JP2007308340A - Clay composite body and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a clay composite body with a regular layer structure where clay and an additive(s) are uniformly dispersed, and to provide its production method. <P>SOLUTION: A clay-containing liquid into which clay and at least one or more kinds of added substances are dispersed is dried, so as to obtain a fused body of the clay and the added substance(s). The fused body is redispersed into a redispersion solvent, so as to obtain a clay-redispersed liquid, and the clay-redispersed liquid is dried. Further, a clay-dispersed liquid obtained by uniformly dispersing clay into a certain solvent and an added substance liquid into which an added substance(s) is uniformly dissolved or dispersed are mixed, so as to obtain a clay-containing liquid. Further, the solvent used for dispersing the clay and the solvent used for uniformly dissolving or dispersing the added substance(s) are different, and the solvent used for dispersing the clay and the solvent used for uniformly dissolving or dispersing the added substance(s) are mixed without being mutually separated. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a homogeneous composite having a regular layer structure composed of clay and additive substances, and a method for producing the same.

In recent years, the need for material design and control using microscopic structures has increased, and various technologies represented by nanotechnology are being developed and put into practical use. Among them, in a system in which two or more molecules associate with each other by intermolecular force to form higher-order tissues and express their functions, controlling the position and orientation of the molecules responsible for these functions is a novel functionality. Important in material creation. For this purpose, research using Langmuir Blodgett films, ultra-thin molecular films, and the like has been actively conducted.
Clay mineral is an aspect ratio with a major axis direction of several tens of nm to 5 μm, with 1 to 3 layers of tetrahedral and octahedral layers mainly composed of oxygen and silicon with a thickness of about 0.22 nm. It is characterized by the presence of large, sheet-like layered inorganic compounds, which are macroscopically present in an orderly laminated state. In these clay-like compounds with a layered structure, it is possible to insert ions and organic molecules with a certain arrangement between layers, and in the case of natural clay, many of them are sodium, calcium, etc. Cationic inorganic ions are adsorbed between the layers to compensate for the negative charge of the layered inorganic compound, and the layered inorganic compound is combined in layers to form a regular layer structure.

  As a method of utilizing the regular layer structure formed by this layered inorganic compound, an array of regular functional molecules is created by inserting molecules responsible for functions between layers, and the arrangement of molecular units on the nanoscale is artificially controlled. Researches to create new functional substances have been actively conducted. For example, an example in which the molecules exhibiting functionality are separated from each other by a layered inorganic compound to suppress the interaction between the molecules and increase the emission intensity from the substance (see, for example, Patent Document 1), and the emission is monochromatic. Examples (for example, see Patent Document 2), examples in which thermal stability is improved when a photochromic material is used as an optical recording material (for example, see Patent Document 3), and an enzyme important as a biocatalyst is interposed between layers. There are many cases including an example in which insertion is improved, enzyme utilization efficiency is improved, and reproducibility of quantitative measurement using an enzyme reaction is improved (for example, see Patent Document 4).

As a method of inserting molecules that express functionality between layers of these layered inorganic compounds, a method of evaporating the solvent by mixing both in a solvent in which both clay and the target molecule are well dispersed or dissolved, a substance to be inserted There have been used a method of mechanically kneading in a molten state by heating or the like, a method of applying energy by ultrasonic irradiation and a physical insertion method.
Since clay is generally a hydrophilic substance that disperses well in water, if it is a substance that dissolves or disperses uniformly in water as well, after mixing them well in a solvent containing water as a main component, In many cases, it is possible to obtain a clay composite in which a target substance is inserted between layers.

  In addition, when a substance that does not dissolve or disperse in water but dissolves or disperses in an organic solvent is inserted between layers of a layered inorganic compound, a hydrophobic organic functional group is used to enable dispersion of clay in the organic solvent. Exchanges exchangeable inorganic ions adsorbed on hydrophilic clay using an ammonium salt with a mark, etc., and performs hydrophobic treatment to give organic functional groups to the surface of layered inorganic compounds, resulting in high affinity for organic solvents In many cases, the desired clay complex can be obtained by obtaining a hydrophobic clay that is easy to disperse, uniformly mixing the hydrophobic clay and the target substance in an organic solvent and then drying the same.

