JP3324399B2 - Clay composite rubber material and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a clay composite rubber material in which a clay mineral is dispersed at a molecular level in a rubber polymer having low polarity, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, addition and mixing of clay minerals have been studied in order to improve the mechanical properties of rubber materials. For example, JP-A-1-198645 discloses a method of organizing a clay mineral using an oligomer having an onium ion introduced into a terminal or a side chain, and mixing the clay mineral into a rubber material. .

[0003]

However, in the above-mentioned conventional clay composite rubber material, it is not always easy to prepare an oligomer into which onium ions are introduced. In addition, swelling between the clay layers was sometimes insufficient because the oligomer was immediately introduced into the clay layers. Also,
According to Giannelis et al., When polystyrene having no polar group is used, one polystyrene molecule is present between the layers.
Only layers can enter, and interlayer swelling is limited (EP Giannelis et al., Chem. Mate.
r. 5,1694-1696 (1993)).

[0004] The inventors of the present application have developed a technique of sufficiently allowing an oligomer or polymer having a polar group in a molecule to penetrate between layers of a clay mineral that has been organically treated by onium ions, and a technique of using an organic clay clay. A technique for introducing an oligomer or polymer having no polar group between the clay layers after introducing a low molecular substance having a polar group between the layers has already been filed (“Clay composite material and its production method”, June 1995). Filed on March 5, “Clay composite material and its manufacturing method,
And blended materials, filed June 30, 1995). However, such a technique is mainly intended for plastics, and is not intended for rubber materials.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a clay composite rubber material having a high dispersibility of a clay mineral in a rubber polymer having a low polarity and a method for producing the same.

[0006]

According to the first aspect of the present invention, an organic onium ion having 6 or more carbon atoms is ionically bonded to an organic clay mineral, and the molecular length of the clay mineral is equal to or smaller than that of the organic onium ion. A first guest molecule in which a polar group in the molecule is hydrogen-bonded to the clay mineral; 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. Wherein the first guest molecule and the second guest molecule are ionic-bonded to a first clay composite material and / or an organic onium ion having 6 or more carbon atoms, at least a part of which enters between layers of the clay mineral. And a third guest molecule having a polar group in the molecule and having a molecular length equal to or larger than that of the organic onium ion. At least a part of the strike molecule enters the interlayer of the clay mineral, and the polar group of the third guest molecule is kneaded with the second clay composite material forming a hydrogen bond with the clay mineral and a rubber material, The clay composite rubber material is characterized in that at least one of the second guest molecule and the third guest molecule is cross-linked to a molecule of the rubber material.

The most remarkable point in the present invention is that the rubber material is kneaded with a clay composite material in which guest molecules are introduced between layers of the clay mineral, and the guest molecules in the clay composite material and the rubber are kneaded. That is, the molecules of the material are cross-linked.

Next, the operation of the clay composite rubber material of the present invention will be described. The clay composite rubber material is prepared by kneading one of various clay composite materials, in which guest molecules are inserted between layers of the clay mineral, which has been organized as described above, into the rubber material and interposing the guest molecules and the molecules of the rubber material. It is one in which a crosslink is formed. Therefore, the clay mineral can be uniformly dispersed with a large interlayer distance even for rubber molecules in which the clay mineral has conventionally been difficult to disperse. The reason is considered as follows.

That is, as shown in FIG. 1, in the first clay composite material 100, since the clay mineral 7 organically formed by the organic onium ions 6 has a large space in space, the polarity is once between the layers. Although oligomers or polymers having a low viscosity can be incorporated, they tend to be immediately excluded due to the polarity of the silicate layer of the clay mineral. However, as described above, by bonding the polar group 10 to the first guest molecule 1, the polar group 10 forms a hydrogen bond with the silicate layer of the clay mineral 7, and stays between the layers. For this reason, between the layers of the clay mineral 7, the second guest molecules 2 which are hydrophobicized and have no polar group can stably stay. Since the second guest molecule 2 has a longer molecular length than the organic onium ion, it significantly swells between the layers.

[0010] As shown in FIG. 2, in the second clay composite material 200, the third group having the polar group 30 between the layers of the clay mineral 7 organized by the organic onium ions 6.
The guest molecules 3 are introduced to form hydrogen bonds with the silicate layer of the clay mineral 7. Therefore, the third guest molecule 3
Can stay between the layers of the clay mineral 7. Since the third guest molecule 3 has a longer molecular length than the organic onium ion 6, the third guest molecule 3 significantly swells between the layers.

As described above, at least one of the first and second clay composite materials in which the interlayer of the clay mineral is sufficiently swollen is kneaded with the rubber material. Then, the clay mineral does not agglomerate in the rubber material and is uniformly dispersed at the molecular level.
Further, since the clay mineral is uniformly dispersed, the barrier property against gas and the like is improved. In addition, the movement of rubber molecules near the silicate layer is restricted. Therefore, it has a good effect on the mechanical properties of the clay composite rubber material.

