JPH0912769A - Clay composite material, manufacturing method thereof, and blended material - Google Patents

Abstract

(57) [Summary] [Object] To provide a clay composite material capable of uniformly dispersing clay minerals at a molecular level in a wide variety of polymers with low polarity, a method for producing the same, and a blend material of clay minerals. . [Structure] A clay mineral 7 organized by an organic onium ion 6 having 6 or more carbon atoms, and a polar group 10 having a molecular length equal to or smaller than that of the organic onium ion and in the molecule.
Is a first guest molecule 1 which is hydrogen-bonded to the clay mineral 7,
The second guest molecule 2 has a molecular length larger than that of the organic onium ion and has no polar group in the molecule.
At least a part of the first guest molecule 1 and the second guest molecule 2 intervenes between the layers of the clay mineral 7.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a clay composite material, and more particularly to a clay composite material capable of dispersing a clay mineral in a low polarity matrix at a molecular level, a method for producing the same, and a clay mineral. Regarding blend materials.

[0002]

2. Description of the Related Art Conventionally, addition and mixing of clay minerals have been studied in order to improve mechanical properties of organic polymer materials. For example, there is a method of dispersing a clay mineral in nylon, vinyl-based polymer, thermosetting polymer such as epoxy, or rubber (Japanese Patent Laid-Open No. 62-74957). These are the method of organizing the clay mineral with organic onium ions and initiating the polymerization of the monomer between the clay layers, the method of incorporating the clay mineral into the growing seeds, or the method of kneading the clay mineral with the polymer and putting the polymer between the layers. .

[0003]

[Problems to be Solved] However, in the above-mentioned conventional clay composite material, the clay mineral is not well compatible with the polymer having low polarity. Therefore, it is not easy to put a polymer with low polarity between the layers of clay minerals to expand the layers. Therefore, it was difficult to uniformly disperse the clay mineral in the polymer with low polarity.

In order to cope with such a problem, as shown in FIG. 2, an onium group 960 is introduced into the terminal or side chain of a polyolefin polymer having a low polarity to form an organic onium ion 96.
It is considered that the clay mineral 97 is organized by using No. 6 (JP-A-1-198645).

However, the introduction of an onium group at the terminal of a polyolefin is chemically very difficult and not easy. Also, the swelling of the layer was not sufficient because the polyolefin was introduced between the layers of the clay mineral in one step. According to Giannelis et al., When polystyrene having no polar group in the main chain or side chain is used,
Only one layer of polystyrene molecules can enter between the layers, and there is a limit to the swelling between layers (EP Giannel).
is et al., Chem. Mater. 5,1694-169
6 (1993)).

[0006] Therefore, the inventors of the present invention have earnestly studied in order to uniformly disperse the clay mineral at the molecular level in the polymer having low polarity. Then, in a prior application (“Clay composite material and method for producing the same” filed on June 5, 1995), as shown in FIG. 3, a guest such as an oligomer having a polar group 910 in a molecule terminal or a side chain is present. It has been disclosed that by introducing the molecule 91 between the layers of the clay mineral 97 organized by the organic onium ion 96, these can be uniformly dispersed in the polymer having low polarity.

However, the types of guest molecules such as oligomers having polar groups are limited. Many low-polarity polymers do not have compatibilizing guest molecules. Therefore, even if the clay mineral is organized, it may not be possible to uniformly disperse the clay mineral in a matrix composed of various polymers having low polarity.

In view of such conventional problems, the present invention is a clay composite material capable of uniformly dispersing a clay mineral at a molecular level in a wide variety of polymers having low polarity, a method for producing the same, and a blend of clay minerals. It is intended to provide materials.

[0009]

Means for Solving the Problems The present invention relates to a clay mineral organized by an organic onium ion having 6 or more carbon atoms, a molecular length equal to or smaller than that of the above organic onium ion, and a polar group in the molecule. First hydrogen bonded to the above clay minerals
A guest molecule and a second guest molecule having a molecular length larger than that of the organic onium ion and having no polar group in the molecule. At least part of the first guest molecule and the second guest molecule is The clay composite material is characterized by intervening between the layers of the clay minerals.

What is most noticeable in the present invention is that a clay mineral organized by an organic onium ion is hydrogen-bonded to a first guest molecule having a polar group, and a polar group is formed between layers of the clay mineral. At least a part of the first guest molecule and the second guest molecule that does not have the intervening, and the molecular length of the first guest molecule is equal to or less than that of the organic onium ion and The molecular length is larger than that of the organic onium ion.

