 2.3%. Then, in order to confirm the dimensional stability of the clay film, use sn

The "TMA/SS220" manufactured by Nanotechnology Co., Ltd. measures the coefficient of linear expansion. The sample has a width of 3 mm and a load of 2 g. Take 5. The heating rate of ()/in in was heated to 233 ° C, and then cooled to 3 It:, and then immediately heated to 3 Torr at a heating rate of 5 ° C / min. (:, the coefficient of linear expansion was measured. As a result, The average linear expansion coefficient in the temperature range of 40 ° C to 250 ° C is 5 4 ppm / ° C, and the value of the linear expansion coefficient is substantially fixed in the above temperature range. To confirm whether the clay film is highly aligned with the clay crystal layer The laminater 'analyzes the x-ray diffraction using the X-ray diffraction device "Rint_ 117849-991014.doc •54·250〇" of Rigaku Co., Ltd. The wavelength of the 乂 line used is Cu/Ka 54056 A. In the X-ray diffraction spectrum (refer to Fig. 2), the position of 2Θ is 7 44 (converted to the interlayer distance, 1.19 nm), the main body of the green can be identified, so that the clay crystal layer in the clay film is highly layered and densely aligned. .

In addition, using the TEM "HF 2〇〇〇" manufactured by Hitachi, Ltd., the electron micrograph of the profile of the clay crucible was taken, and it was found that the average interlayer distance was about L2 nm, the clay crystal layer was aligned, and the dense layer was evenly structured. Body (see Figure 3). Further, in order to confirm the gas barrier property of the clay film, the gas permeability coefficient "Gasperm_i" manufactured by JASCO Corporation was measured. As a result, it was confirmed that the oxygen permeability coefficient at room temperature was less than 3.2 x 10 em sicmHg-i, and it was found that it exhibited high gas barrier properties. [Example 2] When a clay film was produced in the same manner as in Example 1, the clay-containing liquid of a tray made of a polypropylene was changed to produce three pieces of #土膜 having different film thicknesses. The film thickness of the obtained territories was 13, 19 μΓη, and 24 μ〇ι, respectively. The transmittance was measured in the same manner as in Example 1. The transmittance of the film having a thickness of 13 μm was in the range of 278 nmw 00 nm. The transmittance of the film of the film thickness (four) array was in the range of 344 nm to 800 nm, and the film thickness was The transmittance of the film of 24 μm is in the range of 326 nm to 8 〇〇 nm, and both have a transmittance of 85% or more, and coloring cannot be confirmed. Further, the shape of the ultraviolet absorbing light |# was substantially the same as that of the clay mash of Example 1. 117849-991014.doc • 55· 1361171 Further, the total light transmittance was measured in the same manner as in Example 1, and the film thickness was 13 μηη, which was 91.7%, the film thickness was 19 μηη, which was 90.9%, and the film thickness was 24 μιη, which was 91.6. %. Further, in the same manner as in Example 1, the haze (turbidity) was measured, and the film thickness was 13.7%, the film thickness was 19 μm, the film thickness was 19 μm, and the film thickness was 24 μm, which was 2.9%. [Example 3] The same as Example 1 was carried out to obtain a degassed clay-containing liquid. In a brass tray of 4 sizes, a smooth PET film (manufactured by Daisei Laminate Co., Ltd.) having a thickness of 50 μm was applied to the surface of the brass tray of the size of 4, and the PET film was fixed by adhesive tape. A uniform clay film having a thickness of about 22 μm was obtained in the same manner as in Example 1 except that the surface of the pet film was coated with a clay-containing liquid on the surface which was easily peeled off. The obtained clay film has mechanical strength that can be used as a stand-alone film. Moreover, the transparency is high and the flexibility is excellent. In order to confirm the softness of the clay film, it was bent into a cylindrical shape having a radius of 6 mm, but no crack or the like was produced, and no defects were caused. Further, when the transmittance was measured in the same manner as in Example 1, the transmittance was 85% or more in the range of 264 11 〇 1 to 8 〇〇 nm 2 , and coloring could not be confirmed. Further, the shape of the ultraviolet visible absorption spectrum was substantially the same as that of the clay film of the example. Further, in the same manner as in Example 1, the total light transmittance was measured and found to be 92% by weight, and the haze (turbidity) was measured and found to be 1.6 °/. 》At the atmosphere of ten or three. (: The clay film is heated for an hour), and the transmittance is measured in the same manner, and the transmittance is 85% or more in the range of 385 nm to 800 nm, and coloring cannot be confirmed. The shape of the visible absorption spectrum and the heating 117849 -991014.doc •56· 136.1171 Basically the same before and 'measured in the same way' The total light transmittance is 91'1% 'Haze (turbidity) is μ%, and high heat resistance can be considered. 