WO2007088815A1 - Film d'argile et son procede de production - Google Patents

Film d'argile et son procede de production Download PDF

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Publication number
WO2007088815A1
WO2007088815A1 PCT/JP2007/051404 JP2007051404W WO2007088815A1 WO 2007088815 A1 WO2007088815 A1 WO 2007088815A1 JP 2007051404 W JP2007051404 W JP 2007051404W WO 2007088815 A1 WO2007088815 A1 WO 2007088815A1
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WIPO (PCT)
Prior art keywords
clay
film
containing liquid
additive
clay film
Prior art date
Application number
PCT/JP2007/051404
Other languages
English (en)
Japanese (ja)
Inventor
Takeo Ebina
Fujio Mizukami
Hideyasu Tanaka
Norikiyo Nakagawa
Original Assignee
National Institute Of Advanced Industrial Science And Technology
Asahi Kasei Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Institute Of Advanced Industrial Science And Technology, Asahi Kasei Kabushiki Kaisha filed Critical National Institute Of Advanced Industrial Science And Technology
Priority to JP2007556848A priority Critical patent/JP5688783B2/ja
Priority to CN2007800038740A priority patent/CN101374766B/zh
Publication of WO2007088815A1 publication Critical patent/WO2007088815A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28C1/00—Apparatus or methods for obtaining or processing clay
    • B28C1/02—Apparatus or methods for obtaining or processing clay for producing or processing clay suspensions, e.g. slip
    • B28C1/04—Producing suspensions, e.g. by blunging or mixing; with means for removing stones
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28C1/00—Apparatus or methods for obtaining or processing clay
    • B28C1/02—Apparatus or methods for obtaining or processing clay for producing or processing clay suspensions, e.g. slip
    • B28C1/06—Processing suspensions, i.e. after mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28C1/00—Apparatus or methods for obtaining or processing clay
    • B28C1/02—Apparatus or methods for obtaining or processing clay for producing or processing clay suspensions, e.g. slip
    • B28C1/06—Processing suspensions, i.e. after mixing
    • B28C1/08—Separating suspensions, e.g. for obtaining clay, for removing stones; Cleaning clay slurries
    • B28C1/084—De-aerating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols

Definitions

  • the present invention relates to a clay film and a method for producing the same.
  • the present invention also relates to an electronic paper, a substrate, and a gas barrier film that are at least partially composed of a clay film.
  • the manufacturing technology of (D) is dramatically improved, and thin displays that cannot be achieved with conventional CRTs have become a reality.
  • Almost all current FPDs have devices formed on glass substrates, and there is no practical FPD that uses substrates other than glass substrates.
  • the reason for this is that the glass substrate has high heat resistance and is suitable for forming a drive circuit or member for a display that needs to be formed at a high temperature, and is given to such a drive circuit or member having a small linear expansion coefficient. Stress can be suppressed, wiring breakage and component characteristic fluctuations are small, light is easy to extract because it is transparent in the visible light range, and oxygen and water vapor from the outside that has high gas barrier properties can be prevented. It can be used as a gas barrier material to prevent, and can maintain a high vacuum if necessary.
  • the glass substrate is apt to break without flexibility.
  • heavy substrate deformation The difficulty of handling is a problem.
  • glass substrates cannot be used for flexible displays such as electronic paper that can be bent and are intended to be bent and carried, and the device is prone to damage if it is cracked or dropped immediately upon impact. It is not very suitable for mopile use. From this point of view, there is a demand for practical use of a display substrate and a gas barrier film having heat resistance, linear expansion coefficient, transparency, gas barrier properties, and the like equivalent to glass.
  • substrates made of resin such as polyethylene terephthalate, polycarbonate, polyimide, and special glass epoxy substrates are used as flexible circuit boards.
  • resin such as polyethylene terephthalate, polycarbonate, polyimide, and special glass epoxy substrates
  • conductive ink such as conductive paste
  • the heat resistance of the resin is low and the linear expansion coefficient is generally large. Therefore, the high-temperature firing described above cannot be performed and must be performed at a relatively low temperature.
  • the metal foil since the conductive ink does not sufficiently sinter at a low temperature, the metal foil generally has a problem that the conductive performance is inferior to the wiring obtained by vacuum deposition. Since polyimide resin is relatively high heat resistance and expensive, it is difficult to use it for applications such as RFID (Radio Frequency Identification) tags where cost is the most important. From such a point of view, there is a demand for practical use of an inexpensive flexible printed board having high insulation, heat resistance and flame retardancy while having insulating properties.
  • RFID Radio Frequency Identification
  • clay is a mineral that exists in large quantities in nature, and has characteristics such as low cost, harmlessness to the human body, and burning.
  • brown “earth color” found in many natural clays is often derived from impurities such as organic matter and iron, but these impurities are not included by chemical synthesis.
  • a colorless clay can be obtained.
  • Clay minerals are roughly classified into crystalline minerals and amorphous minerals, and all crystalline parts are phyllosilicates meaning ⁇ leafy '', and basically have a layered structure due to their leafy shape. is doing. In other words, minerals generally called layered silicates are included in the category of minerals defined as clay.
  • clays are composed of tetrahedral and octahedral sheets with a thickness of about 0.2 nm to about 0.5 nm composed mainly of oxygen (O), silicon (Si), and aluminum (Al). It is made of a layered inorganic compound in the form of a sheet having a large aspect ratio and having a size in the major axis direction of several tens of nm to 5 ⁇ m.
  • a tetrahedral sheet and an octahedral sheet in such a layered silicate will be described in more detail.
  • the tetrahedron sheet has four tetragons coordinated with Si to form a tetrahedral Si.
  • Si may form an AlO tetrahedron instead of A1.
  • the octahedral sheet is formed by coordinating six hydroxyl groups (OH) or O to A1, and may be formed from magnesium (Mg) or Fe instead of A1.
  • Si is replaced by A1 etc. in the tetrahedral sheet or A1 is replaced by Mg etc. in the octahedral sheet
  • the sheet charge often becomes excessive and insufficient, and the sheet is often charged with a permanent charge.
  • the unit layer to which the sheets are bonded is defined as a clay crystal.
  • a clay crystal For example, as a material composed of clay crystals having only a tetrahedral sheet as a unit layer, it is possible to increase a series of minerals (eg, magadiite) generally called layered polycaic acid.
  • clay minerals called hydrated talcites are formed by having negative ions such as carbonate ions between the octahedral sheet having a positive charge and the octahedral sheet. It has been.
  • a clay mineral in which a clay crystal, which is a unit layer as a mineral, is formed by bonding and laminating a tetrahedron sheet and an octahedron sheet at a ratio of 1: 1, is generally called a carion mineral. Halloysite is famous. In contrast, a tetrahedral sheet and an octahedral sheet 2 and 1 are combined and stacked (ie, tetrahedral sheet, octahedral sheet, and tetrahedral sheet).
  • Clay minerals in which unitary clay crystals are formed include neurophyllite, talc, and smetite. Family clay, vermiculite, mica clay mineral, etc.
  • clays belonging to the smectite group are generally highly polar solvents such as water and alcohol (especially water). It is said that it can be uniformly dispersed in a highly polar solvent, and can be dispersed as far as one unit layer (see Non-Patent Document 1, for example).
  • a transparent film using clay there is an example in which a retardation film of a liquid crystal display is formed by coating a film with a water dispersion of synthetic saponite or synthetic hectorite.
  • This transparent film has a phase difference with respect to the progression of light by effectively utilizing a large difference in refractive index between the sheet in-plane direction and the sheet thickness direction of the clay crystal of the synthetic saponite or synthetic hectorite. Yes.
  • Some of these transparent films are obtained by peeling off a clay film formed on a support (see Patent Document 4).
  • the amount of clay contained in the clay film that is estimated to have the only mechanical strength that can be used as a self-supporting film. Is about 47% by mass, and more than half is composed of additives such as polymers. Therefore, it is presumed that the gas barrier property, which is difficult to say with a film mainly composed of clay, is not sufficient.
  • the phase difference between the in-plane direction and the thickness direction of the film becomes too large, making it suitable as a retardation film for liquid crystal displays. Because it is lost, it becomes independent In order to make a thick film that has properties, the proportion of clay must be reduced.
  • This hydrophobic clay is a hydrophobic clay in which dispersibility in an organic solvent is improved by exchanging inorganic ions contained in a smectite group hydrophilic clay dispersed in water with an organic ammonium salt or the like (Patent Document 5). See). Unlike the clay film described in Patent Document 4 described above, this clay film does not dissolve even when it is exposed to water.
  • Patent Document 5 describes that the clay partially aggregates during the production process unless the clay content is less than 20% by mass. As a result, it has been shown that haze increases and it becomes difficult to say that it is transparent (haze value is 50% or more), and the decrease in toughness becomes significant. In other words, these are equivalent to conventional nanocomposites with a small amount of clay added, and it is difficult to say that the film has a gas barrier property and dimensional stability greatly improved by mainly using clay.
  • a clay film having a strength that can be used as a film can be obtained by the following method.
  • a clay dispersion is prepared to obtain a uniform dispersion, and the dispersion is left to stand horizontally to deposit clay particles, and the dispersion medium liquid is separated into various solid-liquid separation methods (for example, This is a method of separating from a support after separation by centrifugation, filtration, vacuum drying, freeze vacuum drying, or heat evaporation method, and forming it into a film (see Patent Document 6).
  • the clay film which is mainly composed of clay and has a clay crystal layer densely and highly oriented, has (1) high heat resistance compared to the conventional clay with a small proportion of clay, and (2) oxygen. Or water (3) No pinholes in the film, (4) Flexibility, (5) Chemical resistance, (6) Low coefficient of linear expansion, (7) Confirmed that they have the common characteristics of having flame retardancy and (8) insulating properties, the materials that make up the packing, the display members, the flexible circuit board, etc. It was found that it is suitable for use in electronic materials.
  • the additive when an additive is added to the clay dispersion and mixed, the additive sometimes causes the clay to aggregate.
  • the viscosity of the clay dispersion rises rapidly and the additives are not uniformly dispersed in the clay dispersion, and non-uniform aggregates are generated in the clay dispersion, or the clay is agglomerated to form particles. In some cases, the resulting clay film becomes uneven.
  • the solubility and dispersibility of the additive in the dispersion solvent that suitably disperses the clay are low, the additive may not be sufficiently uniformly dispersed, and a problem similar to the above may occur.
  • the clay crystal layer is densely and highly oriented by increasing the proportion of clay in the clay film, it becomes difficult for the gas components remaining in the clay film to escape the clay film force. I know that it will come.
  • bubbles voids
  • the bubbles rapidly expand when heated rapidly, and a circular bulge rises on the surface of the clay film.
  • the transparent clay film there are problems that the clay film is broken and the voids cause internal scattering of light, and the clay film becomes cloudy and haze increases.
  • the gas component remaining in the clay film is derived from the gas component contained in the clay-containing liquid
  • the gas component in the clay-containing liquid is sufficiently removed and then formed into a film on the support and dried. It was considered important to obtain a clay film.
  • the clay film In particular, when preparing a clay film with a high proportion of clay, that is, when the proportion of clay in the clay dispersion is large, the clay-derived viscosity and thixotropy are remarkably exhibited, so the fluidity of the clay dispersion decreases. Shiso It becomes difficult to remove these gas components. Therefore, reducing the gas components in the clay-containing liquid is an important issue for the production of clay films with a high proportion of clay, and the development of effective methods has been required.
  • a method of dispersing clay particles in a solvent a method of shaking with a dispersing device or the like is generally used, but it was necessary to shake with a dispersing device for a long time, particularly when the solid content concentration is high. .
  • a method of shaking with a dispersing device or the like since there is generally an upper limit to the concentration of the clay dispersion that is bound by the liquid limit of the clay, it is difficult to increase the solid concentration of the clay dispersion beyond the value set by the liquid limit. It was.