Next, the details of the present invention will be described. In the clay composite rubber material of the present invention, at least one or both of the first and second clay composite materials are kneaded with the rubber material.

First, the first clay composite material will be described. The first clay composite material is composed of a clay mineral that is organized by an organic onium ion, a first guest molecule, and a second guest molecule.

In the first clay composite material, the clay mineral is organically formed by ionic bonding with an organic onium ion having 6 or more carbon atoms. If the carbon number is less than 6,
The hydrophilicity of the organic onium ion increases, and the compatibility with the first and second guest molecules decreases. As the organic onium ion, for example, hexyl ammonium ion, octyl ammonium ion, 2-ethylhexylammonium ion, dodecyl ammonium ion, octadecyl ammonium ion, dioctyl dimethyl ammonium ion, trioctyl ammonium ion, or distearyl dimethyl ammonium ion is used. Can be.

Further, as unsaturated organic onium ion, 1
-Hexenyl ammonium ion, 1-dodecenyl ammonium ion, 9-octadecenyl ammonium ion (oleyl ammonium ion), 9,12-octadecadienylammonium ion (linol ammonium ion), 9,12,15- Octadecatrienyl ammonium ion (linoleyl ammonium ion) can be used.

Among these organic onium ions, when a clay composite rubber material is produced by the solvent dissolving method according to claim 10 , secondary onium ions are particularly preferred in terms of swelling with respect to a solvent. In addition, although the organic onium ions shown in the figures are represented in a bifurcated manner to indicate that they are secondary onium ions, they are not intended to be limited to secondary onium ions.

It is preferable to use a clay mineral having a large contact area with the first and second guest molecules. Thereby, the interlayer of the clay mineral can be greatly swollen. Specifically, the cation exchange capacity of clay minerals is
It is preferably 50 to 200 milliequivalents / 100 g. If the amount is less than 50 milliequivalents / 100 g, onium ions are not sufficiently exchanged, and it may be difficult to swell between layers of the clay mineral. On the other hand, if it exceeds 200 milliequivalents / 100 g, the bonding strength between the layers of the clay mineral becomes strong, and it may be difficult to swell between the layers of the clay mineral.

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

The first guest molecule has one or more polar groups in the molecule. The polar group is bonded to at least one of the main chain, side chain, or terminal of the first guest molecule. Among them, the polar group is preferably bonded to the terminal of the first guest molecule. Thereby, the interlayer of the clay mineral can be swollen more.

In the present invention, the term "polar group" refers to a substance in which electrons are localized in a molecule and a charge is biased, and does not include a completely polarized ion. Therefore, onium ions are not included in the polar groups. As in the invention of claim 2, the polar group of the first guest molecule and / or the third guest molecule is, for example, a hydroxyl group (OH), a halogen group (F, Cl, Br, I), a carboxyl group (COO).
H), one or two selected from the group consisting of a carboxylic anhydride group, a thiol group (SH), an epoxy group, and an amino group
More than a species. The amino group is a primary, secondary, or tertiary amine (NH ₂ , NH, N).

Incidentally, groups having a relatively strong degree of polarization, such as an imino group, a phosphonyl group, and a sulfonyl group, fall under the above definition of the "polar group", but these groups are more 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 equal to or smaller than that of the organic onium ion. If the molecular length is longer than the organic onium ion, it may be difficult to obtain the first guest molecule, and the type of the first guest molecule that is compatible with the low-polarity polymer 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 a main chain and / or a side chain. Olefin or paraffin. That is, the first guest molecule has, for example, one or more polar groups and a saturated or unsaturated linear or branched structure. Further, the main chain and / or the side chain may contain an aromatic ring.

Examples of the first guest molecule having a polar group include lauryl alcohol (C12), stearyl alcohol (C18), stearic acid (C18), and stearyl chloride (C18).
Can be used. OH, COO at both ends
Polyethylene, polypropylene, polyisoprene, polybutadiene having a polar group such as H, Cl, or an epoxy group, or a hydrogenated product or copolymer thereof may be used. These first guest molecules are selected and used so as to be substantially equal to or less than the molecular length of the organic onium ion. The first guest molecule preferably has 6 or more carbon atoms.

The first guest molecules tend 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 based on 1 part by weight of the organized clay mineral. If the amount 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 a part of the guest molecule penetrates between layers of the clay mineral. Not all of the first guest molecules need to penetrate between layers. For example, as in the invention of claim 5 , if at least 10% by weight of the total amount of the first guest molecules enters between the layers of the clay mineral in the first clay composite material, the layers 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 non-polar or low-polarity oligomer or polymer having no polar group. The second guest molecule has a linear or branched structure, is saturated or unsaturated, and
It may or may not contain an aromatic ring. The molecular length of the second guest molecule is larger than that of the organic onium ion. When the molecular length is equal to or smaller than the molecular length of the organic onium ion, there is a problem that swelling between the layers of the clay mineral becomes insufficient.