1] 'In the same manner as in the first embodiment, the prepared clay dispersion and the additive-containing liquid were placed in a sealed container made of plastic together with a spinner, and shaken vigorously at 25 tons for 2 hours, and then, using a homogenizer (10) The stirring speed of (4) was stirred for 20 minutes to obtain a uniform clay-containing liquid. The soil-containing liquid was not degassed, but was applied to the surface of the PET film in the same manner as in Example 3 to obtain a thickness of about (4). The clay film obtained has the mechanical strength that can be used as a separate film. For the clay film, a large number of visually identifiable bubbles can be identified on the surface, and the bumps can be clearly felt by hand contact. Example 1 The whole light transmittance was 91 8%, and the haze (turbidity) was 51%. [Comparative Example 2] Synthetic saponite (Sumecton SA manufactured by Kunimine Industries Co., Ltd.) was used as the clay, and poly was used. Sodium acrylate (manufactured by Wako Pure Chemical Industries Co., Ltd.) as an additive. Put 5.1 g of clay and 594 ml of pure water together with the rotor into a plastic sealed-barrel, shake it vigorously for 2 hours at 25, to obtain uniformity. A clay dispersion was added, and 0. 9 g of sodium polyacrylate was directly added to the clay dispersion clock, and the mixture was shaken vigorously at 25 C for 2 hours to obtain a clay-containing liquid. The clay-containing liquid was used in the same manner as in Example 3. A subsequent step of obtaining a uniform clay film having a thickness of about 17 μm is obtained. The obtained clay film has mechanical strength which can be used as a stand-alone film. To confirm the softness of the 171849-991014.doc •57- 丄 171 clay film, However, it is bent into a cylindrical shape of 6 Å, but no crack or the like is generated, and no defects are generated. Further, similarly to the embodiment, the transmittance of the ruthenium is more than 85%. The wavelength region (see _. Further, measured in the same manner as in Example i, the total light transmittance was 91.8%, and the haze (turbidity) was 7〇%. [Comparative Example 3] Clay was produced in the same manner as in Example 2. In the case of the film, the clay-containing liquid of the flow-through polypropylene tray was changed to prepare two clay films having the same film thickness*. The film thickness of the obtained clay film was 15 μm and 16 respectively. The transmittance was measured in the same manner as in Example 1. In any of the clay films, there is no wavelength region having a transmittance of 85% or more. Further, when the total light transmittance is measured in the same manner as in the examples, the film thickness is 15%, the film thickness is 16%. The μπι is 91.7%. Further, in the same manner as in Example 1, the haze (turbidity) was measured, and the film thickness was 15.7%, and the film thickness (4) was 65%. [Comparative Example 4] Synthetic saponite (manufactured by Kunimine Industries Co., Ltd.)

Sumecton SA) As a clay, sodium polyacrylate (manufactured by Wako Pure Chemical Industries Co., Ltd.) was used as an additive. 1.8 g of polyacrylic acid and 594 chaotic pure water were placed in a plastic sealed container together with a rotor, and shaken vigorously for 2 hours to obtain an additive-containing liquid. The additive containing liquid was added to 5.1 g of clay at 25. (: The violent shaking for 2 hours, however, the clay is not sufficiently dispersed, and it is considered that there are a large number of large clay aggregates, so that a clay-containing liquid suitable for making a clay film cannot be obtained 8 n7849-9910l4.doc * 58 - 136.1171 [Comparative Example 5] Using a synthetic saponite (Sumecton SA manufactured by Kunimine Industries Co., Ltd.), a sodium sulphate (manufactured by Kokuto Co., Ltd.) was used as an additive. f4 〇g clay and 196 011 pure water together with rotation Put together the plastic seal Gu Yi β ' at 22. (: violently shake for 2 hours, obtain a uniform clay dispersion and put 2g sodium polyacrylate and 198 ml pure water together with the rotor into a plastic sealed container After shaking for 2 hours under hunger, the additive liquid containing the homogenizer at a rotation speed of 1 rpm was used. Then, the clay dispersion and the additive liquid were placed together with the rotor. In a plastic sealed container, the ratio of the amount of the mold-occupied dispersion to the additive contained in the mass ratio is 3 to 7. After shaking for 22 hours at 22t: The mixture was stirred at a rotation speed of 1 rpm for 2 minutes to obtain a uniform clay-containing liquid having a clay content of less than 5% by weight. The clay-containing liquid was used without degassing, and was the same as in Example 3. A uniform clay film having a thickness of about 20 μm was obtained. In order to confirm the softness of the clay film, it was bent into a cylindrical shape having a radius of 6 mm, but no cracks were generated, and no defects were produced. In the same manner, the measurement was carried out in the same manner, the total light transmittance was 91.8%, and the haze (turbidity) was 6.3 〇/〇. [Example 4] Synthetic saponite (manufactured by Kunimine Industries Co., Ltd.) was used.