  • the surface is polished and smoothed, or a layer having a composition different from that of clay such as a transparent resin is applied to form a clay film.
  • a layer having a composition different from that of clay such as a transparent resin is applied to form a clay film.
  • inspection was also performed, physical polishing was difficult because smoothing had to be performed with nano-order accuracy and because of the strength and durability of the clay film.
  • the heat resistance temperature of the applied layer is low, so that the heat resistance of the clay film is greatly reduced, the coefficient of linear expansion with respect to temperature change is different from that of the clay film, the film is warped, and the clay film is defective due to stress. In some cases, such as a problem occurs.
  • the present invention solves the problems of the prior art as described above, and clay and additives are uniformly dispersed, and it is difficult for defects such as cracks and cracks to occur. It is an object to provide a clay film having the same and a method for producing the same. In addition to that It is another object of the present invention to provide a transparent clay film having a high light transmittance and a small haze, and a transparent clay film in which haze does not easily increase with time, and a method for producing the same. Another object is to provide an electronic paper, a substrate, and a gas barrier film having such a clay film.
  • Patent Document 1 Japanese Patent Publication No. 1994 No. 95290
  • Patent Document 2 Japanese Patent Publication No. 254824
  • Patent Document 3 Japanese Patent Publication No. 30255 2002
  • Patent Document 4 Japanese Patent Publication No. 3060744
  • Patent Document 5 Japanese Patent Publication No. 37079 2006
  • Patent Document 6 Japanese Patent Publication No. 2005 No. 104133
  • Patent Document 7 Japanese Patent Publication No. 313604 2005
  • Patent Document 8 Japanese Patent Publication No. 265088 2006
  • Non-Patent Document 1 Sudo discourse meeting, “Invitation to clay science, natural face and attractiveness of clay”, Japan, Sankyo Publishing, p. 6 (2000)
  • Non-Patent Document 2 Satoshi Nakajo, “Development of polymer nanocomposites”, Frontier Publishing, Japan, p. 25-90 (2004)
  • Non-Patent Document 3 Haruo Shiramizu, “Clay Mineralogy, Fundamentals of Clay Science”, Asakura Shoten, Japan, p. 57 (1988)
  • Non-Patent Document 4 Yasushi Umezawa, “Clay Science”, Japan, No. 42, No. 4, 218-222 (2003)
  • the present invention has the following configuration. That is, in the method for producing a clay film of the present invention, a clay dispersion in which clay is dispersed in a solvent and an additive-containing liquid in which an additive is dispersed or dissolved in a solvent are prepared, and the clay and the Preparation of clay-containing liquid to obtain clay-containing liquid by mixing the clay dispersion and the additive-containing liquid so that the ratio of the additive in the total amount of the additive is 0% by mass and 50% by mass or less And a drying step in which the solvent is removed and dried after the clay-containing liquid is disposed on the surface of the support.
  • the method for producing a clay film of the present invention comprises preparing a clay dispersion in which clay is dispersed in a solvent and an additive-containing liquid in which an additive is dispersed or dissolved in a solvent, respectively.
  • the clay dispersion and the additive-containing liquid are mixed to obtain a clay-containing liquid so that the ratio of the additive in the total amount of clay and the additive is 0% by mass to 30% by mass or less. It comprises a clay-containing liquid adjusting step, and a drying step of removing the solvent and then drying the clay-containing liquid disposed on the surface of the support.
  • the said clay containing liquid adjustment process it is preferable to obtain the said clay containing liquid by mixing the said clay dispersion liquid and the said additive containing liquid at temperature higher than normal temperature.
  • the clay-containing liquid is preferably set to a temperature higher than room temperature while the clay-containing liquid is preferably set to a temperature higher than normal temperature and placed under reduced pressure to reduce the gas contained in the clay-containing liquid. It is more preferable to reduce the gas contained in the clay-containing liquid by stirring under reduced pressure.
  • the support may have flexibility.
  • the dried product is dried after the support is dried in a deformable state. Is preferably peeled from the support.
  • the support may be a resin film. Further, the support may be subjected to a peeling facilitation treatment or a water repellent treatment treatment.
  • a liquid that swells the clay or a liquid that dissolves or disperses the additive is disposed on the surface of the dried product obtained by the drying step, and is re-dried.
  • the liquid may be arranged on the surface of the dried product by dipping in the liquid, or the liquid may be arranged on the surface of the dried product by spraying the liquid.
  • the dried product which is swollen at least in the vicinity of the surface by placing the liquid on the surface, is brought into contact with a smooth member having a smooth surface, thereby smoothing the surface.
  • the liquid may be re-dried.
  • This smooth member is flexible In that case, it is preferable to re-dry the liquid in a state where the dried product comes into contact with the smooth member.
  • the clay is preferably a hydrophilic clay that has a high affinity for water and is easily dispersed in water.
  • the clay may be a hydrophobic clay that has a high affinity for an organic solvent and is easily dispersed in the organic solvent.
  • hydrophobic clays that have improved affinity and dispersibility in organic solvents by exchanging inorganic ions of hydrophilic clay with organic ions are preferred.
  • it contains at least one of the following: ion, phosphorium ion, imidazolium ion.
  • the obtained clay film may be transparent.
  • the clay film of the present invention is a clay film produced by the method for producing a clay film of the present invention as described above, and is characterized in that layered clay crystals are laminated in the film thickness direction.
  • the average linear expansion coefficient from 30 ° C to 250 ° C is preferably 10 ppm or less.
  • the clay film of the present invention has a haze of 5% or less and a total light transmittance of 85%.
  • the light transmittance in the wavelength range from 400 nm to 800 nm is preferably 85% to 95%.
  • the haze is more preferably 2% or less, and the haze is more preferably less than 1%.
  • the change with time of haze is 2% or more and 2% or less under the environment of 24 ° C, 1 atm, and humidity 45%.
  • the clay film of the present invention preferably has a film thickness greater than 15 ⁇ .
  • the electronic paper of the present invention is at least partially composed of the clay film obtained by the method for producing the clay film of the present invention as described above or the clay film of the present invention as described above. It is characterized by that.
  • the flexible substrate of the present invention is at least partially composed of the clay film obtained by the method for producing the clay film of the present invention as described above or the clay film of the present invention as described above. It is characterized by.
  • the flexible printed circuit board of the present invention provides the production of the clay film of the present invention as described above.
  • the clay film obtained by the method or the clay film of the present invention as described above is at least partially constituted.
  • the substrate of the present invention is a substrate having a gas barrier property, on which an electronic device including a non-light-emitting organic semiconductor or an amorphous inorganic semiconductor is mounted, and obtained by the above-described method for producing a clay film of the present invention.
  • the clay film or the clay film of the present invention as described above is characterized in that at least a part thereof is formed.
  • the gas barrier film of the present invention is a gas barrier film that protects an electronic device including a non-light-emitting organic semiconductor or an amorphous inorganic semiconductor from a gas, and is obtained by the method for producing a clay film of the present invention as described above.
  • the clay film or the clay film of the present invention as described above is characterized in that at least a part thereof is formed.
  • FIG. 1 is a diagram showing an ultraviolet-visible absorption spectrum of a clay film.
  • FIG. 2 is a diagram showing an X-ray diffraction spectrum of a transparent clay film.
  • FIG. 3 is a diagram showing a cross-sectional photograph of a transparent clay film by TEM.
  • FIG. 4 is a cross-sectional photograph of a clay film by SEM.
  • FIG. 5 is a diagram showing an X-ray diffraction spectrum of a clay film.
  • FIG. 6 is a cross-sectional photograph of a clay film by TEM.
  • FIG. 7 is a view showing a cross-sectional photograph of a clay film by SEM.
  • the clay film of the present invention is a film composed of clay and an additive, but the ratio of the additive in the total amount of clay and additive needs to be more than 0% by mass and 50% by mass or less. It is preferably more than 0% by mass and 40% by mass or less. In order to obtain more suitable characteristics as a clay film, the proportion of the additive is more preferably 0% by mass more than 30% by mass, and more preferably 0% by mass more than 30% by mass. It is particularly preferred that it is more than 0% by mass and 15% by mass or less. Most preferably, it is more than 0% by mass and not more than 10% by mass.
  • the proportion of the additive is 50% by mass or less (especially if it is 30% by mass or less), the proportion of the clay is small, and the characteristics that are different from the conventional nanocomposites (for example, High gas barrier properties) can be obtained.
  • the clay film is obtained by placing a clay-containing liquid containing only clay or clay and an additive on the surface of the support and drying it.
  • the role of the additive in the clay film varies depending on the function and application to be manifested, but it is generally difficult to obtain a strength that can be used as a self-supporting film with clay alone, so the additive is given more or less strength. As a function, it is required.
  • the average aspect ratio of the clay crystal is large, for example, when natural montmorillonite having an average aspect ratio of 300 or more is used, it is possible to obtain a clay film having a strength that can be used as a self-supporting film without an additive.
  • the primary role of the additive is to improve the strength of the clay film.
  • the proportion of an additive having an effect of improving the strength for example, a polymer or a polymerizable monomer
  • usually the strength of the clay film is also improved.
  • the proportion of the additive is large (exceeding 50% by mass) as in the conventional nanocomposite body, the orientation of the clay crystal and the intercalation of the additive (the target substance is inserted between the layers of the clay crystal) )
  • Due to the strength-imparting effect of the additive, etc. without considering some factors such as the degree of delamination and dispersion of the clay crystals and the removal of gas components mixed in the clay-containing liquid.
  • the present inventors have obtained an optimum method for producing a clay film that can obtain a clay film in which clay and additives are uniformly dispersed.
  • a clay dispersion in which clay is dispersed in a solvent and an additive-containing liquid in which the additive is dispersed or dissolved in the solvent are prepared.
  • the clay dispersion and the additive-containing liquid are mixed so that the ratio of the additive in the total amount of the clay and the additive is more than 0% by mass and 50% by mass or less.
  • transparent means that the total light transmittance is 70% or more, the haze is 5% or less, and the light transmittance in the wavelength range of 400 nm to 800 nm is 75% to 95%. .
  • the total light transmittance is preferably 80% or more, more preferably 85% or more, and even more preferably 88% or more.
  • the haze value is preferably 3% or less, more preferably 2% or less, and even more preferably less than 1%.
  • the light transmittance in the wavelength range of 400 nm or more and 800 nm or less is preferably 80% or more and 95% or less, more preferably 85% or more and 95% or less.
  • the total light transmittance and haze are the test methods for the total light transmittance of plastic transparent materials stipulated in Japanese Industrial Standards 3 ⁇ 4JIS K 7361, the optical test methods for plastics 3 ⁇ 4JIS K 7 105, plastic transparent materials How to determine haze of JIS K 7136.
  • the method of the present invention separately prepares a clay dispersion in which clay is dispersed in a solvent and an additive-containing liquid in which an additive is dispersed or dissolved in a solvent, and the two are mixed.
  • a clay-containing liquid an additive having a thickening effect in a solvent dissolution process or a dispersion process, or an additive having a low dispersibility or solubility in a solvent used for dispersing clay.
  • it can be uniformly dispersed in the clay-containing liquid. For this reason, the types and amounts of additive additives that can be used are hardly restricted. Further, since the clay and the additive are mixed in a sufficiently dispersed or dissolved state, the clay is prevented from aggregating and forming a non-uniform lump by the action of the additive.
  • the clay dispersion and the additive-containing liquid by dispersing or dissolving the clay and the additive in a solvent at a temperature higher than normal temperature. Then, the additive can be dispersed or dissolved more uniformly and at a high concentration.
  • the clay-containing liquid is preferably obtained by mixing the clay dispersion and the additive-containing liquid at a temperature higher than room temperature. By doing so, it is possible to prepare a clay-containing liquid having a high solid content concentration in which clay is more uniformly dispersed and the additive is more uniformly dispersed or dissolved.