  In the clay and the above-mentioned clay complex, a layered inorganic compound forms a regular layer structure, and inorganic ions and target molecules are inserted between the layers. Therefore, when an X-ray diffraction spectrum using CuKα rays is measured, A clear bottom reflection peak corresponding to the layer spacing can be recognized. For example, clay obtained by placing and drying on a glass substrate a clay dispersion obtained by dispersing montmorillonite, which is a hydrophilic clay in which sodium enters between layers, in water at a relatively dilute concentration of about 1% by weight or less. When a thin film is used as a sample and an X-ray diffraction spectrum is taken in the vicinity of 40% humidity, a sharp bottom reflection peak is observed around 7.3 degrees as a 2θ value. This corresponds to the fact that the layered inorganic compounds are regularly arranged at a layer interval of about 12 mm.

  On the other hand, when a target molecule or the like is inserted between layers, the interlayer distance increases and a peak appears on the lower 2θ side (see, for example, Patent Document 4). When the target molecules are evenly inserted between most layers, the bottom reflection peak at the 2θ position observed in the sample consisting only of clay disappears, and a new peak appears on the lower 2θ side. Become only. It is possible to analyze how much the target molecule is inserted between the clay composites having a regular layer structure by the position of the peak and the intensity change.

  On the other hand, as a composite containing clay, a nanocomposite material in which clay is used as an additive and clay of about 5% or less in weight concentration is added to an organic substance such as a polymer is known. This improves the heat resistance and gas barrier properties of the material, and is widely used, for example, in heat-resistant engineering plastics and adhesives that impart gas barrier properties (see Non-Patent Document 1, for example).

  The clay content in these nanocomposite materials is usually 5% or less by weight, and at most 10% or less. Increasing the proportion of clay further makes the process of mixing clay difficult, and the strength of the material decreases. However, it is generally difficult due to problems such as the inability to use existing polymer processing techniques. In clay composites with a low content of these clays, it is possible to mix hydrophilic clay and hydrophobic substances by the above-mentioned melting and kneading methods, etc., but in this case, since the proportion of clay is small, The layered inorganic compound does not form a regular layer structure due to a problem caused by the manufacturing method, the layer spacing is greatly increased, and a large distribution is generated in the layer spacing.

  Furthermore, a shape deformation such as bending of the crystal itself may occur due to a force applied during kneading. For this reason, the creation of new functional substances by creating an array of functional molecules using the regular layer structure of clay is a technology that lies on the conventional nanocomposite material with a low proportion of clay and its extension line. Then it is generally impossible. Reflecting the above structure, in general, a nanocomposite material does not have a sharp bottom reflection peak in the X-ray diffraction spectrum, and in many cases, the spectrum rises toward the low 2θ side.

In addition, even when a peak is observed, the result is that the full width at half maximum (FWHM) is very broad and unclear such that 2θ is 7 degrees or more, or the added clay is not dispersed and remains as a laminate. In many cases, a small peak is recognized at substantially the same position as the sharp bottom surface reflection peak observed in the spectrum (see, for example, Non-Patent Document 2).
JP 2004-2491 A JP-A-9-310065 JP-A-11-263615 JP 2005-110550 A Nakatsuji, “Product Development of Polymer Nanocomposites”, Frontier Publishing, (2004) Yano et. al. J. et al. Polym. Sci. A: Polym Chem 35 2289-2294, (1997)

  In the conventional method, since it is difficult to insert a hydrophobic substance that does not dissolve or disperse in water between the layers of the hydrophilic clay, the substances that can be inserted between the layers of the hydrophilic clay are limited. Of course, on the contrary, it has been difficult to uniformly insert a hydrophilic substance between the layers of the hydrophobic clay. In addition, the amount of substances that can be inserted between the layers by melting and kneading methods and ultrasonic waves is limited, and the layer structure is also disturbed. Therefore, a regular layer structure in which hydrophobic substances are uniformly inserted between hydrophilic clay layers is used. It was difficult to make a homogeneous clay complex with.