Sumecton SA) As a clay, sodium carboxymethyl cellulose (manufactured by Aldrich Co., Ltd.) was used as an additive. 117849-991014.doc 1361171 1.0 g of clay and 89 ml of pure water were placed in a plastic sealed container together with a spinner, and shaken vigorously at 25 ° C for 2 hours to obtain a clay dispersion. Also, 'put 0.18 g of dimethylcellulose and 3 〇mi of pure water together with the rotator into a plastic sealed container' and shake it vigorously at 25 °c for 2 hours, and then use a homogenizer at 10,000 rpmi. Stir for 1 minute to obtain an additive containing liquid. Then, the clay dispersion and the additive-containing liquid were mixed and shaken vigorously for 2 hours, and then the mixture was stirred for 10 minutes at a rotational speed of 1 rpm using a homogenizer to obtain a clay-containing liquid having a solid concentration of wt%. In addition, the self-rotating-common-type stirring and deaerator AR-l〇〇 (manufactured by Thinky Co., Ltd.) which has a container that revolves around the axis and rotates around the shaft is used to stir the clay-containing liquid for 5 minutes. The centrifugal force generated by the revolving motion was removed from the degassing mode in which the bubbles were mixed, and degassing was performed for 2 minutes. The obtained clay-containing liquid is placed in a plastic-made tray which can be subjected to any treatment, and is formed into a thin liquid film having a thickness of about 5 mm or less, and is subjected to a pressure reduction environment of 〇〇8 river to below for 1 minute. Vacuum degassing. A PET film prepared in the same manner as in Example 3 was placed in a tray made of a T6-sized brass plate with a thickness of Teflon. The PET film was coated with PET film. 20.1 g of clay-containing liquid (thickness: 3 mm) was applied to the surface of the fluorenone resin. Further, the surface of the applied clay-containing liquid is smoothed by using a glass rod. The tray containing the clay-containing liquid was placed in an oven and heated at a temperature of 6 Torr for about 5 hours to dry. After drying, the clay layer obtained from the film was peeled off to obtain a uniform transparent adhesive 117849-991014.doc -60·1361171 soil film having a thickness of about 卩_. The total light transmittance of the clay film was determined to be 91.3% and the haze (turbidity) was 3.5% as in the case of Example 1. [Example 5] Natural montmorillonite (Kunipia F manufactured by Kunimine Industries Co., Ltd.) was used as the clay, and sodium polyacrylate (manufactured by Wako Pure Chemical Industries Co., Ltd.) was used as an additive. 27.4 g of clay and 658 ml of pure water were placed in a plastic sealed container together with a rotor, and shaken vigorously at 25 ° C for 2 hours to obtain a uniform clay dispersion. In addition, 1.44 g of sodium polyacrylate and 丨42 mi of pure water together with a rotating rotor were placed in a plastic sealed container, and shaken vigorously at 25 ° t for 2 hours, and then 'using a homogenizer at 1 rpm. Mix for 7 minutes at the rotation speed to obtain a uniform additive-containing liquid. At this time, the additive contains liquid heat and the temperature rises to about 60 ° C, and the viscosity of the liquid gradually decreases. Then, the clay dispersion and the additive-containing liquid are placed in a plastic sealed container together with the rotor, at 25. After shaking for 2 hours, the mixture was stirred for 2 minutes at a rotational speed of 10,000 rpm using a homogenizer to obtain a uniform clay-containing liquid. At this time, the clay contains liquid heat and the temperature rises to about 90 ° C, and the viscosity of the clay-containing liquid gradually decreases. Further, immediately, a clay-containing liquid of about 90 ° C was placed in a vacuum degassing apparatus, and degassed under a reduced pressure of 8 Mpa # under 〇 . 8 minutes. Then, the clay-containing liquid was applied to a flat portion in the surface of the brass tray. In the coating process of the clay-containing liquid, a stainless steel cutter rail is used, and the partition member is used as a guide. Thus, a clay having a uniform thickness is formed. s 117849-991014.doc • 61 - 1361171 has a liquid film. The tray was placed in a forced air oven and heated at a temperature of 6 Torr <t for about 6 hours to dry. The $ film produced by peeling off the tray gives a uniform clay film with a thickness of about 40 μm. The obtained clay film can be used as a stand-alone film because of sufficient mechanical strength, and is excellent in softness. In order to confirm the softness of the clay film, it was bent into a cylindrical shape having a radius of 6 mm, but cracks and the like were not generated, and no defects were produced. [Comparative Example 6] Natural montmorillonite (Kunipia F, manufactured by Kunimine Industries Co., Ltd.) was used as a clay. Sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used as an additive. 