  • clay or additive is added to the solvent, heater, warm air .
  • a method of mixing by stirring and shaking while heating is used.
  • the clay dispersion and the additive-containing liquid when mixing the clay dispersion and the additive-containing liquid, they may be mixed at room temperature, but the clay-dispersed liquid and the additive-containing liquid are mixed at a temperature higher than normal temperature to mix the clay-containing liquid.
  • the method of preparing is more preferable in terms of producing a uniform clay-containing liquid, and further in increasing the solid content concentration of the clay-containing liquid.
  • a clay dispersion and an additive-containing liquid are mixed, heated by a method such as a heater, hot air, or a hot water bath, and then mixed by stirring or shaking. , Mixing by shaking, and mixing by stirring and shaking while energizing the clay-containing liquid itself by applying energy with an ultrasonic dispersing device, homogenizer, or the like.
  • one type of clay may be contained in the clay dispersion, or two or more different types of clay may be mixed and used.
  • one additive may be included in the additive-containing liquid, or two or more different clays may be used in combination.
  • a clay-containing liquid may be prepared by using two or more types of clay dispersion liquids having different types of clays, or a clay-containing liquid using two or more types of additive-containing liquids having different types of additives.
  • a liquid may be prepared.
  • a clay-containing liquid may be prepared by mixing a plurality of types of clay dispersions and a plurality of types of additive-containing liquids.
  • the solid content concentration of the clay-containing liquid by mixing the clay and the additive with a solvent at a temperature higher than room temperature. If the solid content concentration of the clay-containing liquid is increased, the drying time can be shortened or a thick clay film can be easily produced.
  • the clay-containing liquid with low viscosity can only be placed on a horizontal surface perpendicular to the direction of gravity on the surface of the support, and if it is placed on an inclined surface, it will flow down. If the partial concentration is increased to form a paste, it can be disposed even on an inclined surface.
  • the fluidity of the support can prevent the clay-containing liquid from flowing out, it is necessary to devise measures to prevent the support from flowing out (for example, there is no need to provide a frame or the like). ).
  • the mixing method in the preparation of the clay dispersion, the additive-containing liquid, and the clay-containing liquid is not particularly limited as long as the clay and the additive can be sufficiently dispersed, but the container is used.
  • the method is powerful if it can disperse or dissolve in a short time due to its strong stirring power and degassing ability, and it can stir even in a gelled state exceeding the liquid limit. It is very suitable for obtaining a clay-containing liquid having a solid content concentration.
  • the clay film may be manufactured by combining a plurality of the above-described methods.
  • the ratio of the additive is 30% by mass or less
  • bubbles voids
  • the bubbles expand during heating and drying to form the clay film.
  • problems such as destruction or a decrease in transparency of the transparent film due to light scattering.
  • the higher the solid content concentration of the clay-containing liquid the higher the viscosity and the thixotropy. Therefore, when stirring is stopped, the tendency to lose fluidity becomes stronger. As a result, it becomes difficult to remove gas components mixed in the clay-containing liquid.
  • a solid-concentrated clay-containing liquid that provides a practical drying rate, it is difficult to reduce the gas components mixed in the clay-containing liquid, which has a strong tendency, without passing through some removal process.
  • the thickness of the clay film is preferably thicker than 10 ⁇ , more preferably 15 ⁇ , more preferably 20 / m, even more preferably 30 / im In particular, it is most preferable that it is thicker than the preferred 50 ⁇ . This is very different from the application of coating film, which does not require independence and is effective in many cases even with a film thickness of several ⁇ m or less.
  • the gas component mixed in the clay-containing liquid becomes less likely to be removed from the inside of the clay film during film formation. It tends to remain inside the clay film. This is because the greater the film thickness, the more likely it is that the transparency caused by light scattering, etc., or the clay film breaks during heating due to defects caused by bubbles remaining inside the clay film. It is shown that.
  • either the method of increasing the clay concentration of the clay-containing liquid or the method of increasing the liquid film of the clay-containing liquid placed on the support is considered to be normal. It is.
  • the viscosity of the clay-containing liquid increases with an increase in the solid content concentration of the clay, and the thixotropy becomes significant and the fluidity of the clay-containing liquid decreases. It is important that the removal of the water is sufficiently performed by some method. Even in the latter method, when the thickness of the liquid film disposed on the support increases, the amount of gas components mixed in increases. Therefore, it is important to sufficiently remove the gas components mixed in by some method. .
  • a method of sufficiently removing the gas component contained in such a clay-containing liquid a method of separating the gas component from the clay-containing liquid force by centrifugation may be used, but by placing the clay-containing liquid under reduced pressure, A method of performing vacuum deaeration is particularly preferable.
  • a method of performing vacuum deaeration is particularly preferable.
  • the viscosity is lowered by setting the clay-containing liquid to a temperature higher than room temperature, it is possible to perform deaeration well even with a clay-containing liquid having a high solid content. That is, before placing the clay-containing liquid on the surface of the support, it is preferable to remove the bubbles contained in the clay-containing liquid by setting the clay-containing liquid to a temperature higher than room temperature and placing it under reduced pressure.
  • the clay-containing liquid is agitated under reduced pressure, the residual gas inside the clay-containing liquid can be moved to the vicinity of the liquid surface, and the clay-containing liquid can be easily discharged. Since the increase in the viscosity of the clay-containing liquid can be suppressed, the deaeration effect is further improved. [0053] If deaeration is performed at a high temperature, the viscosity becomes low as described above, so that the deaeration can be performed well. However, since the solvent of the clay-containing liquid easily evaporates during the deaeration, the solvent is particularly useful. As a result, the solids concentration near the liquid surface rises, and as a result, solids are likely to precipitate.
  • deaeration with further stirring prevents local increase in the solid content concentration in the clay-containing liquid and prevents the viscosity from rising due to thixotropic properties, so that the deaeration is suitably performed at a high temperature. It can be carried out.
  • the degassing operation as described above may be performed after the clay-containing liquid is heated by a method such as a heater, hot air, or a hot water bath, may be performed while being heated by the above method, or may be performed by ultrasonic waves. It can be performed while applying energy with a dispersing device, homogenizer, etc., and heating the clay-containing liquid itself.
  • a stirrer or a stirring blade may be used, or a container that rotates while revolving around the aforementioned axis may be used.
  • the degassing operation as described above may be performed after the clay-containing liquid is disposed on the support.
  • a thin liquid film can be obtained by placing the clay-containing liquid on the support.
  • the gas component can be reduced efficiently.
  • the solid content concentration of the clay-containing liquid is 0.
  • the solid content concentration of the clay-containing liquid is more preferably 1% by mass or more and 15% by mass or less, and further preferably 1% by mass or more and 12% by mass or less.
  • the gas component contained in the clay-containing liquid is reduced by, for example, stirring under reduced pressure, and then the solvent is reduced by heating or the like, thereby increasing the solid content concentration.
  • a clay-containing liquid may be used. In this case, it contains more clay than the above preferred range It is also possible to increase the solid content concentration of the liquid. As a result, the drying time can be shortened while removing the gas components contained in the clay-containing liquid, so that the mass productivity of the clay film can be improved.
  • the fluidity can be lowered by increasing the viscosity and, in some cases, remarkably exhibiting thixotropy, it is possible to remove the limitations of the support as described above. That is, since the paste-like clay-containing liquid has low fluidity, the clay-containing liquid applied to the support does not flow out, and it is necessary to use a support that has a structure that prevents flow-out such as a partitioned container. Absent. Furthermore, the paste-like clay-containing liquid has an advantage that it can be applied to an inclined surface. In addition, the above-mentioned effect can be achieved even if a thickener is added to the clay-containing liquid to form a paste.
  • a heat evaporation method is preferable, but it is not particularly limited, and a known solid-liquid separation technique such as centrifugation, filtration, and pressing may be used. it can.
  • the concentration step for increasing the solid content concentration may be performed under reduced pressure.
  • concentration under reduced pressure when the thickness of the clay-containing liquid is decreased and the clay-containing liquid is caused to flow by stirring or the like, the amount of solvent evaporation increases. It is effective because it can be concentrated in a short time.
  • concentration under reduced pressure because degassing proceeds simultaneously with concentration.
  • the solvent is slowly removed to form a clay film.
  • the method for removing the solvent is not particularly limited, and for example, centrifugation, filtration, vacuum drying, freeze vacuum drying, standing in an inert gas atmosphere, and heating evaporation are preferable. Alternatively, a plurality of these methods may be combined.
  • a flat tray may be used as a support, and a clay-containing liquid may be applied thereto.
  • the material of the support is not particularly limited, but must be able to withstand the temperature during heating.
  • polyethylene Examples include films, substrates, glass and silicon wafers made of resin such as terephthalate (PET) and polypropylene.
  • PET terephthalate
  • substrates made of metal such as brass, copper, stainless steel and aluminum.
  • the support generally has a higher thermal conductivity.
  • the clay-containing liquid must have a structure that prevents the clay-containing liquid from flowing out, such as a tray. It is also possible to use a flat support made of the aforementioned material.
  • a flexible and easily deformable support in order to absorb the stress accompanying volume shrinkage.
  • the clay film itself can be deformed together with the support during drying, or it can be dried while actively deforming the support into a shape that relieves the stress associated with volume shrinkage. Since it is possible, the stress remaining inside the clay film can be relieved and cracking of the clay film can be suppressed.
  • the support is not particularly limited as long as it is flexible and easily deformed.
  • the support is capable of peeling the clay film after drying, continuously producing the clay film in the form of a roll, Considering the impact on the production cost of the soil film, an inexpensive resin film such as PET is suitable.
  • the support is preferably composed of polypropylene, polytetrafluoroethylene or the like having strong water repellency.
  • ultraviolet irradiation treatment electron beam irradiation treatment, ion beam irradiation treatment, corona discharge treatment, plasma treatment (for example, remote plasma treatment, flame plasma treatment), physical treatment (for example, a contact area is reduced). Machine processing) to increase the surface power.
  • a resin such as a silicone resin that lowers adhesion
  • a resin such as a silicone resin that lowers adhesion
  • a softened by physical stimulation such as light and heat.
  • the treatment include applying a peelability-imparting agent that lowers the adhesion by changing the Young's modulus or foaming. Or you can combine more than one of these processes.
  • the surface of the support is preferably as smooth as possible.
  • the surface roughness of the clay film is lowered because the roughness of the surface of the support is transferred to the surface of the clay film. Further, in the transparent film, light is irregularly reflected, which causes an increase in haze.
  • a clay film made of hydrophilic clay the stress generated in the clay film due to drying shrinkage is large immediately after drying, but the internal stress often decreases when left for a while after drying.
  • many transparent films made of hydrophilic clay are curled by internal stress immediately after drying, but if left for about 10 minutes, the internal stress is released and a flat film is formed. Therefore, until the internal stress decreases, the generated stress is released by deforming the support, and after the internal stress is released, the support force is peeled off and the internal It is possible to produce a clay film with less stress and no cracks or curls.
  • the reason why the internal stress decreases when left for a while after drying is thought to be because the flexibility is improved by the absorption of moisture in the air. Therefore, holding the clay film immediately after drying in a humidity-controlled environment for a while is effective in removing the internal stress of the clay film made of hydrophilic clay.
  • a deformable support it is possible to suppress the damage of the clay film due to the stress accompanying the volume shrinkage during the preparation of the clay film. This makes it possible to produce a clay film with a large area with a high yield, which is suitable for applications requiring a film with a large area such as a display. Further, according to the present invention, a continuous clay film can be easily obtained in continuous production using a roll using a support made of a film wound in a roll shape. It becomes easy to produce (for example, clay tape).
  • a forced air oven Etc. should be used. And when it is dried for 10 minutes or more and 7 hours or less under the temperature condition of 30 ° C or more and 120 ° C or less, a clay film is obtained.