  When using hydrophobic clay hydrophobized with ammonium salt with a hydrophobic organic functional group, the clay can be dispersed in an organic solvent and mixed with the hydrophobic substance in the organic solvent. Although the number of types increases dramatically, the organic functional group and ammonium salt modify the surface of the layered inorganic compound, which changes the properties of the clay. Will open and will affect the function expression, and the heat resistance will decrease due to the addition of organic substances, especially the lack of heat resistance of ammonium salts with organic functional groups will greatly increase the high heat resistance of clay. It has become a major obstacle because it is lowered.

  Therefore, the present invention solves the problems of the prior art as described above, and a homogeneous clay composite having a regular layer structure in which a material that has not been able to be inserted uniformly between clay layers is inserted between clay layers. The issue is to provide.

In order to solve the above problems, the present invention has the following configuration. That is, the clay composite of claim 1 according to the present invention comprises clay that is uniformly dispersed in a solvent, and an additive material that is not dissolved or uniformly dispersed in the solvent, and the clay has a layer structure, The clay composite is characterized in that the additive substance is inserted between layers.
Furthermore, the clay composite of claim 2 according to the present invention is the layered structure in the X-ray diffraction spectrum by CuKα rays measured in the atmosphere of 40% or less of the humidity of the clay composite of claim 1. The peak top corresponding to the interval of each layer of the layered inorganic compound taking the form does not exist at the position relative to the peak top position of the thin film made only of the clay and does not contain the additive, or exists on the lower 2θ side than the position. It is characterized by doing.

Furthermore, the clay composite of claim 3 according to the present invention is the clay composite according to claim 1 or 2, wherein the solvent in which the clay is uniformly dispersed is water or a solvent that can be arbitrarily mixed with water and water. It is characterized by being a mixture of
Furthermore, the clay composite of claim 4 according to the present invention is the clay composite according to any one of claims 1 to 3, wherein the additive substance contained in the clay composite is insoluble in water, and is organic. It is soluble in a solvent, and the organic solvent and water are mixed without being separated.
Furthermore, the clay composite of claim 5 according to the present invention is characterized in that the clay composite according to any one of claims 1 to 4 is formed in a thin film on a support.

According to a sixth aspect of the present invention, there is provided a method for producing a clay composite, comprising: drying a clay-containing liquid in which clay and at least one kind of additive substance are dispersed in a dispersion solvent; and fusing the clay and the additive substance together. And obtaining a clay complex by re-dispersing the fusion in a re-dispersion solvent to obtain a clay re-dispersion, and drying the clay re-dispersion.
Furthermore, the method for producing a clay composite according to claim 7 of the present invention is the method for producing a clay composite according to claim 6, wherein the clay dispersion is obtained by uniformly dispersing clay in a solvent, and added to another solvent. A clay-containing liquid is obtained by mixing an additive substance liquid in which a substance is uniformly dissolved or dispersed.

Furthermore, the method for producing a clay composite according to claim 8 of the present invention comprises mixing a clay dispersion in which clay is uniformly dispersed in a solvent and an additive material liquid in which the additive is uniformly dissolved or dispersed in another solvent. The solid material thus produced is separated from the solution, and the solid material is re-dispersed in a re-dispersion solvent to obtain a clay re-dispersion liquid, and the clay re-dispersion liquid is dried to obtain a clay complex. To do.
Furthermore, the method for producing a clay composite according to claim 9 according to the present invention is the method for producing a clay composite according to claim 7 or claim 8, wherein the solvent and additive substance used for dispersing the clay are uniformly distributed. The solvent used for dissolving or dispersing in is different.
Furthermore, the method for producing a clay composite according to claim 10 according to the present invention is the method for producing a clay composite according to claim 9, wherein the solvent and additive used for dispersing the clay are uniformly dissolved or dispersed. The solvents used for the mixing are not separated from each other and are mixed.