27.4 g of clay and 65 8 ml of pure water were placed in a plastic tamper with a spinner and shaken vigorously at 25 C for 2 hours to obtain a uniform clay dispersion. To the clay dispersion, 1.44 g of sodium polyacrylate was added and shaken vigorously at 25 C for 2 hours, however, a large number of large aggregates were produced, so that a clay-containing liquid suitable for making a clay film could not be obtained. [Example 6] Natural montmorillonite (Kunipia F manufactured by Kunimine Industries Co., Ltd.) was used as a clay, and caprolactam (manufactured by Wako Pure Chemical Industries Co., Ltd.) was used as an additive. Place 27.4 g of clay and 6 〇〇 of pure water together with the rotator in a plastic sealed container at 25. . Shake vigorously for 2 hours, & and obtain a uniform clay dispersion. Further, i.44 g of caprolactam and 58 ml of pure water together with a spinner were placed in a plastic sealed container, and they were mixed by a stirrer to obtain a uniform additive-containing liquid of D7849-991014.doc-62. Then, the clay dispersion and the additive-containing liquid were placed in a plastic sealed container together with the rotor, and shaken vigorously for 1 hour at 25°, and then stirred for 2 minutes at a rotation speed of 10,000 rpm using a homogenizer. Obtain a uniform clay containing liquid. At this time, the clay contains liquid heat and the temperature rises to about 9 (TC, the viscosity of the clay-containing liquid gradually decreases. Further, about 9 〇t of the clay-containing liquid is placed in the vacuum degassing device, below 〇〇8 Degassing was carried out under reduced pressure for 40 minutes. After about 5 minutes from the start of degassing, it was almost impossible to determine that bubbles were generated from the clay-containing liquid. Then, the clay-containing liquid was applied to the flat surface of the brass tray. On the knife. In the coating of the clay containing liquid, use the stainless steel cutter guide to 'use the partition as the guide' to form a clay with a uniform thickness and a liquid film. The tray is placed in a forced air blowing type (4). It is heated at a temperature of about 6 hours to dry it. The clay film formed by peeling off the tray 'obtains a uniform clay film with a thickness of about 30. The obtained clay film has sufficient mechanical strength. It is used as a separate film', and it is excellent in softness. It is about 300 ° C per minute, and the field is heated to 3 〇 0 ° C ' at 300. (: Keep a little 睥 德, push to play 1 吋, then enter Observed. As a result, although the clay film was slightly blackened, almost the gold was cut in the female At..., and the 疋3 heart was confirmed by the naked eye. The scanning electron microscope (SEM) was used to make a bubble: The cross section of the clay film was found to be relatively uniform (see Fig. 4). The load was measured to be 5 g in the same manner as in Example 1. The dimensional stability linear expansion coefficient of the clay film was confirmed at 5 °C/min. The sample width is 3 mm 117849-99I0l4.doc • 63 - 1361171 The heating rate is heated to 148. (:, after holding at this temperature for t hours, cool to 38 C. Then, immediately at a heating rate of 5 ° c / min Heat to 2 columns. [, Determine the coefficient of linear expansion. As a result, the coefficient of linear expansion in the temperature range from the thief to the 29th generation is 1.2 to 8.0 ppm/l. To confirm whether the clay film is highly aligned and dense in the clay crystal layer. The laminate was subjected to analysis of x-ray diffraction in the same manner as in Example 1. The obtained X-ray diffraction spectrum (see Fig. 5) was at a position of 6 48 at 20 (converted to interlayer distance, 1.36 nm). Identify the dominant main peak, which indicates the clay crystal in the clay film In addition, the electron micrograph of the cross section of the clay film was taken in the same manner as in Example 1, and the average interlayer distance was also about 12 nm, and the clay crystal layer was aligned and densely laminated (see Fig. 6). The average interlayer distance observed by the microscope photograph is slightly smaller than that obtained from the analysis of the x-ray diffraction. It is generally believed that the reason is that the analysis of the X-ray diffraction is performed under the atmosphere. In the case of high vacuum, it is presumed that the reason is that the average interlayer distance is slightly reduced due to the volatilization of the water mixed in the clay film under vacuum. To confirm the gas barrier property of the clay film, oxygen is measured in the same manner as in the example. Transmission coefficient. As a result, it was confirmed that the oxygen permeability coefficient at room temperature was less than 3-2X10·11 cm2' cmHg·!, and it was found that the gas barrier performance was high. [Comparative Example 7] In the same manner as in Example 6, a degassed clay-containing liquid was obtained. The clay containing liquid is stirred by a homogenizer and the temperature is raised to about 9 〇〇c, and left at room temperature for about 30 minutes to lower the temperature to about 3 (rc, then placed in a vacuum to remove 117849-99l014.doc - 64 - 13.61171 The gas device is degassed for 4 