  • the temperature condition is more preferably 30 ° C or higher and 90 ° C or lower, and further preferably 50 ° C or higher and 70 ° C or lower.
  • the drying time is preferably 20 minutes or more and 3 hours or less, more preferably 20 minutes or more and 2 hours or less.
  • the optimum drying time varies depending on the film thickness of the clay film, the solid content concentration of the clay-containing liquid, and the type of the solvent used. Since water has a large specific heat and takes time to dry, an organic solvent is preferable as the solvent, and a solvent having a relatively low boiling point is particularly preferable. A combination using an organic solvent as the solvent and a hydrophobic clay as the clay is desirable for shortening the drying time. If the boiling point of the solvent is too low, not only will the solvent evaporate and the solids concentration will increase during the preparation of the clay-containing liquid, but the risk of flammable explosion will also increase. In view of both mass productivity and safety, it is preferable to appropriately select the type of solvent.
  • a clay film having mechanical strength that can be used as a self-supporting film and having a small linear expansion coefficient can be produced.
  • uncolored clay such as synthetic clay
  • the surface irregularity may increase with time if left in the atmosphere. This phenomenon is particularly noticeable when hydrophilic synthetic saponite or synthetic hectorite is used as clay, polyacrylate is used as an additive, and water is used as a solvent for the clay-containing liquid. It was.
  • Such a problem is caused by a liquid that swells clay on the surface of a clay film (hereinafter sometimes referred to as a primary dry film) obtained by drying the clay-containing liquid described above.
  • a primary dry film obtained by drying the clay-containing liquid described above.
  • the problem can be solved by arranging a liquid for dissolving or dispersing the additive and re-drying. 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 reduced.
  • the method of arranging the liquid (the liquid that swells the clay or the liquid that dissolves or disperses the additive) on the surface of the primary dry film obtained by drying the clay-containing liquid is not particularly limited.
  • a method of immersing the primary dry film in the liquid may be used, or a method of spraying the liquid on the surface of the primary dry film like a spray may be used.
  • a method of placing a primary dry film in a high-concentration vapor atmosphere of the liquid may be used.
  • the time during which the primary dry film and the liquid are in contact with each other is preferably from a few seconds, which is preferably relatively short, and within a few minutes at the longest.
  • the film when the liquid is disposed so that the surface of the primary dry film is washed away by a method of spraying the liquid onto the surface of the primary dry film or a method of immersing the primary dry film in the flowing liquid, the film In many cases, it is effective for smoothing and suppressing haze increase over time.
  • the liquid When the liquid is arranged on the surface of the primary dry film, the liquid may flow down by tilting the primary dry film from a horizontal state so that the liquid does not stay on the surface of the primary dry film for a long time. .
  • the primary dry film When the liquid is distributed while the primary dry film is held in an inclined state from a horizontal state, the primary dry film is placed on a mesh-like wire or the like used for papermaking. It is preferable to place the liquid. By doing so, the excess liquid easily flows down from the surface of the primary dry film, so that a part or the whole of the primary dry film can be prevented from being re-dispersed or excessively swollen.
  • the type of the liquid is not particularly limited as long as it swells clay or dissolves or disperses the additive, and may be appropriately selected according to the type of clay and additive.
  • water is suitable if it is a hydrophilic clay that swells in water or a clay film having an additive that dissolves in water.
  • the volume of the primary dry film is increased with gelation.
  • a clay film having wrinkles or the like may be generated.
  • the clay film is stretched, the wrinkles are stretched, and the clay film is flattened.
  • a smooth clay film can be obtained.
  • the method for stretching the clay film include a method in which a roller or the like is pressed against the clay film, and a method such as biaxial stretching in which the clay film is pulled.
  • the clay film may be stretched on a member with a smooth surface, or on a mesh-like wire that is used when paper is made, as in a smooth member. It may be performed in a state where it does not come into contact with a proper support.
  • the liquid is disposed on the surface of the primary dry film as described above. Since the deposited additive is removed by the liquid, the effect of the present invention is exhibited. Further, in the primary dry film in which the liquid is arranged as described above, either the clay or the additive agent absorbs the liquid, and the entire primary dry film or at least the primary dry film in contact with the liquid is used. The portion near the surface swells. In such a state, the surface of the primary dry film swells and the surface area increases, so if the smoothness is improved, the surface of the primary dry film becomes a gel and softens.
  • a clay film having a smooth surface can be obtained by disposing the primary dry film in which the liquid is disposed on a glass substrate or resin film having a smooth surface. Furthermore, both sides of the clay film can be smoothed by arranging a similar glass substrate or resin film from above and sandwiching the clay film with a smooth member.
  • the smoothing member used for smoothing is not particularly limited as long as the surface is smooth, and a glass substrate, a silicon substrate, a resin substrate such as a polyethylene terephthalate (PET) film, or the like can be used. Furthermore, on the surface of these smooth members, a peeling facilitation treatment similar to that applied to the support used when producing the primary dry film described above so that the clay film can be easily peeled off after smoothing, A water repellent treatment may be applied.
  • the primary dry film after the liquid is disposed may be disposed on a smooth resin film, and a smooth surface may be smoothed by rolling a roller thereon.
  • the primary dry film may be pressed against the smooth member by smoothing the external force with a screw or the like.
  • the roller or the press device may be brought into direct contact with the primary dry film, or when it is desired to prevent the primary dry film from adhering to the roller press machine or the like, a process for facilitating peeling is performed.
  • An external force may be applied by interposing a smooth resin film or the like applied as necessary.
  • a clay film having the above-described effects of the present invention can be obtained. Drying can be performed on any member or without contact with the member, but in order to finally obtain a clay film with a smooth surface, it was used to smooth the surface of the clay film. It is desirable to carry out on the smooth member having a smooth surface.
  • the method of re-drying is not particularly limited, but for example, centrifugation, filtration, vacuum drying, freeze vacuum drying, standing in an inert gas atmosphere, and heating evaporation are preferable. Alternatively, a plurality of these methods may be combined. Or just leave it in the atmosphere. At this time, in order to prevent foreign matter from adhering to the surface of the clay film and lowering the smoothness of the surface, it is desirable to re-dry in a clean oven or tarrine nolem with as little foreign matter as possible in the dry atmosphere.
  • the smooth member has flexibility and the smooth member force clay film is peeled after re-drying in a state where the smooth member is deformable.
  • the smooth member having flexibility is preferably a resin film.
  • clay crystal layers are highly oriented and laminated, and the additive is averagely inter-forced between the clay layers, and is excellent in uniformity.
  • a clay film with few defects due to mixed gas can be produced.
  • the obtained clay film has a mechanical strength that can be used as a self-supporting film by a dense laminated structure, and has a small linear expansion coefficient.
  • uncolored clay such as synthetic clay
  • transmittance and haze unevenness with a flat spectral characteristic and no coloration are widespread.
  • a clay film that cannot be visually confirmed can be produced.
  • the tensile strength of the clay film is preferably lOMPa or more, more preferably 15 MPa or more, and more preferably 20 MPa or more. More preferably, it is most preferably 25 MPa or more. If it is lOMPa 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 that it has sufficient strength.
  • the clay film obtained by the production method of the present invention gas components contained in the clay-containing liquid are sufficiently removed, so that there are very few internal bubbles (voids) and the like. Therefore, depending on the heat resistance of the additive, for example, even if the film surface is observed rapidly after heating to 300 ° C (for example, at a rate of temperature increase of 15 ° C or more per minute) and holding for 1 hour, No swelling is observed on the surface, and it is a clay film with excellent thermal stability that can be used under high temperature conditions of 300 ° C or higher.
  • the transparent clay film has high transparency over the entire visible light range, has low haze, no coloration, and little in-plane unevenness of transparency.
  • the removal of gas components contained in the clay-containing liquid has a significant effect on haze reduction.
  • reducing haze is a very important issue when applied to optical applications such as displays.
  • the haze immediately after film formation (cloudiness) Can be made 5% or less.
  • the haze is preferably 3% or less, more preferably 2% or less, and even more preferably less than 1%.
  • the change over time in haze under an environment of 24 ° C, 1 atm, and humidity of 45% can be made 2% or less.
  • the change with time of haze is preferably 1% or less, more preferably 0.5% or less.
  • the total light transmittance is 85.
  • the light transmittance of parallel light in the wavelength range of 400 nm or more and 800 nm or less by UV-visible spectrometer is 85% or more95. It is possible to produce one that is less than or equal to 0 .
  • the haze of glass substrates and optical film materials with a smooth surface and low haze is generally around 0.5%, even if it is particularly transparent. /.
  • the clay film obtained when they are used as a support or smooth member has irregularities on the surface. Since it is generally defined by these bases and smooth members, the haze of the resulting clay film is often from 0.5% to a maximum of about 0.2% at best. Further, if the haze change over time is more than 2%, the transparency of the clay film decreases with time, and there may be a disadvantage that desired optical characteristics cannot be obtained.
  • the upper limit of the light transmittance is determined by the refractive index of the film.
  • clay has a refractive index of about 1.5 in many cases. Therefore, even if an additive having a low refractive index is added, the light beam of the parallel light of the clay film produced by the clay film production method of the present invention is used.
  • the transmittance is considered to be about 95%.
  • the surface of the clay film is provided with, for example, a low-refractive index anti-reflection film, a multilayer anti-reflection film utilizing optical interference, or an anti-glare-treated film, the transmittance is further improved. It is possible.
  • the viscosity crystal layer with a small proportion of the additive is highly oriented and laminated, and the additive is inter-layered on average between the layers. It is possible to obtain a clay film with an average linear expansion coefficient force from 40 ° C to around 250 ° C with an absolute value of 20 ppm or less.
  • the linear expansion coefficient is preferably 15 ppm or less, more preferably 10 ppm or less, even more preferably 7 pp or less, particularly preferably 5 ppm or less, and most preferably 3 ppm or less.
  • Such a small linear expansion coefficient is a film made of a conventional resin, or even if clay is contained, the resin is mainly used, and the clay crystal layer is densely and highly oriented and laminated. This is an extremely small value that could not be reached in the conventional nanocomposite body that was not present, and is particularly difficult for a transparent film. Since many electronic devices are made of an inorganic substance having a small linear expansion coefficient, it can be said that the clay film of the present invention has extremely suitable characteristics as a substrate on which such electronic devices are mounted. In addition, when such a clay film is used for packing or the like, since the unevenness of the surface is small, it is possible to obtain the effect of suppressing leakage of gas and the like.
  • the clay and the additive are uniformly dispersed, and the mixed gas is sufficiently removed.
  • a clay film in which the clay crystal layers are highly oriented and laminated is obtained.
  • TEM transmission electron microscope
  • glass It is widely studied and evaluated by X-ray diffraction measurement for the orientation and lamination state of clay films formed on a substrate such as a glass substrate and the dispersion and exfoliation state of clay crystals in nanocomposites containing clay. ing.
  • the intensity and position of the main peak (bottom reflection peak at the lowest 2 ⁇ side) generated in the X-ray diffraction spectrum due to the first-order diffraction of the (001) plane of the clay crystal, and the low 2 ⁇ region It is possible to know the laminating state (average spacing of layers) and the dispersion state of clay crystals by the lifting force S of the background of the X-ray diffraction spectrum.
  • the average interlayer distance in the clay film having the additive ratio of less than 30% by mass is 10 nm or less when converted from the position of the main peak in the X-ray diffraction spectrum.
  • the average interlaminar distance is preferably 7 nm or less, more preferably 5 nm or less, further preferably 4 nm or less, and particularly preferably 3.5 nm or less, most preferably 2 nm or less.
  • the average interlayer distance is 1.5 nm or less, an extremely high gas barrier property that is less than or equal to the measurement limit of the existing measuring apparatus can be exhibited.