The above-mentioned clay mineral is organized by being ionically bonded to an organic onium ion having 6 or more carbon atoms. When the number of carbon atoms is less than 6, the hydrophilicity of the organic onium ion is increased and the compatibility with the first and second guest molecules is reduced. As the organic onium ion, for example, hexyl ammonium ion, octyl ammonium ion, 2-ethylhexyl ammonium ion, dodecyl ammonium ion, octadecyl ammonium ion, dioctyl dimethyl ammonium ion, trioctyl ammonium ion, or distearyl dimethyl ammonium ion can be used. You can

As the clay mineral, it is preferable to use one having a large contact area with the guest molecule. This gives
It is possible to greatly swell the layers of clay minerals. Specifically, the cation exchange capacity of the clay mineral is 50 to 20.
It is preferably 0 milliequivalent / 100 g. If it is less than 50 milliequivalents / 100 g, onium ions may not be sufficiently exchanged, and it may be difficult to swell the layers of the clay mineral. On the other hand, when it exceeds 200 milliequivalent / 100 g, the bonding force between the layers of the clay mineral becomes strong, and it may be difficult to swell the layers of the clay mineral.

Examples of the clay minerals include montmorillonite, saponite, hectorite, beidellite,
There are smectite clay minerals such as stevensite and nontronite, vermiculite, halloysite, or swelling mica. It may be natural or synthetic.

The first guest molecule has one or more polar groups in the main chain and / or side chain. The polar group is bonded to the main chain, side chain or end of the first guest molecule. Among these, the polar group is preferably bonded to the end of the first guest molecule. As a result, the interlayer distance of the clay mineral can be swelled to a greater extent.

In the present invention, the polar group is a group in which electrons are localized in the molecule and a bias of charges is generated, and does not include completely polarized ions. Therefore, onium ions are not included in the polar groups. Examples of the polar group include a hydroxyl group (OH), a halogen group (F, Cl,
There are Br, I), carboxyl groups (COOH), thiol groups (SH), epoxy groups, or amino groups that are primary, secondary, or tertiary amines (NH ₂ , NH, N).

A group having a relatively high degree of polarization, such as an imino group, a phosphonyl group and a sulfonyl group, corresponds to the above definition of "polar group", but these groups are not preferable in the present invention. Absent. This is because the first guest molecule containing these groups has low solubility in a solvent and lacks high temperature stability for melting.

The molecular length of the first guest molecule is the same as or smaller than that of the organic onium ion. When the molecular length is larger than that of the organic onium ion, it may be difficult to obtain the first guest molecule, and the kind of the first guest molecule compatibilized in the polymer having low polarity is limited. There is.

The first guest molecule is, for example, an olefin or paraffin having a linear or branched structure, or a linear or branched structure having an aromatic ring in the main chain and / or side chain. It is an olefin or paraffin. That is, the first guest molecule has, for example, one or more polar groups and has a saturated or unsaturated linear or branched structure. In addition, the main chain and / or side chain may contain an aromatic ring.

Examples of the first guest molecule having a polar group include dodecyl alcohol (having 12 carbon atoms), stearyl alcohol (having 18 carbon atoms), stearic acid (having 18 carbon atoms) and stearyl chloride (having 18 carbon atoms). Can be used. Also, OH, COOH, C at both ends
1, polyethylene having a polar group such as epoxy group, polypropylene, polyisoprene, polybutadiene, or hydrogenated products or copolymers thereof. These first
The guest molecule is selected and used so as to have the same length or less as the molecular length of the organic onium ion.

The first guest molecule tends to expand widely between the layers of the clay mineral as the mixing ratio increases. The mixing ratio of the first guest molecule is preferably 0.1 part by weight or more with respect to 1 part by weight of the organized clay mineral. If it is less than 0.1 part by weight, swelling between layers may be insufficient.

The first guest molecule forms a hydrogen bond with the clay mineral due to its polar group. And the first
At least some of the guest molecules intervene between the layers of clay minerals. Not all first guest molecules need to intervene between layers. If 10 wt% or more of the total amount of the first guest molecules is present, the layers will swell sufficiently. On the other hand, if it is less than 10% by weight, swelling between layers may be insufficient.