minutes in a reduced pressure environment of 0.08 MPa or less. The generation of bubbles from the clay-containing liquid is low-frequency during the degassing process, but it can be confirmed until the end. In the same manner as in Example 6, a clay film having a thickness of about pm can be obtained by using the clay-containing liquid, and the obtained clay film can be used as a separate film because of sufficient mechanical strength, and is excellent in flexibility. The temperature rises by about 18. (: The heating rate is heated to 300 ° C, and it is observed at 30 °C for 1 hour. As a result, the clay film is slightly blackened, and it can be considered that there are many dots. The diameter is a circular protrusion of about 55 to about 5 claws. When the cross section of the film is observed by SEM, a large number of fine voids can be observed (see Fig. 7), and the gas contained in the clay-containing liquid is shown. Incomplete removal of ingredients In the case of a shape, bubbles (voids) derived from a gas component mixed in a clay-containing liquid are mostly left inside the clay film, and a circular protrusion as described above may be generated upon heating. [Example 7] Hydrophobic hectorite is used. (Lucenthe SAN manufactured by C〇〇pchemical Co., Ltd.) As a clay, [451 (made by Asahi Kasei Chemicals Co., Ltd.) was used as an additive. 8.5 g of clay was placed in a triangle together with a mixed solvent of 62 g of toluene and 2 g of methanol. In the flask, stir at a temperature of about 25 ° (for 2 hours) to obtain a uniform clay dispersion. In addition, put the Asaflex L451 and 16 g of toluene into the Erlenmeyer flask, stir the small one by the rotor. At this time, a uniform additive-containing liquid is obtained. Then, the clay dispersion and the additive are mixed in other Erlenmeyer flasks, and 117849-99I014.doc -65-1361171 is liquid, and the force is 25 C and the rotor is given for 2 hours. Thereby, the clay-containing liquid of the hook is obtained. Then, the clay-containing liquid is placed in a reduced environment, and degassed for several minutes while stirring. The cover is used in the same manner as in the fourth embodiment. The two sides of the same brass tray are flattened to the portion of the aluminum foil facing the bottom surface of the tray. The same PET film as the user in the third embodiment is placed in the tray (ie, placed on (4)), The PET film is coated with a soil containing liquid. In the clay containing liquid coating, the steel tool guide rail is used, and the partition member is used as a guide, thereby forming a liquid film containing a uniform thickness of the clay. It is placed on a hot plate and heated under the temperature of a thief for about 3 minutes to separate the clay film formed by peeling the L from the tray to obtain a uniform green film having a thickness of about 57 (four). The obtained clay film can be used as a stand-alone film because of having sufficient mechanical strength, and has flexibility. In order to confirm the transparency of the clay film, the transmittance was measured in the same manner as in the Example, and the transmittance was 85% or more in the range of 360 to 800 nm, and coloring could not be confirmed. Further, the measurement was carried out in the same manner as in Example ι, and the total light transmittance was 9 〇.1%, and the haze (turbidity) was i 6%. At 200. . The clay film was heated for 3 minutes, and the transmittance was measured to have a transmittance of 85% or more in the range of 420 to 800 nm, and the coloring was confirmed by the method. Further, the measurement was carried out in the same manner, and the total light transmittance was 91.1%, and the haze (turbidity) was 1.7. Further, when the clay film is immersed in the water of (10) for 24 hours, there is no change which can be confirmed with the naked eye, and the strength is hardly decreased, so that it has a souther water resistance. According to the weight change before and after the immersion The calculation was carried out, and the water absorption caused by the immersion I17849-991014.doc -66 - 13*61171 was about 1.9 ° / 〇. [Comparative Example 8] Hydrophobic hectorite (manufactured by Coopchemical Co., Ltd.) was used.

Lucentite SAN) As clay, use Asaflex L451 (Asahi Kasei

Chemicals Co., Ltd.) as an additive. 8.0 g of clay and 80 g of toluene were placed in an Erlenmeyer flask and mixed by a rotator at about 25 ° C for 3 hours to obtain a uniform clay dispersion. Further, 1.5 g of Asaflex L451 and 10 g of toluene were placed in an Erlenmeyer flask, and stirred at about 25 ° C for about a few hours by a rotator to obtain a uniform additive-containing liquid. Using this clay-containing liquid, a uniform clay film having a thickness of about 84 μm was obtained in the same manner as in Example 7. . The obtained clay film can be used as a separate film because of sufficient mechanical strength, and has flexibility.

The rate was 90.8% and the haze (turbidity) was 23 8 〇/〇. [Example 8] In the same manner as in Example 1, the clay-containing liquid having the same composition was adjusted.