  • This preferable average interlayer distance when converted to the top position of the first-order diffraction peak (value of 2 ⁇ ), is a measurement using a wavelength of 1.54 ⁇ which is a general copper ⁇ ray.
  • a clay film made of smectite group clay or synthetic mica group clay where the thickness of one layer of the clay crystal is about lnm, it corresponds to the region of 0.8 to 9.0 in 2 ⁇ .
  • the minimum value of the average interlaminar distance is equivalent to that of a composition consisting only of clay.
  • the additive is averaged inter-layered between the layers, so that the composition consisting only of clay.
  • the average interlayer distance is larger than that of As a method for confirming this, whether or not the peak top position of the main peak in the X-ray diffraction spectrum is shifted to the lower 2 ⁇ side than that of the composition consisting only of clay, or The guideline is whether the peak width is broad 2 ⁇ . Whether or not the average interlayer distance in the clay film is within the above-mentioned preferable range can also be confirmed by measuring the interlayer distance directly from an image obtained by TEM photography.
  • the clay film obtained by the method for producing a clay film of the present invention generally has a high level and barrier property against inorganic gases such as hydrogen, oxygen, and nitrogen.
  • Gas barrier property is the viscosity used Although it varies greatly depending on the type of soil and additives, when it is defined by the transmittance, it is less than half that of the film consisting only of the additive.
  • the transmittance is preferably 1/10 or less of the film made of only the additive used, more preferably 1/100 or less, and even more preferably 1/1000 or less.
  • the gas barrier property may be below the measurement limit of the current general-purpose gas permeability measuring device (for example, Mocon device).
  • the clay film of the present invention has strength that can be used as a self-supporting film, it can be used for various purposes. For example, it is possible to directly form an active matrix drive circuit as a backplane for flexible electronic paper on a clay film at high temperatures by taking advantage of heat resistance, gas barrier properties, flexibility, and low linear expansion. In this case, it is not necessary to use a conventional method such as forming a drive circuit on a heat-resistant glass substrate and then transferring it to a resin film, so that the manufacturing process of electronic paper can be reduced, It is also superior in terms of cost.
  • the clay film is transparent, it can be used as a substrate or gas barrier film on the front plane side of the electronic paper.
  • the type of electronic paper to which the clay film of the present invention can be applied is not particularly limited, and examples thereof include electro-spinning drive type and electronic powder fluid type electronic paper.
  • a clay film can be widely used as a flexible substrate of an electric circuit by virtue of an insulating characteristic. Even when used as a substrate for an electric circuit, the clay film of the present invention is more preferable for the purpose of preventing the disconnection of the wiring and the like, where the unevenness of the substrate surface and the linear expansion coefficient are smaller.
  • the conductive portion of the substrate is covered with a flexible printed circuit board formed by applying or printing conductive ink, and the conductive ink is heated to a higher temperature by utilizing the heat resistance and low linear expansion coefficient of the clay film. Therefore, the resistivity of the conductor portion formed by coating or printing can be further reduced. Suitable applications of such flexible boards and flexible printed boards include RFID tag boards and copper clad laminates.
  • a transparent clay film can be applied to a device that needs to pass light, such as a solar cell.
  • organic semiconductors typified by pentacene and thiophenes are generally deteriorated by oxygen and moisture.
  • Amorphous inorganic semiconductors are also less acidic than organic semiconductors. Susceptible to moisture and moisture. Therefore, it is necessary to sufficiently prevent oxygen and water vapor from entering the device using them.
  • the clay film of the present invention has a high gas barrier property, it is a substrate for an electronic device having an organic semiconductor or an amorphous inorganic semiconductor sensitive to deterioration due to oxygen or the like, or as a gas barrier film for protecting the organic semiconductor or the amorphous inorganic semiconductor. Is also suitable.
  • the clay film retains flexibility even at high temperatures, the above electronic device can be made flexible.
  • the clay film of the present invention When applying the clay film of the present invention to the electronic paper, the flexible substrate, the flexible printed board, the electronic device having the organic semiconductor or the amorphous inorganic semiconductor, the clay film is applied as it is. If necessary, a film having another function on the clay film (e.g., a water vapor barrier film mainly made of inorganic material, a reinforcing material made of a resin material, a protective layer to prevent scratches, a smooth surface to smooth the surface) Or the like may be used.
  • a film having another function on the clay film e.g., a water vapor barrier film mainly made of inorganic material, a reinforcing material made of a resin material, a protective layer to prevent scratches, a smooth surface to smooth the surface
  • a film having another function on the clay film e.g., a water vapor barrier film mainly made of inorganic material, a reinforcing material made of a resin material, a protective layer to prevent scratches, a smooth surface
  • a film having a different function from clay such as the water vapor barrier film, a reinforcing material such as a resin material, a protective layer for preventing scratches, a smoothing layer for smoothing the surface, etc.
  • a liquid may be placed on the surface of the clay film to swell, and then dried again to improve the smoothness of the clay film portion.
  • the film made of clay and resin film is immersed in a liquid, or swollen by spraying a liquid on the clay surface, and then dried again Good.
  • the improvement by the above method is possible.
  • the kind of clay used in the present invention is not particularly limited, and may be natural clay or synthetic clay.
  • mica, vermiculite, montmorillonite, iron montmorillonite, piderite, sabonite, hectorite, steepensite, nontronite, magadiite, hyde mouth talcite, caryonite, and halloysite are preferred.
  • synthetic clay is preferred for transparent clay films.
  • Synthetic clay is preferably synthetic saponite, synthetic hectorite, synthetic stevensite, synthetic mica, synthetic hydrated talcite, synthetic lionite, etc., but clay belonging to the smectite group is more preferred in terms of dispersibility. That's right.
  • natural montmorillonite having a large aspect ratio of the clay crystal layer and clay belonging to the mica group are preferable.
  • a synthetic smectite group clay having a high aspect ratio, synthetic mica, and hydrated talcite are also preferable.
  • a hydrophobic clay having improved dispersibility in an organic solvent by treatment with a salt having an organic ion such as ammonium salt, phosphorium salt, imidazolium salt, carboxylic acid or the like is used. Also good.
  • This treatment is a treatment for exchanging inorganic ions of hydrophilic clay with organic ions.
  • a process of converting the hydroxyl group of the octahedral sheet which many clay minerals have as a component of the layer structure into another hydrophobic substituent by a chemical reaction for example, dehydration with an arbitrary silane coupling agent
  • Hydrophobic clay with improved water resistance or controlled dispersibility in an organic solvent by a process of substituting a hydroxyl group with another organic group by bonding may be used.
  • an organic smectite obtained by hydrophobizing clay belonging to the smectite group by the above treatment is preferable from the viewpoints of the ease of performing the above treatment and dispersibility.
  • ammonium salts include ammonium salts having an alkyl group, benzyl group, polyoxyethylene group, oxyethylene group, oxypropylene group, dimethyl distearyl ammonium salt, trimethyl. Examples include quaternary ammonium salts such as stearyl ammonium salts.
  • Phosphonium salts and imidazolium salts are known to be resistant to decomposition and coloring even at high temperatures where heat resistance is high. Therefore, a clay film having excellent heat resistance can be obtained by using hydrophobic clay treated with phosphonium salt or imidazolium salt. Since hydrophobic clay has a low affinity with water, the resulting clay film also has a low affinity with water, resulting in excellent water resistance.
  • the clay in the present invention includes both the hydrophilic clay and the hydrophobic clay.
  • hydrophobic clay the organic ions bound to the surface of the tetrahedral sheet or octahedral sheet are defined as part of the clay.
  • the presence of organic ions in the hydrophobic clay slightly increases the interlayer distance of the clay crystals, causing the demerit of lowering the gas barrier property, but is strongly bound to the surface of the tetrahedral sheet or octahedral sheet, so the clay
  • the effect on the transparency and dimensional stability of the film is generally small, and it is suitable in that it has the merit of water resistance not found in hydrophilic clay.
  • Hydrophobic clay is generally obtained by exchanging inorganic ions such as alkali metals existing between layers of hydrophilic clay with organic ions. Is. Therefore, in principle, it is possible to obtain a clay film containing almost no alkali metal by using hydrophobic clay that has been sufficiently ion-exchanged. Therefore, it is considered suitable for electronic device applications that dislike alkali metals.
  • the type of additive used in the present invention is not particularly limited, but the main role of the additive is to increase the flexibility and strength of the clay film, and to remove the solvent of the clay-containing liquid.
  • the additive itself has flexibility, elasticity, or fluidity because of relaxation of the stress due to volume shrinkage (to ensure surface smoothness and uniformity inside the clay film). It is preferable.
  • the additive itself may be in the form of a liquid or a sol-gel, as long as it is uniformly dissolved or dispersed in a solvent that need not be solid.
  • the additive is also preferably transparent or less colored.
  • a polymer mainly containing carbon or silicon in the main chain is particularly preferable.
  • it may be a monomer having a polymerizability that polymerizes with another monomer or polymer in a clay film to convert it into a polymer. It may also contain organic ions that interact with the clay.
  • the additive is hydrophilic and has high dispersibility or solubility in water.
  • a water-dispersed material such as latex-emeraldion may be used. Since they are highly dispersible or soluble in water, their water resistance is generally low. Therefore, the additive may be insolubilized in water by adding salt, other reactive monomers, polymers or oligomers. However, when an aqueous dispersion material such as latex emulsion is used, the water resistance of the film can be improved by heat treatment after film formation. [0095] It should be noted that when a clay other than hydrophobic clay such as organic smectite is used as the clay, and when a solvent other than water is used as the solvent or a mixed solvent of water and another hydrophilic solvent is used, the hydrophilicity is increased.
  • additives include styrene resins, acrylic resins, aromatic polycarbonate resins, aliphatic polycarbonate resins, aromatic polyester resins, aliphatic polyester resins, aliphatic polyolefin resins, cyclic resins.
  • thermoplastic resins such as polyolefin resin, polyamide resin, polyphenylene ether resin, thermoplastic polyimide resin, polyacetyl resin, polysulfone resin, and amorphous fluorine resin.
  • epoxy resins thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, urea resins, aryl resins, silicon resins, benzoxazine resins, phenol resins, unsaturated polyester resins, bismaleimide triazines
  • Thermosetting resins such as resins, alkyd resins, furan resins, melamine resins, polyurethane resins, and aniline resins can also be used.
  • a photocurable resin can also be used, for example, an epoxy resin containing a latent light power thione polymerization initiator.
  • a curing agent, a curing catalyst, etc. may be used in combination with the thermosetting resin and the photocurable resin, but they are generally used for curing the thermosetting resin and the photocurable resin. If it is possible, there is no particular limitation.
  • Specific examples of the curing agent include polyfunctional amines, polyamides, acid anhydrides, phenol resins, and specific examples of the curing catalyst include imidazole. These curing agents and curing catalysts can be used alone or in combination of two or more. Furthermore, the above-described resins may be used alone or in combination of two or more.
  • the above is a force in which the main chain is mainly a resin composed of carbon atoms.
  • the main chain need not be a carbon atom force.
  • a resin in which the main chain is composed of silicon atoms may be used.
  • salts containing organic ions such as ammonium salt, phosphonium salt, imidazolium salt and the like used in the above-described clay treatment may be used as an additive.
  • Such a salt is suitable as an additive because of its high binding strength with clay.
  • an additive containing two or more organic salt sites in one molecule improves the water resistance and gas barrier properties of the clay film by crosslinking the clay crystal layers and improving the bonding strength between the clay crystal layers.
  • Examples of such an additive containing two or more organic salt sites include a chain composed of two or more units containing the organic salt sites or a chain composed of a key atom and an oxygen atom (for example, polysilane). And molecules that are connected with each other. Further, there may be mentioned molecules having in one molecule a unit containing the organic salt moiety and a moiety having a polymerization property such as a bur group or an epoxy group.