Furthermore, the method for producing a clay composite according to claim 11 according to the present invention is the method for producing a clay composite according to any one of claims 6 to 10, wherein the solvent for dispersing the clay is water or water. A mixture of a solvent that can be mixed with water and water, and the redispersion solvent for redispersing the fusion product and the solid material is either water or a solvent that can be optionally mixed with water, or a mixture thereof. To do.
Furthermore, the method for producing a clay composite according to claim 12 according to the present invention is the method for producing a clay composite according to any one of claims 6 to 10, wherein the solvent for dispersing the clay is water or water. It is a mixture of a solvent that can be mixed with water and water, and the re-dispersion solvent for re-dispersing the fusion product and the solid material is an organic solvent.

  In the clay composite of the present invention, an additive substance that could not be inserted uniformly between the layered inorganic compounds is inserted between the layered inorganic compounds. In addition, the method for producing a clay composite of the present invention can produce a clay composite in which clay and additives that have not been conventionally produced are uniformly dispersed. As a result, a new functional substance can be created.

  The clay complex is generally obtained by placing a solution containing clay and an additive substance on an arbitrary base such as a tray or a glass substrate and drying the solution. In order to uniformly insert the additive substance between the layers of the layered inorganic compound and improve the homogeneity of the clay composite, it is important how to uniformly disperse or dissolve the clay and the additive substance in the solution. Ideally, the layered inorganic compounds are completely separated one by one, and the additive substances are dispersed to the molecular level and dissolved in the meantime. In this state, the card house is based on the interaction between the layered inorganic compounds. A clay complex having a high degree of homogeneity can be obtained by taking a solution structure such as a structure and allowing the solvent to desorb and dry while gelling.

However, actually, even if the additive substance is put in the solution, the additive substance is not uniformly dissolved or dispersed in the solution, and the resulting clay composite may become non-uniform. As a result, functions that should be expected, such as strength, flexibility, and light emission characteristics, may not be obtained.
Therefore, as a result of intensive studies to solve the above problems, the present inventors have regularly ordered additive substances that have not been able to be inserted uniformly between the layered inorganic compounds, between the layered inorganic compounds. A method for producing a homogeneous clay composite having a layer structure was found. That is, in the method for producing a clay composite of the present invention, a clay-containing liquid in which clay and at least one additive substance are dispersed is dried to obtain a fusion body of clay and the additive substance, and the fusion body is reused again. It is characterized by being obtained by redispersing in a dispersion solvent to obtain a clay redispersion, and drying the clay redispersion.

  Furthermore, a clay dispersion liquid in which clay is uniformly dispersed in a solvent and an additive substance liquid in which additive substances are uniformly dissolved or dispersed are mixed to obtain a clay-containing liquid, and the solvent used to disperse clay The solvent used to uniformly dissolve or disperse the additive substance is different, and the solvent used to disperse the clay and the solvent used to uniformly dissolve or disperse the additive substance are not separated from each other and mixed. Also features. In addition, a solid material formed by mixing a clay dispersion liquid in which clay is uniformly dispersed in a solvent and an additive material solution in which the additive material is uniformly dissolved or dispersed is separated from the solution, and the solid material is again reused. It is characterized by being obtained by redispersing in a dispersion solvent to obtain a clay redispersion, and drying the clay redispersion.

Hereinafter, the clay composite of the present invention will be described in more detail.
The kind of clay used in the present invention is not particularly limited, and may be natural clay or synthetic clay. As such clay, for example, one or more of mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, and nontronite are preferable, and in terms of dispersibility, the smectite group A clay belonging to is particularly preferred.

  In general, the clay is a hydrophilic clay that has natural ions such as sodium and calcium between clay layers, and is easily dispersed in water when water enters between the clay layers. As a solvent for dispersing the hydrophilic clay, water mixed with an organic substance such as acetamide, N, N-dimethylformamide, N-methylpyrrolidone, ethanol, or a salt can be used in addition to water. The purpose of adding organic substances, salt, etc. is to change the viscosity of the clay dispersion, to change the ease of drying, to control the wettability with the substrate or the substrate when clay is formed into a film, etc. It is.