A clay having a uniform thickness is formed to contain a liquid film. . In the ugly 4, put the same ρΕΤ film as that of the third embodiment (the ρΕΤ is set on the tray), apply the clay-containing liquid to the enamel film, and apply the separator to the clay-containing coating. The guide, by means of 117849-991014.doc -67· 1361171, the tray is placed in a forced air oven, and heated at 6 (rc temperature for about 6 hours, in a state where the pET film as a support is deformable) After the drying is completed, the PET film is bent integrally with the clay film, and a part thereof is not in contact with the bottom surface of the tray to be separated. The generated clay film is taken out together with the PET film in the atmosphere. After leaving for 30 minutes, the f-curve was substantially removed, and the clay film was peeled off from the ρΕτ film to obtain a uniform clay film having a thickness of about 22 μη. The obtained clay film has mechanical strength which can be used as a stand-alone film. Further, the flexibility is excellent. Further, cracks or cracks cannot be found in the entire film. To confirm the softness of the clay film, the f-curve is a circle having a radius of 6 :: No cracks were formed in the cracks, etc. Further, the transmittance was measured in the same manner as in Example 1, and the transmittance at a wavelength of 5 〇〇 nm was 89.3%, and 8 〇 in the range of 264 11 „1 to 80 〇 nm. The transmittance of % or more was measured in the same manner as in Example 1. The total light transmittance of the clay film was 92.0%, and the haze (turbidity) was 丨6%. [Example 9] The thickness was obtained in the same manner as in Example 8. A uniform clay film of about 21 μηι (one-man dry film). The obtained clay film has mechanical strength which can be used as a stand-alone film, high transparency, and excellent flexibility. The same as in Example 1. The total light transmittance of the 'Clay film was 91.5%, and the haze was %. The surface roughness of the clay film was measured by X Ra〇10, using the surface roughness meter P Step IQ manufactured by KLA-Tencor. Is 39 nm ° H7849-991014.doc -68-

I36117J Immediately after film formation, the clay film was immersed in pure water for about 5 seconds. After lifting, it was sandwiched between the same ρΕτ film coated with fluorenone resin on the surface. The smooth surface is in contact with the clay film. Then, after the glass film was stretched on the PET film to smooth the clay film and the excess moisture was squeezed out, one of the PET films was peeled off and placed under a pressure of about 2 Torr to dry. The dried clay film was peeled off from the other PET film to obtain a uniform clay film having a thickness of about 10 μm. The obtained transparent clay film has a tensile strength of 32 MPa and has mechanical strength which can be used as a stand-alone film. Also, the transparency is high and the flexibility is excellent. Be sure. The soft clay film was tolerated and bent into a cylindrical shape with a radius of 6 mm, but cracks and the like were not generated, and no defects were generated. In addition, in order to confirm the transparency of the clay film, the transmittance in the wavelength range of 190 nm or more and 800 nm or less is measured in the same manner as in Example ,, and the transmittance is 85% or more in the range of 312 nm to 800 nm. And can't be sure to have coloring. Further, in the same manner as in Example 1, the total light transmittance of the transparent clay film was measured to be 91 7%, and the haze was . Further, the surface roughness of the clay film measured by Ra was also 35 nm. The transparent clay film was placed at 1 atmosphere and the temperature was 24. After one week in a clean room having a humidity of 45%, the total light transmittance and haze were measured in the same manner as above, and the total light transmittance was 91.8%, and the haze was 1.6%. Further, after the same measurement was carried out for one month, the total light transmittance was 91.9%', and the haze was 1.5%. [Comparative Example 9] As in Comparative Example 2, a uniform clay film having a thickness of about 17 μηη was obtained. Place

S 117849-991014.doc -69- 1361171 The obtained clay film has mechanical strength which can be used as a stand-alone film. Moreover, the transparency is high and the flexibility is excellent. The measurement was carried out in the same manner as in Example 1. The total light transmittance of the clay film was 91.8%, and the haze was 7.0%. Further, the surface roughness of the clay film measured in the same manner as in Example 9 was 5 5 ηηι. The clay film was placed in a clean room maintained at 24 ° C, 1 atmosphere, and 45% humidity, and the haze increased to 21.4% after one week and increased to 27.0% after one month. Further, the surface roughness of the clay film after being placed for one month was 122 nm by Ra. [Example 10] The primary dried film in which the haze was increased to 27.0% in Comparative Example 9 was immersed in pure water for about 5 seconds, and after being lifted, it was sandwiched between pET films having an anthrone resin coated on the surface. At