As in the third aspect of the present invention, the second guest molecule is preferably a non-polar or low-polarity oligomer or polymer having a molecular weight of 1,000 to 500,000. If it is less than 1,000, swelling between layers of the clay mineral may be insufficient. On the other hand, 500000
If the melting point of the clay mineral is exceeded, the solvent may become insoluble or the softening point or melting point may be higher than the decomposition point of the clay mineral. It is more preferable that the second guest molecule has a molecular length of about 3 to 4 times or more of the organic onium ion. As the second guest molecule, for example, liquid polybutadiene, liquid polyisoprene, and liquid butyl rubber can be used.

The second guest molecules tend 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 based on 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 enters between layers of the clay mineral. Not all of the second guest molecules need be involved.

Next, the second clay composite material will be described. The second clay composite material is composed of a clay mineral that has been organized by an organic onium ion and a third guest molecule.

In the second clay composite material, it is preferable to use any of the clay minerals and organic onium ions listed above as the clay mineral and organic onium ions. Further, the third guest molecule has one or more polar groups in the main chain and / or the side chain. As the polar group, it is preferable to use any of the groups listed as the polar group of the first guest molecule. The polar groups of the clay mineral, the organic onium ion, and the third guest molecule in the second clay composite material are the same as those of the clay mineral, the organic onium ion, and the first guest molecule in the first clay composite material.
Either the same type or different types may be used.

The molecular length of the third guest molecule is equal to or larger than that of the organic onium ion. When the molecular length of the organic onium ion is smaller than the molecular length of the organic onium ion, the third guest molecule does not protrude outside the region where the organic onium ion exists at the clay interface, so that the clay mineral is less likely to be dispersed in the rubber material.

The third 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 a main chain and / or a side chain. Olefin or paraffin. That is, the third guest molecule has, for example, one or more polar groups and a saturated or unsaturated linear or branched structure. The main chain and / or side chain may contain an aromatic ring.

As the third guest molecule, for example, lauryl alcohol (carbon number 12), stearyl alcohol (carbon number 18), stearic acid (carbon number 18), stearyl chloride (carbon number 18) and the like are particularly preferable. .
In addition, polyethylene, polypropylene, polyisoprene, polybutadiene having polar groups such as OH, COOH, Cl, and epoxy groups at both terminals may be used, or a hydrogenated product or copolymer thereof. These third guest molecules are selected and used so as to be equal to or longer than the molecular length of the organic onium ion.

As the mixing ratio of the third guest molecule increases, the interlayer between the clay minerals tends to expand widely. The mixing ratio of the third guest molecule is preferably 0.5 part by weight or more based on 1 part by weight of the organized clay mineral. If the amount is less than 0.5 part by weight, the swelling between layers of the clay mineral may be insufficient.

Also, as in the fourth aspect of the present invention, the third
The molecular weight of the guest molecule is preferably from 500 to 100,000. If it is less than 500, the swelling between layers of the clay mineral may be insufficient. On the other hand, 10,000
If it exceeds 0, it may become insoluble in the solvent or its softening point or melting point may be higher than the decomposition point of the clay mineral. The third guest molecule is composed of 3 to 4 organic onium ions.
More preferably, it has a molecular length about twice or more.

At least a part of the third guest molecule enters between layers of the clay mineral. It is not necessary for all of the third guest molecules to enter between the layers of the clay mineral.
For example, as in the invention of claim 6 , if 10% by weight or more of the total amount of the third guest molecules enters between the layers of the clay mineral in the second clay composite material, the layers expand sufficiently. If it is less than 10% by weight, the swelling between layers of the clay mineral may be insufficient. In particular, in the case where the third guest molecule is a polymer having a molecular weight of about 1,000 to 10,000, the interlayer expansion is sufficient if 10% by weight of the total amount of the third guest molecule is contained.

Next, as in the invention of claim 7 , the rubber material includes natural rubber, isoprene rubber, chloroprene rubber, styrene rubber, nitrile rubber, ethylene-propylene rubber, butadiene rubber, styrene-butadiene rubber,
Butyl rubber, epichlorohydrin rubber, acrylic rubber,
One or more kinds selected from the group consisting of urethane rubber, fluorine rubber, and silicone rubber can be used.

The second guest molecule or the third guest molecule contained in the first and second clay composite materials is, for example, sulfur cross-linking called “vulcanization” between the second guest molecule and the rubber material molecule. Alternatively, a cross-linking bond or the like corresponding thereto is formed. As a cross-linking equivalent thereto, for example, a peroxide cross-linking can be mentioned.