Next, the second guest molecule is a low-polarity oligomer or polymer having no polar group. The molecular length of the second guest molecule is larger than that of the organic onium ion. When the molecular length is the same as or smaller than that of the organic onium ion, there is a problem that the swelling between layers of the clay mineral is insufficient.

The second guest molecule has a molecular weight of 1,000.
It is preferably an oligomer or polymer having a low polarity of ˜500,000. When it is less than 1000, the swelling between layers of the clay mineral may be insufficient. on the other hand,
If it exceeds 500,000, it may be difficult to dissolve in a solvent, or the softening point or melting point may be higher than the decomposition point of the clay mineral.

The second guest molecule tends to swell between the layers of the clay mineral as the mixing ratio increases. The mixing ratio of the second guest molecule is preferably 0.1 part by weight or more with respect to 1 part by weight of the organized clay mineral. If the amount is less than 0.1 part by weight, the swelling between layers of the clay mineral may be insufficient. At least a part of the second guest molecule intervenes between the layers of the clay mineral. Not all of the second guest molecules need be intervening.

As a method for producing the clay composite material, for example, a clay mineral is brought into contact with an organic onium ion having 6 or more carbon atoms to form an ionic bond between the clay mineral and the organic onium ion. And then organicize the clay mineral, and then the first guest molecule having a molecular length equal to or smaller than the organic onium ion and having a polar group in the molecule, and a molecular length longer than the organic onium ion. The second guest molecule, which is large and does not have a polar group in the molecule, is brought into contact with the clay mineral to hydrogen bond the polar group of the first guest molecule to the clay mineral, and thus the surface of the clay mineral. Is made hydrophobic and at least a part of the second guest molecule is allowed to intervene between the layers of the clay mineral.

What is most noticeable in the present invention is that the clay mineral is contacted with an organic onium ion to be organically modified, and then contacted with the first and second guest molecules.

First, as a method of bringing the clay mineral into contact with an organic onium ion, there is, for example, an ion exchange method. This ion exchange method is, for example, a method of immersing a clay mineral in an aqueous solution containing an organic onium ion and then washing the clay mineral with water to remove an excess of the organic onium ion.

When the first and second guest molecules are brought into contact with the organized clay mineral, the order of bringing them into contact does not matter. That is, both may be administered at the same time and brought into contact with each other, or one of them may be brought into contact with another and then brought into contact with the other. In any case, the same action / effect can be obtained as a result.

As the method for contacting the first and second guest molecules, for example, a method in which the first and second guest molecules are dissolved in a solvent and brought into contact with the organized clay mineral, There is a method of bringing the second guest molecule into contact with the organized clay mineral in a state of being softened or melted by heat.

According to the former method, the first and second guest molecules can intervene between the layers of the clay mineral at room temperature. Solvents that can be used in this method include, for example, toluene, benzene, xylene, hexane, octane, and other low-polarity solvents. On the other hand, in the latter method, in order to soften or melt the first and second guest molecules, the first and second guest molecules are heated to a temperature equal to or higher than the softening temperature or melting temperature. This heating is performed at a temperature at which the first and second guest molecules and the clay mineral are not decomposed and stably exist. For example, the heating temperature is preferably 250 ° C. or lower. If it exceeds 250 ° C, the organized clay mineral may be decomposed.

The above clay composite material can be used as it is as a composite material for molding material, reinforcing material, filling material and the like.

Further, using the above clay composite material as a seed material,
It is also possible to obtain a clay mineral blend material by blending a resin material that is the same as or different from the second guest molecule.

That is, as such a blend material, for example, a clay mineral organically modified with an organic onium ion having 6 or more carbon atoms, a molecular length equal to or smaller than the organic onium ion, and having The first guest molecule has a polar group hydrogen-bonded to the clay mineral, and the second guest molecule has a molecular length larger than that of the organic onium ion and does not have a polar group in the molecule.
The guest molecule and the second guest molecule are added to the clay composite material, at least a part of which intervenes between the clay mineral layers,
There is a blend material of a clay mineral, which is prepared by mixing a resin material composed of the same or different kind of oligomer or polymer as the second guest molecule.

In the above blended material, the layers of the clay mineral can be further expanded. Further, it is even more preferable that the layers are in an expanded state in order to evenly disperse the clay mineral. In order to change the layer interval, for example, the mixing ratio of the resin material and the clay mineral is adjusted.