this time, the smooth surface of the two PET films was brought into contact with the clay film. Then, after the glass film was stretched on the PET film to smooth the clay film and the excess moisture was squeezed out, one of the PET films was peeled off and left to stand at about 20 ° C for a day and dried. The dried clay film was peeled off from the other PET film to obtain a uniform clay film having a thickness of about 12 μm. The obtained transparent clay film had a tensile strength of 35 MPa and had mechanical strength which can be used as a stand-alone film. Moreover, the transparency is high and the flexibility is excellent. In order to confirm the softness of the transparent clay film, it was bent into a cylindrical shape having a radius of 6 mm, and cracks and the like were not generated, and no defects were caused. In addition, in order to confirm the transparency of the clay film, the transmittance in the wavelength range of 190 nm or more and 800 nm or less is measured in the same manner as in Example ,, and the transmittance is 85% or more in the range of 3^ nm to 800 nm. And can't be sure to have coloring. Further, the total light transmittance of the transparent clay film measured in the same manner as in Example I was 92.%, and the haze was 〇83%. Further, the surface roughness of the clay film measured in the same manner as in Example 9 I17849-991014.doc 136, 1171 was 32 nm in terms of Ra. The transparent clay film was placed in a clean room maintained at 1 atmosphere, a temperature of 24 ° C, and a humidity of 45% for one week, and the total light transmittance and haze were measured in the same manner as above, and the total light transmittance was 9.2. .0%, the haze was Ό "86%. Further, after performing the same measurement for one month, the total light transmittance was 92.1%, and the haze was 0.84%. [Example 11] The mist in Comparative Example 9 The dry film is increased to 27.0%, and the pure water is sprayed by rinsing the surface to swell the clay film, and then sandwiched between the PET film coated with the fluorenone resin. At this time, the two pet films are made. The smooth surface is in contact with the clay film. Then, in the same manner as in the example, the glass roll is stretched on the ΡΕτ film to form a glass roll elongated clay film, and the excess PET is peeled off, and then one of the PET films is peeled off and placed under about 2 art. It is dried overnight. The dried clay film is peeled off from the other PET film to obtain a uniform clay film having a thickness of about ημηι. The obtained transparent clay film has a tensile strength of 3 MPa and can be used as a stand-alone film. Mechanical strength, and high transparency, In order to confirm the softness of the transparent clay film, it is bent into a cylindrical shape with a radius of 6 mm, and no cracks or the like are generated, and no defects are produced. Also, in order to confirm the transparency of the clay film' In the same manner, when the transmittance in the wavelength range of 19 nm or more and 800 nm or less is measured in the same manner, the transmittance in the range of 305 nm to 800 nm is 85% or more, and coloring cannot be confirmed. EXAMPLES: The measurement was carried out in the same manner, and the total light transmittance of the transparent clay film was 91.9% 'haze (10). Further, to ^

S 117849-991014.doc -71 - 1361171 Calculated, the surface roughness of the clay film measured in the same manner as in Example 1 was 26 nm. The transparent clay film was placed at a pressure of 24 C C, humidity. After one week in a 45% clean room, the total light transmittance and the haze were measured in the same manner as above, and the total light transmittance was 92.0%, and the haze was 〇.64%. Further, after the same measurement was carried out for one month, the total light transmittance was 92.1%, and the haze was 0.65%. [Industrial Applicability] The method for producing a clay film of the present invention can produce a clay film in which clay and additives are uniformly dispersed, and it is difficult to cause cracks and cracks, and the like, which can be used as an independent film. The clay film-based clay and the additive of the present invention are uniformly dispersed, are hard to cause defects such as cracks and cracks, and have a clay film which can be used as the strength of the independent film. In addition, the light transmittance is high and the haze is small, and even if it is placed in the atmosphere, it is difficult to cause a transparent clay film whose haze increases over time. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the ultraviolet visible absorption spectrum of a clay film. Figure 2 is a graph showing the X-ray diffraction spectrum of a clay film. Fig. 3 is a view showing a cross-sectional photograph of a TEM of a transparent clay film. Fig. 4 is a view showing a cross-sectional photograph of a Sem of a clay film. Fig. 5 is a view showing the X-ray diffraction spectrum of the clay film. Fig. 6 is a view showing a cross-sectional photograph of a TEM of a clay film. Fig. 7 is a view showing a cross-sectional photograph of a Sem of a clay film.