  Instead of hydrophilic clay, organic inorganic group-containing ammonium salt, phosphonium salt, imidazolium salt, pyridinium salt, etc. are used to exchange the pre-inorganic ions between the layers of hydrophilic clay, and organically form the layered inorganic compound surface. A clay complex composed of hydrophobic clay can also be prepared by using hydrophobic clay that has been hydrophobized by performing a treatment for imparting organophilicity to impart a functional group. Examples of ammonium salts for hydrophobizing clay include ammonium salts having alkyl groups, alkoxy groups, benzyl groups, polyoxyethylene groups, oxyethylene groups, oxypropylene groups, dimethyl distearyl ammonium salts, and trimethyl stearyl ammonium salts. And quaternary ammonium salts such as

  Solvents for dispersing the hydrophobic clay include aromatic hydrocarbons such as toluene and xylene, ethers such as ethyl ether and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, aliphatic hydrocarbons such as n-octane, methanol, ethanol , Alcohols such as isopropanol, halogenated hydrocarbons such as chloroform, dichloromethane and 1,2 dichloroethane, other N, N-dimethylformamide, N-methylpyrrolidone, dioctyl phthalate, dimethyl sulfoxide, methyl cellosolve, etc. it can. Since the kind of the organic solvent in which the hydrophobic clay thus obtained can be dispersed greatly depends on the kind of the organic functional group on the surface of the layered inorganic compound that exhibits hydrophobicity, it is necessary to select an appropriate one.

  As a method for dispersing clay, stirring may be performed with a rotor, or a general-purpose commercially available stirrer may be used. In particular, a method of dispersing using a container that rotates while revolving around an axis is suitable because it can be effectively dispersed in a short time and mixed bubbles can be removed. Furthermore, it is preferable to carry out the dispersion method under reduced pressure because bubbles can be removed more effectively.

  In this way, a clay-containing liquid in which clay and an additive substance are mixed is obtained by adding an additive substance to a clay dispersion liquid dispersed in an organic solvent in the case of hydrophobic clay in a solvent mainly composed of hydrophilic clay. be able to. However, in order to obtain a clay composite in which a desired additive substance is inserted between the clay layers, even if the additive substance is put into a clay dispersion and the clay-containing liquid is dried, the additive substance is uniformly dissolved in the solvent. In general, it is difficult to obtain a desired clay complex unless it is finely dispersed to a desired size and uniformly dispersed.

For example, hydrophilic clay is dispersed in a mixed solvent obtained by mixing an organic solvent mixed with water and water to obtain a clay dispersion, and then the additive substance soluble in the organic solvent mixed with water is mixed with the clay dispersion. Even if the mixture is thoroughly stirred and the liquid is dried, it is difficult to obtain a homogeneous clay composite having an ordered layer structure in which the additive substance is uniformly inserted between the clay layers.
In the present invention, as a method for producing a homogeneous clay composite having a regular layer structure in which additive substances are inserted between clay layers, first, a clay-containing liquid in which clay and at least one kind of additive substances are dispersed is dried to obtain clay. Basically, a fusion product of the additive and the added substance is obtained, the fusion product is re-dispersed in a re-dispersion solvent to obtain a clay re-dispersion, and the clay re-dispersion is dried.

The method for preparing the clay-containing liquid is not particularly limited, and may be obtained by dispersing the clay in a solvent and then adding the added substance and stirring well, or dissolving or dispersing the added substance in the solvent. Later, clay may be added and stirred well. The solvent to be used may be one kind or a mixed solvent comprising two or more kinds of a solvent having a high affinity for clay and a solvent having a high affinity for the additive substance.
In particular, an effective method for preparing a clay-containing liquid in the present invention is to mix a clay dispersion liquid in which clay is uniformly dispersed in a solvent and an additive substance liquid in which the additive substance is uniformly dissolved or dispersed to mix the clay-containing liquid. Is the way to get. Since the clay-containing liquid obtained by this method is in a state in which clay and additive materials are sufficiently uniformly dispersed and dissolved, it is ideal for obtaining a desired homogeneous clay complex.