As the resin material, the same or different resin as the second guest molecule is used. Examples of such resin material include polyethylene, polypropylene, polybutylene, polyisoprene, polystyrene, acrylic resin,
There are, but are not limited to, low polar or non-polar polymers or oligomers such as polyamides and polyesters. The clay mineral blend material can be used, for example, as an injection molding material, an extrusion molding material, a press molding material, a paint resin material, or the like.

[0036]

FUNCTION AND EFFECT In the clay composite material of the present invention, as shown in FIG. 1, the clay mineral 7 is combined with the organic onium ion 6 to be organized. Therefore, some space is generated between the layers of the clay mineral 7.

Further, the first and second guest molecules 1 and 2 intervene between the layers of the clay mineral. The first guest molecule 1 is
Since it has the polar group 10, it bonds with the silicate group of the clay mineral 7 and stays between the layers of the clay mineral 7. Therefore, the layers of the clay mineral 7 are made hydrophobic. The hydrophobicized layer is well compatible with the second guest molecule 2 having no polar group, and stably retains the second guest molecule. Since the second guest molecule 2 has a larger molecular length than the organic onium ion,
Swells between layers significantly.

Therefore, the layer between the clay minerals is remarkably expanded as compared with the conventional one, and becomes infinitely swollen. Therefore, according to the present invention, the clay mineral, which is originally a polar substance, can be uniformly dispersed at the molecular level in a matrix composed of a polymer having a low polarity. Further, it can be dispersed sufficiently even in a non-polar polymer.

Further, since the clay mineral is in an infinitely swollen state, its surface area is remarkably larger than that in the case of the conventional limited swelling. Therefore, it has a high barrier property against gas or liquid (water, oil, etc.). The first and second guest molecules are
The behavior is limited by the presence of clay minerals. for that reason,
Entanglement of the first and second guest molecules is less likely to be loosened.
Therefore, the member manufactured from the clay composite material has high mechanical strength such as tensile strength and elastic modulus. Also, the creep resistance is improved.

Further, the first guest molecule having a small molecular length as described above often has a polar group originally. Further, even if it does not originally have a polar group, the introduction of the polar group is easy because the molecular length is small. On the other hand, since the second guest molecule having a large molecular length does not have a polar group, it is not necessary to introduce a polar group. Therefore, it is possible to avoid the difficult operation of introducing a polar group into a substance having a large molecular length. Therefore, in the present invention, the acquisition and handling of the first and second guest molecules are extremely easy. Also, a wide variety of polymers or oligomers can be used as the first and second guest molecules.

Next, in the method for producing a clay composite material of the present invention, first, the clay mineral is organized by binding an organic onium ion to the clay mineral. This creates some space between the layers of clay minerals.

Next, when the first and second guest molecules are brought into contact with the organized clay mineral, the first and second guest molecules 1 and 2 intervene in the space between the layers. The first guest molecule 1 has a polar group 10. Therefore, clay mineral 7
It is hydrogen-bonded with and stays between the layers of the clay mineral 7 to make the layers of the clay mineral 7 hydrophobic. It is not excluded by the polarity of the clay mineral 7. Therefore, the second guest molecule 2 having a low polarity intervening between the layers of the clay mineral 7 is not excluded by the polarity of the clay mineral, and remains stable between the layers.

The second guest molecule 2 has a larger molecular length than the organic onium ion 6 and is bulky. Therefore, when the second guest molecule stays between the layers of the clay mineral, the layers become infinitely swollen with unlimited swelling. Therefore, according to the production method of the present invention, it is possible to obtain a clay composite material in which a clay mineral, which is originally a polar substance, can be uniformly dispersed at a molecular level in a matrix having low polarity.

The clay mineral blend material of the present invention is a mixture of the above-mentioned clay composite material and resin material. In the clay composite material, the layers of clay minerals are infinitely swollen. Therefore, the clay mineral is evenly dispersed in the matrix made of a resin material having low or no polarity. Further, the above blended material contains such a clay composite material. Therefore, various molded members produced using this blended material are excellent in tensile strength, mechanical strength such as elastic modulus, and creep resistance.