Next, the upper Symbol least one organic onium ion in the first clay composite or second clay composite material, said at least one of the second guest molecules or the third guest molecule, of the rubber material It is preferable that a crosslink is formed between the molecule and the molecule. As a result, the interface between the silicate layer of the clay mineral and the rubber is very strongly bonded.
Therefore, the movement of the rubber molecules near the silicate layer is further restricted, and the mechanical properties, particularly the hardness and the elastic modulus, are improved.

The clay composite rubber material of the present invention is formed by, for example, a press molding method or an extrusion molding method. The clay composite rubber material of the present invention can be used for various uses of ordinary rubber. In particular, the effect of the present invention can be most effectively exerted when it is used when improvement in barrier properties against gas and the like and mechanical properties of a rubber material are required.

Next, a first method for manufacturing the clay composite rubber material, for example, as in the invention of claim 8,
By contacting the clay mineral with an organic onium ion having 6 or more carbon atoms, an ionic bond is formed between the clay mineral and the organic onium ion to organically form the clay mineral. A first guest molecule which is the same as or smaller than the organic onium ion and has a polar group in the molecule; and a first guest molecule having a molecular length larger than that of the organic onium ion and having an unsaturated group in the molecule. A second guest molecule having no polar group is brought into contact with the clay mineral to form a hydrogen bond with the polar group of the first guest molecule in the clay mineral to hydrophobize the surface of the clay mineral. At the same time, a first clay composite material is obtained by causing at least a part of the second guest molecule to enter between the layers of the clay mineral, and the first clay composite material is kneaded with a rubber material. There are provided methods for producing the clay composite rubber material, characterized in that the formation of crosslinks between the molecules of the unsaturated group and the rubber material of the serial second guest molecules.

The most remarkable point in the first method is that the surface of the organized clay mineral is hydrophobized by a first guest molecule having a polar group, and the second guest molecule having an unsaturated group is converted to a clay. To penetrate between mineral layers,
And forming a cross-linking between the unsaturated group and the molecule of the rubber material.

Next, the operation of the first method will be described. In the above manufacturing method, first, as shown in FIG. 1, an organic onium ion 6 is bonded to a clay mineral 7 to make the clay mineral organic. As a result, some space is generated between the layers of the clay mineral 7.

Next, when the first and second guest molecules are brought into contact with the organic clay mineral, the first and second guest molecules 1 and 2 enter the space between the above-mentioned layers. The first guest molecule 1 has a polar group 10. Therefore, clay mineral 7
And hydrogen bonds between the layers of the clay mineral 7 to make the layers of the clay mineral 7 hydrophobic. Therefore, the second guest molecules 2 having low polarity that have entered the layers of the clay mineral 7 are not eliminated by the polarity of the clay mineral, but can stably remain 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 molecules 2 stay between the layers of the clay mineral 7, the layers are infinitely swollen with the layers being swollen indefinitely.
Therefore, the first clay composite material 10 in the infinite swelling state
By kneading 0 into a rubber material, a clay composite rubber material can be obtained in which clay minerals, which are naturally polar substances, are uniformly dispersed at a molecular level in a rubber material having low polarity.

The second guest molecule has an unsaturated group. The unsaturated groups crosslink with molecules of the rubber material when kneaded with the rubber material. Therefore, the movement of the rubber molecules in the vicinity of the silicate layer is restricted, which has a favorable effect on the mechanical properties of the clay composite rubber material.

Next, the upper Symbol organic onium ion has an unsaturated group, in the step of the first clay composite material is kneaded with a rubber material, and the unsaturated group of the organic onium ion, the second guest molecule It is preferable to form a crosslink between the unsaturated group and the unsaturated group in the rubber material. When the organic onium ion is used, when the second guest molecule and the rubber material are kneaded and crosslinked, the unsaturated group of the organic onium ion, the unsaturated group of the second guest molecule, and the molecule of the rubber material are mixed. Crosslinks are formed. Therefore, the silicate layer of the clay mineral and the interface of the rubber are bonded very firmly. Therefore, the movement of the rubber molecules in the vicinity of the silicate layer is further restricted, and the hardness elastic modulus is improved during the mechanical properties.

First, as a method of bringing the clay mineral into contact with an organic onium ion, for example, there is 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 excess organic onium ion.

Next, as the first guest molecule, those described above can be used. As the second guest molecule, liquid polybutadiene, liquid polyisoprene, liquid butyl rubber or the like having an unsaturated group can be used. The order in which the first and second guest molecules are brought into contact with the organic clay mineral does not matter. That is, both may be administered simultaneously and brought into contact,
You may contact another person after contacting any one person. In any case, the same operation and effect can be obtained as a result.

As a method of contacting the first and second guest molecules, for example, as in the tenth aspect of the present invention, the first and second guest molecules are dissolved in a solvent, and the organic clay is dissolved. There is a method of contacting with minerals. Claim 11
As in the invention, there is a method in which the first and second guest molecules are brought into contact with the above-mentioned organic clay mineral in a state of being softened or melted by heat.