  • the additive is not limited to one that contributes to improving the strength of the clay film.
  • an inorganic flame retardant such as antimony trioxide is added.
  • a plasticizer such as dimethyl phthalate.
  • the above additives are also transparent or less colored.
  • the kind of the solvent used in the present invention is not particularly limited, but water or an organic solvent can be used.
  • Water in which organic substances such as acetamide, N, N-dimethylformamide, ethanol, methanol, and salts are dissolved in a small amount can also be used.
  • the purpose of adding organic matter, salt, etc. is to change the dispersibility of the clay in the clay-containing liquid, change the viscosity of the clay-containing liquid, change the dryness of the clay film, and improve the uniformity of the clay film. And so on.
  • the applied force of a highly polar solvent such as methanol is effective.
  • the main solvent is a low polarity solvent such as toluene
  • the amount of the highly polar solvent such as methanol is preferably 0.1% by mass or more and 20% by mass or less of the main solvent, more preferably 0.5% by mass or more and 15% by mass or less.
  • aromatic hydrocarbons for example, toluene, xylene
  • ethers for example, ethyl ether, tetrahydrofuran
  • ketones for example, for example
  • aliphatic hydrocarbons eg, n-octane
  • alcohols eg, methanol, ethanol, isopropanol
  • halogenated hydrocarbons eg, chloroform, dichloromethane, 1,2-dichloroethane
  • the type of the organic solvent in which the hydrophobic clay can be dispersed greatly depends on the type of the organic functional group on the surface of the clay crystal that develops the hydrophobic property, and therefore it is necessary to select an appropriate one. In addition, it is necessary to carefully select the solubility and dispersibility of the additive to be finally mixed in the clay-containing liquid, and both the dispersibility of the clay and the solubility and dispersibility of the additive are good. It is preferable to select an organic solvent. However, it is not necessary that the solvent of the clay dispersion liquid and the solvent of the additive-containing liquid be the same type. If there is no particular limitation.
  • Synthetic saponite (Sumecton SA manufactured by Kunimine Industries Co., Ltd.) was used as the clay, and sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the additive.
  • the clay dispersion and the additive-containing liquid were placed in a plastic sealed container together with a rotor, shaken vigorously at 25 ° C for 2 hours, and then further rotated at a rotational speed of lOOOOrpm using a homogenizer. Stir for minutes to obtain a uniform clay-containing liquid. At this time, the clay-containing liquid exothermed and the temperature rose to about 90 ° C, and the viscosity of the clay-containing liquid was reduced. Then, the clay-containing liquid at about 90 ° C was placed in a vacuum deaerator and deaerated for 20 minutes under a reduced pressure of 0.08 MPa or less.
  • this clay-containing liquid was applied to a flat portion of the surface of the polypropylene tray.
  • a clay-containing liquid film having a uniform thickness was formed by using a stainless steel ground plate and a spacer as a guide for applying the clay-containing liquid.
  • the tray was placed in a forced air oven and dried by heating at 60 ° C for about 6 hours.
  • the formed clay film was peeled from the tray to obtain a uniform clay film having a thickness of about 22 / m.
  • the obtained clay film had mechanical strength that could be used as a free-standing film. In addition, it was highly flexible with high transparency.
  • the linear expansion coefficient was measured with “TMAZSS220” manufactured by SII Nano Technology Co., Ltd.
  • the sample width was 3 mm and the load was 2 g.
  • the sample was heated to 233 ° C at a heating rate of 5 ° CZmin, cooled to 31 ° C, and immediately heated to 300 ° C at a heating rate of 5 ° CZmin, and the linear expansion coefficient was measured.
  • the average linear expansion coefficient in the temperature range from 40 ° C to 250 ° C was 5.4 ppm / ° C, and the value of the linear expansion coefficient was almost constant in the temperature range.
  • the oxygen transmission coefficient was measured with a gas transmission measuring device “Gasperm — 100” manufactured by JASCO Corporation. As a result, it was confirmed that the oxygen permeability coefficient at room temperature was less than 3.2 X 10 _ 11 cm 2 s _ 1 cmHg _ 1 and showed high gas barrier performance.
  • Example 2 When preparing a clay film in the same manner as in Example 1, the amount of clay-containing liquid poured into the polypropylene tray was changed to prepare three clay films having different film thicknesses.
  • the film thicknesses of the resulting clay films were 13 / im, 19 / im, and 24 ⁇ m, respectively.
  • the film thickness of 13 / m was in the range from 278 nm to 8 OOnm, and the film thickness of 19 ⁇ was in the range from 344 nm to 800 nm.
  • the range from 326 nm to 800 nm had a transmittance of 85% or more, and no coloring was observed.
  • the shape of the UV-visible absorption spectrum was almost the same as that of the clay film of Example 1.
  • the thickness 13 f or 91.7 0/0 things xm, f or 90.9 0/0 those having a thickness of 19 zm was f or 91.6 0/0 that of S ⁇ 24 mu m.
  • the haze (haze) was measured in the same manner as in Example 1, it was 1.9% for a film thickness of 13 zm, 3.4% for a film thickness of 19 xm, and 24 zm for a film thickness of 24 zm. 2. 9%.
  • Example 2 In the same manner as in Example 1, a degassed clay-containing liquid was obtained. Inside a B4 size brass tray After peeling facilitating treatment put a smooth PET film (manufactured by Taisei laminating one coater, Ltd.) having a thickness of 50 mu m was applied to the surface to fix the periphery of the PET film with adhesive tape, the! 3 ET film A clay-containing liquid was applied to the surface that had been subjected to the easy peeling treatment, and a uniform clay film having a thickness of about 22 zm was obtained in the same manner as in Example 1. The resulting clay film had mechanical strength that could be used as a free-standing film. In addition, the transparency was high and the flexibility was excellent.
  • a smooth PET film manufactured by Taisei laminating one coater, Ltd.
  • the clay dispersion prepared in the same manner as in Example 1 and the additive-containing liquid were put together with a rotor in a plastic sealed container, shaken vigorously at 25 ° C for 2 hours, and then further rotated using a homogenizer. The mixture was stirred at lOOOOrpm for 20 minutes to obtain a uniform clay-containing liquid.
  • the clay-containing liquid was applied to the surface of the PET film in the same manner as in Example 3 without degassing, to obtain a uniform clay film having a thickness of about 17 zm.
  • the obtained clay film had mechanical strength that could be used as a self-supporting film.
  • a large number of bubbles that can be visually confirmed were observed on the surface, and unevenness was clearly felt with the finger.
  • the total light transmittance was measured in the same manner as in Example 1, it was 91.8%, and the haze (haze) was measured and found to be 5.1%.
  • Synthetic saponite (Smecton SA manufactured by Kunimine Industries Co., Ltd.) as clay, as additive Sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used.
  • Clay 5 lg and 594 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.
  • 0.9 g of poly (sodium acrylate) was added as it was and shaken vigorously at 25 ° C. for 2 hours to obtain a clay-containing liquid.
  • the clay-containing liquid thus obtained was used, and the subsequent steps were carried out in the same manner as in Example 3 to obtain a uniform clay film having a thickness of about 17 zm.
  • the obtained clay film had mechanical strength that could be used as a free-standing film.
  • no force S, cracks, etc., curved into a cylindrical shape with a radius of 6 mm were generated, and no defects occurred.
  • the transmittance was measured in the same manner as in Example 1, there was no wavelength region having a transmittance of 85% or more (see FIG. 1).
  • the total light transmittance was measured in the same manner as in Example 1. As a result, it was 91.8% and the haze (haze) was 7.0%.
  • Example 2 When the transmittance was measured in the same manner as in Example 1, none of the clay films had a wavelength region having a transmittance of 85% or more. Further, the total light transmittance was measured in the same manner as in Example 1. As a result, the film having a film thickness of 15 / im was 92.0%, and the film having a film thickness of 16 ⁇ was 91.7%. Further, haze (haze) was measured in the same manner as in Example 1. As a result, the film thickness of 15 ⁇ was 7.7%, and the film thickness of 16 ⁇ was 6.5%.
  • Synthetic saponite (Sumecton SA manufactured by Kunimine Industries Co., Ltd.) was used as the clay, and sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the additive.
  • Synthetic saponite (Kunimine Industries Co., Ltd. Sumenon SA) was used as the clay, and sodium polyacrylate (Wako Pure Chemical Industries, Ltd.) was used as the additive.
  • Clay 4 196 ml of Og and pure water were placed in a plastic sealed container together with a rotor and shaken vigorously at 22 ° C. for 2 hours to obtain a uniform clay dispersion. Also, add 2 g of sodium polyacrylate and 198 ml of pure water into a plastic sealed container with a rotor, shake vigorously for 2 hours at 22 ° C, and then stir for 7 minutes at a rotation speed of lOOOOrpm using a homogenizer. An additive-containing liquid was obtained.
  • the clay dispersion and the additive-containing liquid were placed in a plastic sealed container together with a rotor.
  • the quantity ratio of the clay dispersion to the additive-containing liquid is 3 to 7 in mass ratio.
  • the mixture was further stirred for 20 minutes at a rotational speed of lOOOOrpm using a homogenizer to obtain a uniform clay-containing liquid having a clay content of less than 50% by mass.
  • Example 3 Using this clay-containing liquid without degassing, a uniform clay film having a thickness of about 20 / m was obtained in the same manner as in Example 3. In order to confirm the flexibility of the clay film, it was bent into a cylindrical shape with a radius of 6 mm, but no cracks occurred and no defects occurred. Further, when the total light transmittance was measured in the same manner as in Example 1, it was 91.8%, and the haze (haze) was measured, which was 6.3%.
  • Synthetic saponite (Kunimine Kogyo Co., Ltd. Sumenon SA) as clay and sodium carboxymethylcellulose (Aldrich Co., Ltd.) as additive Clay 1.
  • Og and 89 ml of pure water with a rotor and plastic sealed container The mixture was shaken vigorously at 25 ° C. for 2 hours to obtain a clay dispersion.
  • an additive-containing liquid was obtained.
  • the clay dispersion and the additive-containing liquid were mixed and shaken vigorously for 2 hours. Furthermore, the mixture was stirred for 10 minutes at a rotational speed of lOOOOrpm using a homogenizer to obtain a clay-containing liquid having a solid content concentration of 1% by mass. Then, the clay-containing liquid was stirred for 5 minutes with a rotation / revolution type stirring and degassing apparatus AR-100 (manufactured by Sinky Co., Ltd.) equipped with a container that rotates while revolving around the shaft. After that, the rotation was stopped and degassing was performed for 2 minutes in a degassing mode in which the mixed bubbles were removed by centrifugal force with only revolving motion. The obtained clay-containing liquid was put into a plastic disposable tray to form a thin liquid film having a thickness of about 5 mm or less and vacuum degassed for 10 minutes under a reduced pressure of 0.08 MPa or less.
  • the tray containing the clay-containing liquid was placed in an oven and dried by heating at 60 ° C for about 5 hours. After drying, the obtained clay layer was peeled from the PET film to obtain a uniform transparent clay film having a thickness of about 14 ⁇ m.
  • Natural montmorillonite (Kunimine F manufactured by Kunimine Industries Co., Ltd.) was used as clay, and sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used as an additive.
  • the clay dispersion and the additive-containing liquid are placed in a plastic sealed container together with a rotor, shaken vigorously at 25 ° C for 2 hours, and then further rotated at a rotational speed of lOOOOrpm using a homogenizer. Stir for minutes to obtain a uniform clay-containing liquid.
  • the clay-containing liquid The exotherm increased the temperature to about 90 ° C, and the viscosity of the clay-containing liquid decreased.
  • the clay-containing liquid at about 90 ° C was immediately put into a vacuum deaerator and deaerated for 20 minutes under a reduced pressure of 0.08 MPa or less.
  • this clay-containing liquid was applied to a flat portion of the surface of the brass tray.