According to the present invention, it is intended to provide a clay composite material capable of uniformly dispersing clay minerals at a molecular level in a wide variety of polymers having low polarity, a method for producing the same, and a blend material of clay minerals. You can

[0046]

【Example】

Example 1 A clay composite material according to an example of the present invention will be described.
As shown in FIG. 1, the clay composite material of this example is a clay mineral 7 that is organized with an organic onium ion 6 having 6 or more carbon atoms.
And a first guest molecule 1 having a molecular length equal to or smaller than that of the above organic onium ion, and a polar group 10 in the molecule forming a hydrogen bond with a clay mineral 7, and a molecular length of the above organic onium ion And a second guest molecule 2 which is large and has no polar group in the molecule. At least a part of the first guest molecule 1 and the second guest molecule 2 intervenes between the layers of the clay mineral 7.

Clay mineral is sodium type montmorillonite (produced in Yamagata prefecture, ion exchange capacity 120 meq / 100).
g). The organic onium ion is distearyldimethylammonium ion and has 38 carbon atoms. The first guest molecule is stearic acid and its carbon number is 18. The second guest molecule is liquid butyl rubber (made by Hardman, trade name Karen 800), and its molecular weight is about 5,000.

Next, a method for producing the clay composite material will be described. First, 80% of 20.0 g of montmorillonite
It was dispersed in 2000 ml of water at 0 ° C. Next, 21.0 g of distearyldimethylammonium chloride was dissolved in 1500 ml of water at 80 ° C. The dispersion liquid and the dissolution liquid were mixed at once. The precipitate was washed twice with water at 80 ° C. to obtain montmorillonite organized with distearyldimethylammonium ion. This is called DSD
M-It is called Montmorillonite.

The inorganic content of DSDM-montmorillonite determined by the cauterization method was 54.2% by weight. The swelling behavior was observed by measuring the interlayer distance of DSDM-montmorillonite by the X-ray diffraction method. The interlayer distance between DSDM and montmorillonite was 32.8Å.

Next, to 20 g of toluene as a solvent, 1.0 g of the above DSDM-montmorillonite, 0.5 g of stearic acid, and 1.0 g of liquid butyl rubber (made by Hardman Co., Ltd., Karen 800) are added, Mix for 6 hours. The toluene was then evaporated under reduced pressure.
As a result, a clay composite material was obtained.

When the interlayer distance of montmorillonite in the clay composite material was measured by the X-ray diffraction method, it was 54.8.
Was Å. From this, by adding stearic acid and liquid butyl rubber, compared to the case without addition,
It can be seen that the interlayer distance of montmorillonite increases and swells.

Example 2 The clay composite material of this example was prepared by changing the mixing ratio of the first guest molecule of stearic acid and the second guest molecule of liquid butyl rubber (made by Hardman Co., Ltd., Karen 800).
It has been added. As an organized clay mineral,
1.0 g of DSDM-montmorillonite of Example 1 was used. The other manufacturing method is the same as that of the first embodiment. The interlayer distance of montmorillonite, which is a clay mineral, was measured by the X-ray diffraction method. The results are shown in Table 1. From the table, it can be seen that the interlayer distance of montmorillonite increases as the addition amount of stearic acid, which is the first guest molecule, increases.

[0053]

[Table 1]

Example 3 The clay composite material of this example uses stearyl alcohol as the first guest molecule. The mixing ratio of the first guest molecule and the second guest molecule was changed. Others are the same as the second embodiment. The interlayer distance of montmorillonite, which is a clay mineral, was measured by the X-ray diffraction method. The results are shown in Table 2. From the table, it can be seen that the addition of stearyl alcohol, which is the first guest molecule, increases the interlayer distance of montmorillonite.

[0055]

[Table 2]

Example 4 The clay composite material of this example was a liquid polyisoprene (produced by Kuraray Co., Ltd., trade name Klaprene LIR-3 as the second guest molecule.
0) was used. This liquid polyisoprene has a molecular weight of 2
It is 9000 and has no functional group. The amount of liquid polyisoprene added was 1.0 g. Others are the same as the first embodiment. The interlayer distance of the clay mineral (montmorillonite) in the clay composite material was measured by the X-ray diffraction method. As a result, the interlayer distance was 55.9Å.

Example 5 In the clay composite material of this example, liquid polybutadiene (manufactured by Nippon Soda, trade name B-2000) was used as the second guest molecule. This liquid polybutadiene has a molecular weight of 1800-2
It is 200 and has no functional group. The amount of liquid polybutadiene added was 1.0 g. Others are the same as the first embodiment. The interlayer distance of the clay mineral (montmorillonite) in the clay composite material was measured by the X-ray diffraction method. As a result, the interlayer distance was 59.2Å.