117849-99l0J4.doc •72·

Claims (1)

f. Patent application scope: · A method for manufacturing a clay film' is characterized by the following steps: The clay contains liquid adjustment step, which separately prepares a clay dispersion in which the clay is dispersed in a solvent, and disperses the additive or Dissolving in the solvent, the additive-containing liquid is mixed with the above-mentioned point soil dispersion liquid and the additive-containing liquid, so that the ratio of the above-mentioned additives in the total amount of the clay and the additive is more than 0 wt% and 30 wt% or less. The clay liquid is obtained; and the dried/dry step #' is obtained by disposing the clay-containing liquid on the surface of the support and removing the solvent. 2. The method for producing a clay film according to (1), which comprises a degassing step of reducing a gas contained in the clay-containing liquid. 3. The method of producing a clay film according to claim 1 or 2, which comprises a peeling step of peeling off the dried product obtained through the above drying step from the support. 4. The method for producing a clay film according to claim 1 or 2, wherein in the clay containing liquid adjusting step, the clay dispersion liquid and the additive-containing liquid are mixed at a temperature higher than a normal temperature to obtain the clay-containing liquid. [5] The method for producing a clay film according to claim 2, wherein the temperature of the clay-containing liquid is higher than a normal temperature and is placed under a reduced pressure environment to reduce a gas contained in the clay-containing liquid. 6. The method for producing a clay film according to the item 2, wherein the temperature of the clay-containing liquid is higher than a normal temperature and stirred under a reduced pressure atmosphere, whereby the gas contained in the clay-containing liquid is reduced. H7849-991014.doc 7: The method of claim 3, wherein the support has the softness of the support body after being dried in a deformable state, and the dried product is dried. Peeling from the above support. 8. The method for producing a clay film according to claim 7, wherein the support system is a resin film. In the above-mentioned support body, the method for producing a clay film according to Item 7 is subjected to a peeling facilitation treatment. 10. The method of producing a clay film according to the item 7, wherein the support is subjected to a water repellent treatment. U. The method for producing a clay film according to claim 1 or 2, which comprises the step of re-drying the liquid on which the clay is swollen or the liquid in which the additive is dissolved or dispersed, on the surface of the dried product obtained through the drying step described above. 'Re-drying>> 12. The method of claim 1, wherein the liquid is applied to the surface of the dried object by dipping in the liquid. η. The method of manufacturing a clay joint according to claim η, wherein said liquid is applied to said dried object surface by spraying said liquid. 14. The method of producing a clay film according to claim η, wherein the smoothing member having a smooth surface of the above-mentioned dry matter disk which is at least partially swollen near the surface is contacted by arranging the liquid on the surface, and after the surface is smoothed, the liquid is made The method of producing a clay film according to claim 14, wherein the smoothing member has flexibility and is deformable, and the liquid is dried again in a state where the dried product is in contact with the smoothing member. 117849-991014.doc 13*61171 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. According to the method for producing a clay film of claim 1 or 2, the water has a high affinity and is easily dispersed. Hydrophilic in water ': clay' soil pair: a method for producing a clay film of claim 1 or 2, wherein the above-mentioned clay is compatible with a solvent having a high affinity for an organic solvent and easily dispersed in an organic solvent:: production of a film The method wherein the hydrophobic clay is obtained by exchanging inorganic ions contained in a hydrophilic material into an organic ion having an affinity and dispersibility with respect to an organic solvent, wherein the organic ion comprises an ammonium ion, a scale ion, and an imidazolium ion. For example, the method for producing a clay film of claim 17 wherein the hydrophobic clay is exchanged for the hydroxyl group of the octahedral thin layer of the constituent elements of the clay into other hydrophobic substituents. The method for producing a clay film according to claim 1 or 2, wherein the obtained clay film is transparent. A clay film characterized by being a clay film of any one of claims 1 to 2 Manufacturing method, manufacturer, layered clay Crystallization is formed in the film thickness direction. As in the clay film of claim 21, the average line expansion coefficient of #自至至代代 is 20 ppm or less. For the clay film of Item 21, the tensile strength is 丨〇 The clay film of any one of Claims 21 to 23, which has a haze of 5% or less. The clay film of any one of Items 21 to 23 has a haze of 5% or less, and The total light transmittance is 85% or more, and the light transmittance in the wavelength range of 4 〇〇 nm or more and 800 nm or less is 85% or more and 95% or less. S 117849-991014.doc 1361171 26. As in any of claims 21 to 23 The clay film of the item has a haze of 2q/. The following 'and the total light transmittance is 85% or more, and the light transmittance in the wavelength range of 400 nm or more and 800 nm or less is 85% or more and 95% or less. The clay film of any one of 21 to 23 has a haze of less than 1%, and the total light transmittance is 85% or more, and the light transmittance in the wavelength range of 400 nm or more and 800 nm or less is 85% or more and 95% or less. 28. The clay raft of claim 25, which has a haze change in haze at 24 〇c, i air pressure, and humidity of 45%. _ 2% or more and 2% or less. 29. The clay film of claim 21, wherein the film thickness is greater than 丨5 μηη. 30. An electronic paper characterized in that at least a portion thereof is utilized by claim 1 or 2. A clay film obtained by a method for producing a clay film, or a clay film of claim 21. 31. A flexible substrate, characterized in that at least a part thereof is produced by the method for producing a clay film according to claim 1 or 2. The obtained clay film, or the clay film of claim 21. A flexible printed circuit board characterized in that at least a part thereof is composed of a clay film obtained by the method for producing a clay film of claim 1 or 2, or a clay film of claim 21. 33. A seed substrate characterized in that it is mounted with an electronic component having a non-light-emitting organic semiconductor or an amorphous inorganic semiconductor and has gas barrier properties, at least a part of which is made of clay using the request item or The clay film obtained by the method for producing a film or the clay film of claim 21. 34. A gas barrier film characterized in that it protects an electronic component having a non-emitting organic semiconductor or an amorphous inorganic semiconductor from being affected by a gas, and H7849-991014.doc 1361171 is at least partially utilized by a request The clay film obtained by the method for producing a clay film of item 1 or 2, or the clay film of claim 21. E 117849-991014.doc