[0052] According to the method of the former claims 10, it is possible to enter the first, the second guest molecules between the layers of the clay mineral at room temperature. Solvents that can be used in this method include, for example, low polarity solvents such as toluene, benzene, xylene, hexane, and octane. On the other hand, in the latter method of claim 11 , 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. Heat. This heating is performed at a temperature at which the first and second guest molecules and the clay mineral do not decompose and stably exist. For example, the heating temperature is preferably 250 ° C. or less. If the temperature exceeds 250 ° C., the organized clay mineral may be decomposed.

As the method of kneading the first clay composite material and the rubber material, a general method of kneading rubber can be used. In particular, a method of kneading with a rubber roll at a temperature of 100 ° C. or less is preferable. If the temperature exceeds 100 ° C., the crosslinking reaction may proceed during kneading.

When kneading the first clay composite material and the rubber material, it is necessary to form a sulfur cross-linking called "vulcanization" or a cross-linking equivalent thereto between them. For that purpose, in the case of the first clay composite material, the second guest molecule needs to contain an unsaturated group.
An unsaturated group refers to a group having a double or triple bond formed between carbon atoms. Examples of the second guest molecule having an unsaturated group include liquid polybutadiene, liquid polyisoprene, and liquid butyl rubber. In kneading, for example, it is preferable to add a vulcanizing agent such as sulfur, a vulcanization accelerator, a crosslinking agent such as a peroxide, and a filler such as carbon.

Next, a second method for producing the clay composite rubber material, for example, as in the invention of claim 9,
By contacting the clay mineral with an organic onium ion having 6 or more carbon atoms, an ionic bond is formed between the clay mineral and the organic onium ion to organically form the clay mineral. Contacting a third guest molecule having a polar group and an unsaturated group in the molecule and having a molecular length equal to or larger than that of the organic onium ion to form a third layer between the clay mineral layers; After at least a part of the guest molecules are allowed to enter and form a hydrogen bond with the clay mineral to obtain a second clay composite material, the second clay composite material is kneaded with a rubber material, and the third clay composite material is mixed. There is a method for producing a clay composite rubber material, which comprises forming a cross-link between an unsaturated group of a guest molecule and a molecule of the rubber material.

The most remarkable point of the second method is that a third guest molecule having a polar group and an unsaturated group is introduced between the layers of the organized clay mineral, and the unsaturated group and the rubber The formation of cross-links between the molecules of the material.

The second method is different from the first method in which the third guest molecule is used, in that the first and second guest molecules are used.
Different from the method. The third guest molecule has a polar group and an unsaturated group, and its molecular length is the same as or longer than the organic onium ion. As the third guest molecule, for example, polybutadiene having -OH groups at both ends, polyisoprene having -OH groups at both ends, or the like can be used. Others are the same as in the first method.

Next, the operation of the second method will be described. In the above method, first, as shown in FIG. 2, a certain amount of space is generated between the layers of the clay mineral 7 by bonding the organic onium ions 6 to the clay mineral 7. Next, a third guest molecule 3 having a polar group 30 is brought into contact with the organic clay mineral 7. Then
The third guest molecule 3 enters the space between the layers of the clay mineral 7 and hydrogen bonds with the silicate layer of the clay mineral 7 by the polar group 30. Thereby, the third guest molecule 3
Remains between the layers without being excluded by the polarity of the surface of the clay mineral 7. For this reason, similarly to the above-mentioned first method, the interlayer of the clay mineral 7 further swells to an infinite swelling state. Therefore, by kneading the second clay composite material 200 in the infinitely swollen state into the rubber material, the clay mineral which is originally a polar substance can be uniformly dispersed at the molecular level in the rubber material.

The third guest molecule has an unsaturated group. For this reason, the unsaturated group cross-links with the molecules of the rubber material, thereby similarly favorably affecting the mechanical properties of the clay composite rubber material.

Next, the upper Symbol organic onium ion has an unsaturated group, in the step of kneading the rubber material the second clay composite material, the unsaturated group of the organic onium ion, the third guest molecule It is preferable to form a cross-link between the unsaturated group and the unsaturated group of the rubber material. When an organic onium ion is used, a cross-linking is formed between the unsaturated group of the organic onium ion, the third guest molecule, and the rubber material molecule. Affect.

Further, both the first clay composite material and the second clay composite material may be kneaded with a rubber material to form a cross-link between the second and third guest molecules and the rubber material molecules. it can. In this case, the same effect as above can be obtained.

As described above, as a method of bringing the third guest molecule into contact with the organic clay mineral,
As in the tenth aspect of the present invention, there is a method in which the third guest molecule is brought into contact with an organized clay mineral in a state of being dissolved in a solvent. Further, there is a method as in the eleventh aspect , wherein the third guest molecule is brought into contact with the organic clay mineral in a state of being softened or melted by heat.