  At this time, when the solvent used to disperse the clay and the solvent used to uniformly dissolve or disperse the additive substance are different, the clay and the additive substance differ from the case where the additive substance is dispersed in the same solvent. It is possible to select and use a solvent with good affinity for each additive substance, and the restrictions on the combination of clay and additive substance can be relaxed, and a clay complex composed of a wide variety of clay and additive substances can be obtained. become. In particular, when the solvent used to disperse the clay and the solvent used to uniformly dissolve or disperse the additive can be mixed without separation from each other, the clay dispersion with the clay dispersed uniformly and the additive Since a clay-containing liquid in which the dissolved or dispersed additive substance liquid is more uniformly mixed can be obtained, it is most ideal for obtaining a desired homogeneous clay complex.

  A wide variety of additive substances can be selected according to the function of the desired clay composite, and they can be uniformly dissolved in the selected solvent or even in a state of being reduced to the desired size. If it can disperse | distribute to, it will not be limited. For example, resin such as rubber, urethane, nylon, epoxy, acrylic, polyolefin, polystyrene, and polycarbonate may be added to give strength and flexibility, or heat resistant polyimide resin may be added to provide high heat resistance. May be formed. Further, they may have characteristics such as photocuring property and thermosetting property.

  Furthermore, a light emitting material such as a complex containing a metal or a rare earth element or an organic dye may be added to form a light emitter, or a conductive material such as conductive nanoparticles, a charge transfer complex, or a conductive polymer. Alternatively, an electronic material having conductivity or semiconductivity may be formed by adding an organic semiconductor material typified by pentacene and its derivatives or a thiophene polymer. The solvent for dissolving or dispersing them may be a single type of solvent or a mixed solvent in which a plurality of types of solvents are mixed. Especially when hydrophilic clay is used, clay is often dispersed in water or a solvent mainly composed of water. Therefore, water or a solvent that can be mixed with water at an arbitrary ratio is ideal. Is.

  After obtaining a clay-containing liquid in which the clay and the additive are sufficiently well mixed, the clay-containing liquid is once dried to remove the solvent to obtain a fusion body of the clay and the additive substance. At this time, when the solvent constituting the clay-containing liquid is a mixed solvent, the clay and the additive substance are dispersed in the mixed solvent, and the evaporation rate of each solvent forming the mixed solvent is different, so that the drying proceeds. As the ratio of each solvent in the mixed solvent changes, the dispersion state of the clay and the additive substance changes. Since such a process occurs, it is generally difficult to obtain the target clay complex at the stage of drying the clay-containing liquid.

  In the present invention, a homogenous clay complex can be obtained by dispersing the fused body obtained by drying the clay-containing liquid again in the redispersion solvent and drying the clay redispersion liquid. As the redispersion solvent, when hydrophilic clay is used, it is preferable to use either water or a solvent that can be arbitrarily mixed with water, or a mixture thereof, but there is no particular limitation. Any appropriate one can be used.

  Also when a hydrophobic clay is used, a hydrophobic organic solvent is similarly preferred, but there is no particular limitation. When the interaction between the hydrophobic additive and the hydrophilic clay is strongly expressed and the hydrophobic additive is bonded to the surface of the layered inorganic compound, the quaternary ammonium salt is used. Hydrophobic of the clay similar to the organic processing of the clay that has been performed occurs, and in some cases, a hydrophobic organic solvent is more suitable for redispersion than water or a hydrophilic solvent.