Example 6 The clay composite material of this example is composed of an organically modified clay mineral and a first
The guest molecules and the second guest molecules are mixed at a mixing ratio (weight ratio) of 1: 1: 10. As the clay mineral, swelling mica made by Corp Chemical was used. Laurylamine ammonium ion (carbon 12) was used as the organic onium ion. As the first guest molecule,
Lauric acid (carbon 12) was used. Polystyrene (molecular weight 25000) was used as the second guest molecule. Others are the same as the first embodiment.

The interlayer distance of the clay mineral (mica) in the clay composite material was measured by the X-ray diffraction method. As a result, the interlayer distance was 120 Å or more. On the other hand, when the first guest molecule, lauric acid, was not added, the interlayer distance of the clay mineral was as small as 18Å.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a clay composite material of the present invention.

FIG. 2 is an explanatory diagram of a clay composite material of a conventional example.

FIG. 3 is an illustration of another conventional clay composite material.

[Explanation of symbols]

 1. . . First guest molecule, 10. . . Polar group, 2. . . Second guest molecule, 6. . . 6. organic onium ions, . . Clay minerals,

Claims (10)

[Claims] 1. A clay mineral organized by an organic onium ion having 6 or more carbon atoms, and a molecular length which is the same as or smaller than that of the above organic onium ion, and whose polar group in the molecule is the above-mentioned clay mineral and hydrogen. A first guest molecule that is bound,
The second guest molecule has a molecular length larger than that of the organic onium ion and does not have a polar group in the molecule. At least a part of the first guest molecule and the second guest molecule is of the clay mineral. Clay composite material characterized by intervening layers. 2. The clay composite material according to claim 1, wherein 10% by weight or more of the total amount of the first guest molecules intervenes between layers of the clay mineral. 3. The polar group of the first guest molecule according to claim 1 or 2, is one or more selected from the group consisting of a hydroxyl group, a halogen group, a carboxyl group, a thiol group, an epoxy group and an amino group. A clay composite material characterized by being. 4. The method according to claim 1, wherein
The second guest molecule has a molecular weight of 1,000 to 50,000.
Clay composite material, characterized in that it is a non-polar oligomer or polymer of zero. 5. The clay mineral is brought into contact with an organic onium ion having 6 or more carbon atoms to form an ionic bond between the clay mineral and the organic onium ion to organicize the clay mineral, and then, A first guest molecule having a molecular length equal to or smaller than the above organic onium ion and having a polar group in the molecule, and a first guest molecule having a molecular length larger than that of the above organic onium ion and having a polar group in the molecule. By contacting the second guest molecule with the clay mineral, the polar group of the first guest molecule is hydrogen-bonded to the clay mineral to hydrophobize the surface of the clay mineral, and the interlayer of the clay mineral is formed. A method for producing a clay composite material, wherein at least a part of the second guest molecule is allowed to intervene. 6. The method for producing a clay composite material according to claim 5, wherein the first guest molecule is first brought into contact with the organized clay mineral, and then the second guest molecule is brought into contact. . 7. The method for producing a clay composite material according to claim 5, wherein the first guest molecule and the second guest molecule are simultaneously contacted with the organized clay mineral. 8. The method according to claim 5, wherein
The method for producing a clay composite material, wherein the first guest molecule and / or the second guest molecule is brought into contact with the organized clay mineral in a state of being dissolved in a solvent. 9. The method according to claim 5, wherein
The method for producing a clay composite material, wherein the first guest molecule and / or the second guest molecule is brought into contact with the organized clay mineral in a state of being softened or melted by heat. 10. A clay mineral organized by an organic onium ion having 6 or more carbon atoms, a molecular length of which is the same as or smaller than that of the organic onium ion, and a polar group in the molecule thereof is the same as that of the clay mineral and hydrogen. The first guest molecule and the second guest molecule having a molecular length larger than that of the organic onium ion and having no polar group in the molecule, and the first guest molecule and the second guest molecule are bonded to each other. , A mixture of a clay composite material, at least a portion of which intervenes between the layers of the clay mineral, and a resin material composed of an oligomer or a polymer which is the same as or different from the second guest molecule. Characteristic clay mineral blend material.