[0063]

BEST MODE FOR CARRYING OUT THE INVENTION

First Embodiment A clay composite rubber material according to an embodiment of the present invention will be exemplified and described. In the clay composite rubber material of the present example, the first clay composite material and the rubber material are kneaded, and the second guest molecules in the first clay composite material are cross-linked with the molecules of the rubber material.

As shown in FIG.
A clay mineral 7 organically treated with 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 being hydrogen bonded to the clay mineral 7 And a second guest molecule 2 having a larger molecular length than the organic onium ion and having no polar group in the molecule. At least a part of the first guest molecule 1 and the second guest molecule 2 penetrates between layers of the clay mineral 7.

The clay mineral is sodium-type montmorillonite (produced in Yamagata Prefecture, with an ion exchange capacity of 120 meq / 100).
g). The organic onium ion is distearyl dimethyl ammonium ion (hereinafter referred to as DSDM) and has 38 carbon atoms. The first guest molecule is stearic acid, which has 18 carbon atoms. The second guest molecule is liquid butyl rubber (manufactured by Hardman Co., trade name: Karen 800), and its molecular weight is about 5,000.

Next, a method for producing the above-mentioned clay composite rubber material will be described. First, 20.0 g of montmorillonite was dispersed in 2000 ml of water at 80 ° C. Next, 21.0 g of distearyl dimethyl ammonium chloride was added to 80
Dissolved in 1500 ml of water at ℃. The dispersion and the solution were mixed at once. The precipitate was washed twice with water at 80 ° C. to obtain montmorillonite organically treated with DSDM. This is hereinafter referred to as DSDM-montmorillonite.

The inorganic content in the DSDM-montmorillonite determined by the burning method was 54.2% by weight. The interlayer distance between DSDM and montmorillonite was measured by an X-ray diffraction method, and the swelling behavior was observed. The interlayer distance between DSDM and montmorillonite was 32.8 °.

Next, in 20 g of toluene as a solvent, 1.0 g of the above-mentioned DSDM-montmorillonite, 0.5 g of stearic acid, and 1.0 g of liquid butyl rubber (trade name: Karen 800, manufactured by Hardman) were added. Mix for 6 hours. Next, the toluene was evaporated under reduced pressure.
Thus, a first clay composite material was obtained.

The interlayer distance of montmorillonite in the clay composite material was measured by an X-ray diffraction method.
Was Å. From this, the addition of 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.

Next, the first clay composite material and the rubber material were kneaded with a roll according to ASTM D 3182. The rubber material is butyl rubber (Nippon Synthetic Rubber But)
yl268) was used. The mixing ratio of the clay composite rubber material is such that the first clay composite material 2
0 parts by weight (including 5 parts by weight of clay mineral), 20 parts by weight of carbon (Asahi Carbon # 70), 1 part by weight of zinc white, 1 part by weight of sulfur.
75 parts by weight and 1 part by weight of a vulcanization accelerator.

Next, after uniformly kneading, at 150 ° C., 40
A sheet having a thickness of 2 mm was formed by vulcanization for one minute. A dumbbell No. 3 test piece was cut out from the sheet and subjected to a tensile test. As a result, the tensile strength was 18.0 MPa. Also, a sheet having a thickness of 0.5 mm was formed in the same manner, and gas permeability with nitrogen was evaluated. As a result, the gas permeability coefficient was 1.9 × 10 ⁻¹¹ cm ³ · cm · cm ⁻² · sec ⁻¹
-It was cmHg- ¹ .

Embodiment 2 In this embodiment, a sheet was formed by changing the mixing ratio of the clay composite rubber material (samples 1 to 16), and the mechanical properties were evaluated. As shown in Table 1, a second clay composite material was used as the clay composite rubber material. The second clay composite material is
It consists of an organized clay mineral and a third guest molecule. As the organized clay mineral, DSDM-montmorillonite (referred to as DSDM-Mt) was used. DSD
In M-montmorillonite, the weight ratio between DSDM and montmorillonite was always the same. As the third guest molecule, liquid polybutadiene having a -OH group at both ends (trade name G2000, trade name of Nippon Soda Co., Ltd.) (denoted as liquid rubber) was used. As a rubber material, butyl rubber (Nippon Synthetic Rubber Butyl 268) was used. For comparison, untreated montmorillonite (denoted as Na-Mt) was used as an unorganized clay mineral.

The mechanical properties of the molded sheet of the clay composite rubber material were evaluated by gas permeability coefficient, storage modulus, tensile strength, elongation, and tensile stress. The storage modulus was measured with a viscoelastic spectrometer. Tensile stress was measured by a tensile test.

Table 1 shows the measurement results of the mechanical characteristics. In the same table, in the numerical value column of the composition ratio of DSDM-Mt,
Figures in parentheses indicate the weight ratio of montmorillonite,
The numerical value on the left indicates the weight ratio of DSDM-Mt in parts by weight. In the numerical value column of Table 1, "-",
“X” indicates that measurement is not possible.