  • a clay-containing liquid film having a uniform thickness was formed by using a stainless steel ground plate and a spacer as a guide for applying the clay-containing liquid.
  • the tray was placed in a forced air oven and dried by heating at 60 ° C for about 6 hours.
  • the generated clay film was peeled off by tray to obtain a uniform clay film having a thickness of about 40 zm. Since the obtained clay film had sufficient mechanical strength, it could be used as a self-supporting film and had excellent flexibility.
  • Natural montmorillonite (Kunimine F manufactured by Kunimine Industries Co., Ltd.) was used as clay, and sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used as an additive.
  • Natural montmorillonite (Kunimine F manufactured by Kunimine Industries Co., Ltd.) was used as the clay, and Ypsilon force prolatatum (Wako Pure Chemical Industries, Ltd.) was used as the additive.
  • the clay dispersion and the additive-containing solution are placed in a plastic sealed container together with a rotor, shaken vigorously at 25 ° C for 1 hour, and then further rotated at a rotational speed of lOOOOrpm using a homogenizer. Stir for minutes to obtain a uniform clay-containing liquid.
  • the clay-containing liquid The exotherm increased the temperature to about 90 ° C, and the viscosity of the clay-containing liquid decreased.
  • the clay-containing liquid at about 90 ° C was placed in a vacuum deaerator and deaerated for 40 minutes under a reduced pressure of 0.08 MPa or less. After about 15 minutes from the start of degassing, almost no foam was generated from the clay-containing liquid.
  • this clay-containing liquid was applied to a flat portion of the surface of the brass tray.
  • a clay-containing liquid film having a uniform thickness was formed by using a stainless steel ground plate and a spacer as a guide for applying the clay-containing liquid.
  • the tray was placed in a forced air oven and dried by heating at 60 ° C for about 6 hours.
  • the generated clay film was peeled off by tray to obtain a uniform clay film having a thickness of about 30 zm. Since the obtained clay film had sufficient mechanical strength, it could be used as a self-supporting film and had excellent flexibility.
  • This clay film was observed after being heated to 300 ° C at a rate of temperature increase of about 18 ° C per minute and held at 300 ° C for 1 hour. Then, although the clay film was slightly blackened, no swelling that could be confirmed with the naked eye was not observed. When the cross section of this clay film was observed with a scanning electron microscope (SEM), it was found that the inside was fairly uniform (see Fig. 4).
  • SEM scanning electron microscope
  • the linear expansion coefficient was measured in the same manner as in Example 1.
  • the sample width was 3 mm and the load was 5 g.
  • the sample was heated to 148 ° C at a heating rate of 5 ° C / min, maintained at that temperature for 1 hour, and then cooled to 38 ° C. And immediately the heating rate 5.
  • the linear expansion coefficient was measured by heating to 299 ° C at CZ min. As a result, the linear expansion coefficient in the temperature range from 40 ° C to 299 ° C was 1.2 to 8.0 ppm / ° C.
  • Example 2 an electron micrograph of a cross section of the clay film was taken. Similarly, it was found that the clay crystal layers were oriented and densely laminated with an average interlayer distance of about 1.2 nm. (See Figure 6). The average interlayer distance estimated from the electron micrographs is slightly smaller than that from the X-ray diffraction analysis, whereas the X-ray diffraction analysis is under air. However, it seems that electron micrographs are taken under high vacuum. In other words, it is presumed that the average inter-layer distance was slightly reduced because the moisture mixed in the clay film volatilized under vacuum.
  • a clay-containing liquid was obtained in the same manner as in Example 6.
  • the clay-containing liquid whose temperature has risen to about 90 ° C due to stirring with a homogenizer is left at room temperature for about 30 minutes to lower the temperature to about 30 ° C, and then placed in a vacuum degassing apparatus. Deaeration was performed for 40 minutes under a reduced pressure of 0.08 MPa or less. The generation of foam from the clay-containing liquid was observed to the end although it was infrequent during deaeration.
  • Example 6 In the same manner as in Example 6, a uniform clay film having a thickness of about 30 ⁇ m was obtained using this clay-containing liquid. Since the obtained clay film had sufficient mechanical strength, it could be used as a self-supporting film and had excellent flexibility.
  • the clay film was observed after being heated to 300 ° C at a rate of temperature increase of about 18 ° C per minute and held at 300 ° C for 1 hour. As a result, the clay film turned slightly black and a large number of circular bulges with a diameter of about 1 to 5 mm were spotted. When the cross section of this film was observed by SEM, many fine voids were observed (see Fig. 7). When the removal of the gas component contained in the clay-containing liquid is insufficient, many bubbles (voids) derived from the gas component mixed in the clay-containing liquid remain in the clay film, and the above-mentioned during heating. This indicates that a circular bulge like this may occur.
  • Hydrophobic hectorite (Lucentite SAN manufactured by Corp Chemical Co., Ltd.) was used as clay, and Asaflex L451 (Asahi Kasei Chemicals Co., Ltd.) was used as an additive.
  • the clay dispersion and the additive-containing liquid were mixed in another conical flask and stirred with a rotor at about 25 ° C. for 2 hours to obtain a uniform clay-containing liquid. Then, the clay-containing liquid was placed under reduced pressure and deaerated for several minutes while stirring.
  • Example 4 The inner surface of the same brass tray used in Example 4 was covered with aluminum foil, and the portion of the aluminum foil facing the bottom of the tray was leveled.
  • the same PET film as used in Example 3 was placed in a tray (that is, placed on an aluminum foil), and a clay-containing liquid was applied to the PET film.
  • a clay-containing liquid film having a uniform thickness was formed by using a glass rod for applying the clay-containing liquid and a spacer as a guide.
  • This tray was placed on a hot plate and dried by heating at 80 ° C for about 30 minutes.
  • the formed clay film was peeled from the PET film to obtain a uniform clay film having a thickness of about 57 zm. Since the obtained clay film had sufficient mechanical strength, it could be used as a self-supporting film and had flexibility.
  • the transmittance was measured in the same manner as in Example 1. As a result, the transmittance was 85% or more in the range from 360 nm to 800 nm, and no coloring was observed. Furthermore, when the total light transmittance was measured in the same manner as in Example 1, it was 90.1%, and the haze (haze) was 1.6%.
  • This clay film was heated in the atmosphere at 200 ° C for 30 minutes, and the transmittance was measured in the same manner.
  • the transmittance was 85% or more in the range from 42 Onm to 800 nm, and coloring was observed. There wasn't. Further, when the total light transmittance was measured in the same manner, it was 91.1% and haze (haze) was measured to be 1.7%.
  • this clay film was immersed in water at 24 ° C for 24 hours, it was found that it had high water resistance with almost no change in strength that could be confirmed with the naked eye.
  • the water absorption rate associated with immersion calculated from the weight change before and after immersion, was about 1.9%.
  • Hydrophobic hectorite (Lucentite SAN manufactured by Corp Chemical Co., Ltd.) was used as clay, and Asaflex L451 (Asahi Kasei Chemicals Co., Ltd.) was used as an additive.
  • Clay 8 Put 80g of Og and 80g of toluene into an Erlenmeyer flask and stir with a rotor at about 25 ° C for 3 hours. To obtain a uniform clay dispersion. Asaflex L451 (1.5 g) and toluene (10 g) were placed in a Erlenmeyer flask and stirred with a rotator at about 25 ° C. for 1 hour to obtain a uniform additive-containing solution.
  • Example 7 Using this clay-containing liquid, a uniform clay film having a thickness of about 84 ⁇ m was obtained in the same manner as in Example 7. Since the obtained clay film had sufficient mechanical strength, it could be used as a self-supporting film and had flexibility.
  • the transmittance was measured in the same manner as in Example 1. As a result, no coloring was observed in the region having a transmittance of 85% or more. Further, when the total light transmittance was measured in the same manner as in Example 1, it was 90.8%, and the haze (haze) was measured, which was 23.8%.
  • Example 2 In the same manner as in Example 1, a clay-containing liquid having the same composition was prepared.
  • the same PET film as in Example 3 was placed in a B4 size brass tray (PET film was not fixed to the tray with adhesive tape), and the clay-containing liquid was applied to the surface of the PET film coated with silicone resin. .
  • a clay-containing liquid film having a uniform thickness was formed by using a stainless steel ground plate for applying the clay-containing liquid and using a spacer as a guide.
  • the tray was placed in a forced air oven and heated at 60 ° C for about 6 hours to dry the PET film as a support in a deformable state. Immediately after the drying was finished, the PET film was integrated with the clay film and curved, and a part of the PET film was not in contact with the bottom surface of the tray. After the formed clay film was taken out together with the PET film, it was left in the atmosphere for 30 minutes, and when the curve almost disappeared, the clay film was peeled off from the PET film to obtain a uniform clay film with a thickness of about 22 ⁇ m .
  • the obtained clay film had mechanical strength that could be used as a self-supporting film.
  • the transparency was high and the flexibility was excellent. Furthermore, no cracks or cracks were observed throughout the film.
  • the clay film In order to confirm the flexibility of the clay film, it was bent into a cylindrical shape with a radius of 6 mm, but no cracks occurred and no defects occurred. Further, when the transmittance was measured in the same manner as in Example 1, the transmittance at a wavelength of 500 nm was 89.3%, up to 264 nm force, up to 800 nm. In this range, the transmittance was 80% or more. The total light transmittance of the clay film measured in the same manner as in Example 1 was 92.0%, and the haze (haze) was 1.6%.
  • a B4 size polypropylene tray was prepared, which has a frame around it and is thick and cannot be easily deformed. And the clay containing liquid similar to what was used in Example 8 was apply
  • a clay-containing liquid film with a uniform thickness was formed by using a stainless steel ground plate for applying the clay-containing liquid and using a spacer as a guide.
  • This tray was placed in a forced air oven and heated at 60 ° C for about 6 hours to dry.
  • the tray was not deformed at the end of drying, and almost the entire surface of the clay film adhered to the surface of the tray, and cracks occurred in a part of the clay film.
  • the formed clay film was peeled from the tray to obtain a uniform clay film having a thickness of about 22 zm.
  • the obtained clay film had mechanical strength that could be used as a free-standing film. Moreover, it was excellent in flexibility with high transparency. However, as described above, cracks occurred in a part of the clay film, so the clay film was split into multiple parts, and a B4 size clay film could not be obtained.
  • Example 8 In the same manner as in Example 8, a uniform clay film (primary dry film) having a thickness of about 21 ⁇ m was obtained.
  • the obtained clay film had mechanical strength that could be used as a self-supporting film. Also, the transparency was high and the flexibility was excellent.
  • the total light transmittance of the clay film measured in the same manner as in Example 1 was 91.5%, and the haze was 1.8%. Further, the surface roughness of the clay film measured by a surface roughness meter “Alphastep IQ” manufactured by KEL-Tencor Corporation was 39 ⁇ m in Ra.
  • this clay film was immersed in pure water for about 5 seconds, pulled up, and then silicone resin was sandwiched between PET films similar to those described above coated on the surface. At this time, the smooth surfaces of both PET finorems were in contact with the clay film. Next, roll a glass roller with a smooth surface on the PET film to stretch out the clay film and extrude excess water, then peel off one PET film and leave it at about 20 ° C overnight to dry. It was. The dried clay film was peeled from the other PET film to obtain a uniform clay film with a thickness of about 10 zm. The obtained transparent clay film had a tensile strength of 32 MPa and had a mechanical strength that could be used as a self-supporting film. Moreover, it was excellent in flexibility with high transparency.
  • the transmittance in the wavelength range of 190 nm to 800 nm was measured in the same manner as in Example 1.
  • the transmittance of 85% or more was observed in the range of 312 nm to 800 nm. And no coloring was observed.
  • the total light transmittance of the transparent clay film measured in the same manner as in Example 1 was 91.7%, and the haze was 1.5%.