  Similarly, with respect to the fusion of the hydrophilic additive and the hydrophobic clay, even though the hydrophobic clay is used, either water or a solvent that can be arbitrarily mixed with water or a mixture thereof is more preferable. Sometimes suitable for dispersion. As a method for redispersing the fusion material of clay and additive substance, as in the dispersion of clay, stirring may be performed with a rotor, or a general-purpose commercially available stirrer may be used. In particular, a method of dispersing using a container that rotates while revolving around an axis is suitable because it can be effectively dispersed in a short time.

In addition, bubbles are likely to be mixed into the clay redispersion liquid due to the influence of stirring in the redispersion, so if necessary, it is possible to remove bubbles mixed in the liquid by vacuum defoaming and the like. It is effective in obtaining. Vacuum defoaming is preferably performed while stirring the clay redispersion. When stirring under reduced pressure, a stirrer or stirring blade may be used, or a container that rotates while revolving around the aforementioned axis. It may be used.
By drying the clay re-dispersed liquid thus prepared, a desired homogeneous clay complex can be obtained. There is no restriction | limiting in particular as a base for drying a dispersion | distribution solvent, According to the intended purpose of the final clay complex, a suitable thing can be used suitably. For example, it may be on a glass substrate, may be on a resin film, may be placed in a plastic tray or the like and dried, or may be dried in a container to be formed into a desired shape.

Alternatively, as long as it has electronic functionality, it may be formed on a substrate on which electric wiring is formed or on a silicon wafer on which an IC or the like is formed. The drying speed is not particularly limited as long as it is below the temperature at which the solvent boils, but in general, the clay composite is more homogeneous when dried slowly.
In the homogeneous clay composite obtained in this manner, since the additive substance is uniformly inserted between the layered inorganic compound layers, the interlayer distance is increased as compared with the case of only the clay not containing the additive substance. As a result, in the X-ray diffraction spectrum, a phenomenon in which the peak position corresponding to the layer interval of the layered inorganic compound is shifted to the low 2θ side can be recognized.

  A solid substance may precipitate by mixing a clay dispersion liquid and an additive substance liquid. When the solid is composed of clay and additive substances, the solid is separated from the mixed solution by a technique such as filtration, and washed with a liquid that does not dissolve the solid as necessary. The homogeneous clay composite in the present invention can be obtained by dispersing in a re-dispersing solvent and drying the clay re-dispersed liquid. There is no restriction | limiting in particular in a re-dispersion solvent, A suitable thing can be used suitably according to clay and an additive substance.

Below, the manufacturing method of the clay complex of this invention is demonstrated.
First, hydrophilic clay is used as clay, and an additive substance that is insoluble in water is used. Pure water is used as a solvent for dispersing the hydrophilic clay, an organic solvent mixed with water is used as a solvent for dissolving the additive substance, and pure water is used as a redispersion solution for redispersing the fusion of the hydrophilic clay and the additive substance.
Hydrophilic clay and pure water are placed in a plastic sealed container together with a rotor and shaken vigorously to obtain a uniform clay dispersion. Further, the additive substance and the organic solvent are put together with a rotor in a plastic sealed container, and similarly shaken vigorously to obtain a uniform additive substance liquid.

Next, the clay dispersion and additive dispersion are placed in a plastic sealed container together with a rotor, and shaken vigorously to obtain a uniform clay-containing liquid. And this clay containing liquid is put into a vacuum degassing apparatus, and deaeration is performed.
This clay-containing liquid is applied to the base and dried in a temperature environment of room temperature or higher to obtain a fusion of hydrophilic clay and additive substance. After the fusion is peeled off from the base, it is put into a plastic sealed container together with pure water and shaken vigorously to obtain a uniform clay redispersion. And this clay redispersion liquid is put into a vacuum degassing apparatus, and deaeration is performed.
This clay redispersion is applied to the base and dried in a temperature environment of room temperature or higher to obtain a uniform clay composite.