First, based on the results shown in Table 1, the presence or absence of montmorillonite is considered. Sample 9 using Organized Montmorillonite (DSDM-Mt)
And non-organized montmorillonite (Na-M
Comparing with sample 12 using t), sample 9 has
Excellent storage modulus and gas barrier properties. From this, it can be seen that organic properties of montmorillonite can provide better mechanical properties.

The reason is that when montmorillonite is made organic, liquid butyl rubber enters between the layers of montmorillonite, the layers swell, and the montmorillonite is uniformly dispersed at the molecular level in the rubber material. It is considered that the montmorillonite constrained the molecular motion of the rubber material and had a good effect on the mechanical properties such as the storage elastic modulus and gas barrier properties of the clay composite rubber material.

On the other hand, when the montmorillonite is not made organic, liquid butyl rubber cannot enter between the layers, and the layers do not swell. Therefore, montmorillonite is not uniformly dispersed in the rubber material. Therefore, the molecular motion of the rubber material is hardly restricted. For this reason,
It is considered that the mechanical properties of the clay composite rubber material were not improved.

Next, the storage elastic modulus of the clay composite rubber material will be considered. Samples 5, 6, and 7 show that when the montmorillonite content was increased to 5, 10, and 15 parts by weight, the storage modulus was significantly improved. The reason is that the more liquid butyl rubber enters between the layers of the organized montmorillonite, the more the layers swell and the more easily the montmorillonite is easily dispersed in the rubber material. It is considered that the storage elastic modulus was increased by the uniform dispersion of montmorillonite. Also,
Samples 9 and 10 each had zero carbon, but also in this case, sample 10 having a higher content of montmorillonite had an improved storage modulus.

Next, the gas barrier properties of the molded sheet will be considered. Sample 1 has a large amount of carbon and no montmorillonite. On the other hand, Samples 9 and 10 have a small amount of carbon and a large amount of montmorillonite. When these are compared, the gas permeability of Samples 9 and 10 containing more montmorillonite was reduced by 60 to 70%. This indicates that the higher the content of montmorillonite, the higher the gas barrier properties.

[0080]

[Table 1]

Embodiment 3 In this embodiment, a sheet was formed by changing the compounding ratio of the clay composite rubber material (samples 21 to 26), and its mechanical properties were evaluated. The clay composite rubber material is obtained by kneading a second clay composite material and a rubber material. As the clay mineral, sodium-type montmorillonite (produced in Yamagata Prefecture, ion exchange capacity: 120 meq / 100 g) was used. As the organic onium ion, an oleyl ammonium ion having an unsaturated group in the molecule was used. As the third guest molecule, polyisoprene having a hydroxyl group (manufactured by Kuraray: LIR506)
Was used.

Next, a method for producing the above-mentioned clay composite material will be described. First, add 20.0 g of montmorillonite to 80
Dispersed in 2000 ml of water at ℃. Next, 8.8 g of oleylamine hydrochloride was dissolved in 1500 ml of water at 80 ° C. The two aqueous solutions were mixed at once. The precipitate was washed twice with water at 80 ° C. to obtain montmorillonite organically treated with oleyl ammonium ion. This is OL-
Montmorillonite. The inorganic content in OL-montmorillonite determined by the burning method was 69.4% by weight. When the interlayer distance of montmorillonite was measured by the X-ray diffraction method, the interlayer distance of OL-montmorillonite was 22.5 °.

The above OL was used for 100 g of polyisoprene.
-70, 140, 210 g of montmorillonite respectively
The mixture was mixed at 80 ° C. for 4 hours to obtain three kinds of second clay composite materials. When the interlayer distance of montmorillonite in the clay composite material was measured by the X-ray diffraction method,
Met. To this, 3.0 g of sulfur, 5.0 g of zinc white, 3.0 g of stearic acid, and 1.5 g of a vulcanization accelerator (Noxeller MSA-G manufactured by Ouchi Shinko Chemical Co., Ltd.) were added and kneaded.

The kneaded product was kneaded with butyl rubber and carbon in the composition shown in Table 2 to form a sheet (Sample 2).
1-26). Further, for comparison, those formed into sheets without adding the second clay composite material were produced, and these were designated as Samples 21 to 23. The mechanical properties of the samples 21 to 26 were measured in the same manner as in Example 2. Table 2 shows the measurement results.

Table 2 shows the measurement results of the mechanical characteristics. In the same table, in the numerical value column of the composition ratio of OL-montmorillonite, the numerical value in parentheses indicates the weight ratio of montmorillonite, and the numerical value to the left of () indicates the weight ratio of OL-montmorillonite in parts by weight. Things. In the numerical value column of Table 2, "-" and "x" indicate that measurement is impossible.

[0086] From the table, it can be seen that the samples 24-26 using OL-montmorillonite have better mechanical properties as compared with the sample 22 not using OL-montmorillonite. I understand. Also,
Samples 24 to 26 of this example had higher storage elastic modulus, tensile strength, elongation, and tensile stress than Samples 5 to 7 of Embodiment 2 described above. Also, the gas shutoff performance was high.