  • the surface roughness of the clay film measured in the same manner was 35 nm in Ra.
  • Example 8 In the same manner as in Example 8, a uniform clay film having a thickness of about 19 ⁇ was obtained.
  • the obtained clay film had mechanical strength that could be used as a free-standing film. Moreover, it was excellent in flexibility with high transparency.
  • the total light transmittance of the clay film measured in the same manner as in Example 1 was 91.7%, and the haze was 2.3%. Further, the surface roughness of the clay film measured in the same manner as in Example 9 was 47 nm in Ra.
  • the primary dry film produced in the same manner as in Comparative Example 9 was left for 1 month in a clean room maintained at 1 atm, temperature 24 ° C and humidity 45%.
  • a clay film having a thickness of about 23 x m with a haze increased to 26.5% was obtained.
  • the clay film was sprayed with pure water so that the surface was washed away to swell the clay film, and then sandwiched between PET films coated with silicone resin on the surface. At this time, the smooth surfaces of both PET films were in contact with the clay film.
  • a glass roller with a smooth surface was rolled on the PET film in the same manner as in Example 9 to stretch the clay film, extrude excess water, and then peel off one of the PET films. It was left to dry overnight at ° C.
  • the dried clay film was peeled from the other PET film to obtain a uniform clay film with a thickness of about 12 x m.
  • the obtained transparent clay film had a tensile strength of 22 MPa and had mechanical strength that could be used as a free-standing film. Also, the transparency was high and the flexibility was excellent.
  • the transmittance in the wavelength range from 190 nm to 800 nm was measured in the same manner as in Example 1. As a result, a transmittance of 85% or more was observed in the range from 328 nm to 800 nm. And no coloring was observed. Further, the total light transmittance of the transparent clay film measured in the same manner as in Example 1 was 91.8%, and the haze was 0.63%. Further, the surface roughness of the clay film measured in the same manner as in Example 1 was 23 nm in Ra.
  • This transparent clay film was allowed to stand for 1 week in a clean room maintained at 1 atm, temperature of 24 ° C and humidity of 45%, and then the total light transmittance and haze were measured in the same manner as described above.
  • the total light transmittance was 91.7% and the haze was 0.68%.
  • the total light transmittance was 91.9% and the haze was 0.65%.
  • the primary dry film having a haze increased to 27.0% was immersed in pure water for about 5 seconds, pulled up, and then sandwiched between PET films coated with a silicone resin on the surface. At this time, the smooth surfaces of both PET films were in contact with the clay film. Next, roll a glass roller with a smooth surface on the PET film to stretch the clay film and push out excess moisture, then peel off one PET film and leave it at about 20 ° C overnight. Dried. The dried clay film was peeled from the other PET film to obtain a uniform clay film with a thickness of about 12 x m. The resulting transparent clay film had a tensile strength of 35 MPa and had mechanical strength that could be used as a free-standing film. In addition, the transparency was high and the flexibility was excellent.
  • the transmittance in the wavelength range of 190 nm to 800 nm was measured in the same manner as in Example 1. As a result, a transmittance of 85% or more was observed in the range of 321 nm to 800 nm. And no coloring was observed. Furthermore, the total light transmittance of the transparent clay film measured in the same manner as in Example 1 was 92.0%, and the haze was 0.83%. Further, the surface roughness of the clay film measured in the same manner as in Example 9 was 32 nm in Ra.
  • Example 12 PET film in which the primary dry film whose haze increased to 27.0% in Comparative Example 11 was sprayed with pure water so that the surface was washed away to swell the clay film, and then the silicone resin was applied to the surface Between them. At this time, the smooth surfaces of both PET films were in contact with the clay film.
  • a glass roller with a smooth surface was rolled on the PET film to stretch the clay film, extrude excess water, and then peel off one of the PET films to a temperature of about 20 ° C. And left to dry overnight.
  • the dried clay film was peeled from the other PET film to obtain a uniform clay film having a thickness of about 10 ⁇ m.
  • the obtained transparent clay film had a tensile strength of 31 MPa and had a mechanical strength that could be used as a self-supporting film. Moreover, it was excellent in flexibility with high transparency.
  • the transmittance in the wavelength range from 190 nm to 800 nm was measured in the same manner as in Example 1. As a result, a transmittance of 85% or more was observed in the range from 305 nm to 800 nm. And no coloring was observed. Further, the total light transmittance of the transparent clay film measured in the same manner as in Example 1 was 91.9%, and the haze was 0.62%. Further, the surface roughness of the clay film measured in the same manner as in Example 1 was 26 nm in Ra.
  • the method for producing a clay film of the present invention can produce a clay film having a strength that can be used as a self-supporting film in which clay and additives are uniformly dispersed and defects such as cracks and cracks are unlikely to occur. it can.
  • the clay film of the present invention is a clay film having a strength that can be used as a self-supporting film in which clay and additives are uniformly dispersed and there are few defects such as cracks and cracks.
  • it is a transparent clay film that has a high light transmittance and is less prone to increase over time even when left in the atmosphere where the haze is small.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un film d'argile transparent dans lequel de l'argile et un additif sont dispersés uniformément et la valeur de trouble augmente avec le temps même lorsque le film est exposé à l'air ambiant. En outre, le film d'argile transparent ne présente pratiquement pas de défauts tels qu'une rupture et un craquelage. L'invention porte aussi sur un procédé permettant de produire un tel film d'argile transparent. On obtient en particulier une dispersion d'argile en mélangeant une saponite synthétique pour l'argile et de l'eau pour le solvant. On obtient aussi une solution contenant l'additif en mélangeant du polyacrylate de sodium pour l'additif et de l'eau pour le solvant. Puis, on obtient une solution uniforme contenant de l'argile en mélangeant la dispersion d'argile et la solution contenant l'additif. Ensuite, la solution contenant de l'argile est désaérée sous vide et la solution désaérée contenant de l'argile est appliquée sur une partie plane de la surface d'un plateau en polypropylène. A la suite du séchage, le film d'argile ainsi formé est séparé du plateau.
PCT/JP2007/051404 2006-01-31 2007-01-29 Film d'argile et son procede de production WO2007088815A1 (fr)

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JP2007308340A (ja) * 2006-05-19 2007-11-29 Asahi Kasei Corp 粘土複合体及びその製造方法
JP2009274924A (ja) * 2008-05-15 2009-11-26 National Institute Of Advanced Industrial & Technology ゲル状粘土膜あるいはそれから製造した乾燥粘土膜
JP2010155752A (ja) * 2008-12-26 2010-07-15 Asahi Kasei Corp 層状無機化合物を含有する固体材料の製造方法、固体材料及びこれを用いて形成された形成体
JP2011213111A (ja) * 2010-03-19 2011-10-27 Asahi Kasei Corp 層状無機化合物のナノシートを含有するガスバリアシート
JP2011230504A (ja) * 2010-04-05 2011-11-17 Asahi Kasei Corp 層状無機化合物を含有するガスバリアシート
JP2012061682A (ja) * 2010-09-15 2012-03-29 Ricoh Co Ltd 中空構造体の製造方法
WO2012137527A1 (fr) * 2011-04-04 2012-10-11 株式会社村田製作所 Carte de connexion flexible
JP2013010662A (ja) * 2011-06-29 2013-01-17 Asahi Kasei Corp 層状無機化合物分散液
JP2013047310A (ja) * 2011-08-29 2013-03-07 Sumitomo Seika Chem Co Ltd 不燃水蒸気バリアフィルム、不燃水蒸気バリアフィルムの製造方法、太陽電池バックシート、及び、太陽電池
CN103466932A (zh) * 2008-09-17 2013-12-25 霓佳斯株式会社 耐热辊、以及使用该耐热辊的平板玻璃的制造方法
JP2014055961A (ja) * 2008-03-20 2014-03-27 Inmat Inc ナノ複合材バリア被膜を有する採取容器組立品
JP2016117810A (ja) * 2014-12-19 2016-06-30 大建工業株式会社 不燃塗料組成物、それを用いた不燃性板材及び耐火性構造
JP2018193276A (ja) * 2017-05-17 2018-12-06 クニミネ工業株式会社 スメクタイトスラリー
JP2022112552A (ja) * 2021-01-22 2022-08-03 富士電機機器制御株式会社 電磁接触器

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US20110259415A1 (en) * 2010-04-27 2011-10-27 Du Pont Apollo Limited Backsheet for a photovoltaic module
TWI433625B (zh) 2011-07-04 2014-04-01 Ind Tech Res Inst 軟性電子元件的製法
CN105126641B (zh) * 2015-08-04 2017-10-24 东华大学 一种柔性凹凸棒土膜及其制备方法
CN107459045B (zh) * 2017-07-26 2020-11-24 华南理工大学 一种黏土薄膜及其制备方法

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Cited By (18)

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JP2007308340A (ja) * 2006-05-19 2007-11-29 Asahi Kasei Corp 粘土複合体及びその製造方法
JP2014055961A (ja) * 2008-03-20 2014-03-27 Inmat Inc ナノ複合材バリア被膜を有する採取容器組立品
US9782776B2 (en) 2008-03-20 2017-10-10 Inmat, Inc. Collection container assembly with nanocomposite barrier coating
JP2016153785A (ja) * 2008-03-20 2016-08-25 インマット・インコーポレーテッド ナノ複合材バリア被膜を有する採取容器組立品
JP2009274924A (ja) * 2008-05-15 2009-11-26 National Institute Of Advanced Industrial & Technology ゲル状粘土膜あるいはそれから製造した乾燥粘土膜
CN103466932B (zh) * 2008-09-17 2017-12-29 霓佳斯株式会社 耐热辊、以及使用该耐热辊的平板玻璃的制造方法
US9604867B2 (en) 2008-09-17 2017-03-28 Nichias Corporation Heat-resistant roll, production method thereof, and method of producing sheet glass using heat-resistant roll
CN103466932A (zh) * 2008-09-17 2013-12-25 霓佳斯株式会社 耐热辊、以及使用该耐热辊的平板玻璃的制造方法
JP2010155752A (ja) * 2008-12-26 2010-07-15 Asahi Kasei Corp 層状無機化合物を含有する固体材料の製造方法、固体材料及びこれを用いて形成された形成体
JP2011213111A (ja) * 2010-03-19 2011-10-27 Asahi Kasei Corp 層状無機化合物のナノシートを含有するガスバリアシート
JP2011230504A (ja) * 2010-04-05 2011-11-17 Asahi Kasei Corp 層状無機化合物を含有するガスバリアシート
JP2012061682A (ja) * 2010-09-15 2012-03-29 Ricoh Co Ltd 中空構造体の製造方法
WO2012137527A1 (fr) * 2011-04-04 2012-10-11 株式会社村田製作所 Carte de connexion flexible
JP2013010662A (ja) * 2011-06-29 2013-01-17 Asahi Kasei Corp 層状無機化合物分散液
JP2013047310A (ja) * 2011-08-29 2013-03-07 Sumitomo Seika Chem Co Ltd 不燃水蒸気バリアフィルム、不燃水蒸気バリアフィルムの製造方法、太陽電池バックシート、及び、太陽電池
JP2016117810A (ja) * 2014-12-19 2016-06-30 大建工業株式会社 不燃塗料組成物、それを用いた不燃性板材及び耐火性構造
JP2018193276A (ja) * 2017-05-17 2018-12-06 クニミネ工業株式会社 スメクタイトスラリー
JP2022112552A (ja) * 2021-01-22 2022-08-03 富士電機機器制御株式会社 電磁接触器

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CN101374766A (zh) 2009-02-25
JP5688783B2 (ja) 2015-03-25
TW200740694A (en) 2007-11-01
KR101003029B1 (ko) 2010-12-21
CN101374766B (zh) 2012-07-18
JPWO2007088815A1 (ja) 2009-06-25

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