Moreover, another manufacturing method of the clay composite of this invention is demonstrated below.
First, hydrophilic clay is used as clay, and an additive substance that is insoluble in water is used. Pure water is used as a solvent for dispersing the hydrophilic clay, an organic solvent mixed with water is used as a solvent for dissolving the additive substance, and an organic solvent is used as a redispersion solution for redispersing the fusion of the hydrophilic clay and the additive substance.
Hydrophilic clay and pure water are placed in a plastic sealed container together with a rotor and shaken vigorously to obtain a uniform clay dispersion. Further, the additive substance and the organic solvent are put together with a rotor in a plastic sealed container, and similarly shaken vigorously to obtain a uniform additive substance liquid.

Next, the clay dispersion and the additive dispersion are put together with a rotor in a plastic sealed container and shaken vigorously. The generated solid is filtered and washed with pure water.
This solid is put together with an organic solvent into a plastic sealed container and shaken vigorously to obtain a uniform clay redispersion. And this clay redispersion liquid is put into a vacuum degassing apparatus, and deaeration is performed.
This clay redispersion is applied to the base and dried in a temperature environment of room temperature or higher to obtain a uniform clay composite.

  The homogeneous clay composite comprising the clay of the present invention and an additive substance and having a regular layer structure can be suitably used in the field of substrate materials used for electronic devices and the like.

Claims (12)

  A clay that is uniformly dispersed in a solvent; and an additive that does not dissolve or uniformly disperse in the solvent, wherein the clay has a layer structure, and the additive is inserted between layers. Clay complex.   In the X-ray diffraction spectrum by CuKα ray measured in an atmosphere of humidity of 40% or less, the peak top corresponding to the interval between the layers of the layered inorganic compound having the layer structure is composed only of the clay and includes the additive. 2. The clay composite according to claim 1, wherein the clay composite does not exist at the position of the peak top of the clay thin film which is not present, or exists at a lower 2θ side than the position.   3. The clay composite according to claim 1, wherein the solvent in which the clay is uniformly dispersed is water or a mixture of a solvent that can be arbitrarily mixed with water and water.   The additive material contained in the clay composite is insoluble in water, soluble in an organic solvent, and further mixed without separating the organic solvent and water. The clay complex according to one item.   The clay composite according to any one of claims 1 to 4, wherein the clay composite is formed in a thin film on a support.   A clay-containing liquid in which clay and at least one or more additive substances are dispersed in a dispersion solvent is dried to obtain a fusion body of the clay and the addition substance, and the fusion body is re-dispersed in a redispersion solvent again. A method for producing a clay complex, comprising obtaining a clay redispersion liquid and drying the clay redispersion liquid to obtain a clay complex.   The clay-containing liquid according to claim 6, wherein a clay dispersion liquid in which clay is uniformly dispersed in a solvent and an additive substance liquid in which the additive substance is uniformly dissolved or dispersed in another solvent are mixed to obtain a clay-containing liquid. A method for producing a clay composite.   A solid dispersion formed by mixing a clay dispersion liquid in which clay is uniformly dispersed in a solvent and an additive substance liquid in which an additional substance is uniformly dissolved or dispersed in another solvent is separated from the solution, and the solid is again obtained. A method for producing a clay composite, comprising: redispersing in a redispersion solvent to obtain a clay redispersion, and drying the clay redispersion to obtain a clay composite.   9. The method for producing a clay composite according to claim 7, wherein the solvent used for dispersing the clay and the solvent used for uniformly dissolving or dispersing the additive substance are different.   The method for producing a clay composite according to claim 9, wherein the solvent used to disperse the clay and the solvent used to uniformly dissolve or disperse the additive substance are mixed without being separated from each other.   The solvent in which the clay is dispersed is water or a mixture of water and a solvent that can be arbitrarily mixed with water, and the redispersion solvent that redisperses the fusion and the solid is either water or a solvent that can be arbitrarily mixed with water. The method for producing a clay composite according to any one of claims 6 to 10, which is one or a mixture thereof.   7. The solvent for dispersing clay is water or a mixture of water and water optionally mixed with water, and the re-dispersing solvent for re-dispersing the fusion and the solid is an organic solvent. The manufacturing method of the clay complex as described in any one of thru | or 10.