The reason is presumed as follows. That is, the polyisoprene as the third guest molecule and the oleyl ammonium ion as the organic onium ion each have an unsaturated group in the molecule. Therefore, when both are kneaded and sulfurized, a cross-link is also formed in the organic onium ion at the same time. Therefore, the interface between the montmorillonite silicate layer and the butyl rubber is very strongly bonded. Therefore, it is considered that the movement of the rubber molecules near the silicate layer is restricted, and the mechanical properties, particularly the hardness and the elastic modulus, are improved.

[0088]

[Table 2]

[0089]

As described above, according to the present invention, the dispersibility of a clay mineral in a rubber polymer having a low polarity is high,
A clay composite rubber material having excellent mechanical properties and a method for producing the same can be provided.

[Brief description of the drawings]

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

FIG. 2 is an explanatory view of a second clay composite material according to the present invention.

[Explanation of Codes] . . First guest molecule, 10, 30. . . Polar group, 100. . . 1. first clay composite material; . . Second guest molecule, 200. . . 2. second clay composite, . . 5. third guest molecule, . . 6. organic onium ions, . . Clay minerals,

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-9-12769 (JP, A) JP-A-8-333114 (JP, A) JP-A-4-357108 (JP, A) JP-A-4-127108 357107 (JP, A) JP-A-52-111945 (JP, A) JP-A-1-198645 (JP, A) JP-A-51-106147 (JP, A) JP-A-61-213231 (JP, A) JP-A-55-13791 (JP, A) JP-A-5-194485 (JP, A) JP-A-10-7418 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 21/00 C08K 3/34 C08K 9/04

Claims (11)

(57) [Claims] An organic onium ion having 6 or more carbon atoms is ionically bonded to the clay mineral, and a clay mineral having a molecular length equal to or smaller than that of the organic onium ion and having a polar group in the molecule. A first guest molecule hydrogen-bonded to the clay mineral; 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. The second guest molecule is composed of the first clay composite material, at least a part of which is penetrated between the layers of the clay mineral, and / or a clay mineral organically formed by ionic bonding of an organic onium ion having 6 or more carbon atoms. A third guest molecule having a polar group in the molecule and having a molecular length equal to or larger than that of the organic onium ion, wherein the third guest molecule is at least Of the second guest composite material, in which the polar group of the third guest molecule forms a hydrogen bond with the clay mineral, is kneaded with a rubber material; A clay composite rubber material, wherein at least one of a guest molecule and a third guest molecule is cross-linked to a molecule of the rubber material. 2. The method according to claim 1 , wherein the polar group of the first guest molecule and / or the third guest molecule includes a hydroxyl group, a halogen group, a carboxyl group, a carboxylic anhydride group, a thiol group, an epoxy group, and an amino group. A clay composite rubber material comprising one or more members selected from the group. 3. The method of claim 1 or 2, the second guest molecule, clay composite rubber material having a molecular weight characterized in that it is a non-polar oligomers or polymers of 1,000 to 500,000. 4. A any one of claims 1 to 3
The third guest molecule has a molecular weight of 500 to 100,000.
A clay composite rubber material, characterized by being a non-polar oligomer or polymer. 5. according to any one of claims 1-4,
A clay composite rubber material, wherein at least 10% by weight of the total amount of the first guest molecules enters between layers of the clay mineral in the first clay composite material. 6. A any one of claims 1 to 5
A clay composite rubber material, wherein at least 10% by weight of the total amount of the third guest molecules enters between layers of the clay mineral in the second clay composite material. 7. A any one of claims 1 to 6
The rubber materials include natural rubber, isoprene rubber, chloroprene rubber, styrene rubber, nitrile rubber, ethylene-propylene rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, epichlorohydrin rubber, acrylic rubber, urethane rubber, fluorine rubber, and silicone rubber A clay composite rubber material, characterized in that it is at least one member selected from the group consisting of: 8. The clay mineral is contacted with an organic onium ion having 6 or more carbon atoms, thereby forming an ionic bond between the clay mineral and the organic onium ion to organically convert the clay mineral. A 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 first guest molecule having a molecular length larger than the organic onium ion and having an unsaturated group in the molecule. And contacting the clay mineral with a second guest molecule having no polar group to form a hydrogen bond between the polar group of the first guest molecule and the clay mineral to form the clay mineral. After the surface is made hydrophobic and at least a part of the second guest molecule is inserted between the layers of the clay mineral, a first clay composite material is obtained. Then, the first clay composite material is mixed with a rubber material. While manufacturing method of the clay composite rubber material, characterized in that the formation of crosslinks between the molecules of the unsaturated group and the rubber material of the second guest molecule. 9. 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 organically convert the clay mineral. Contacting the clay mineral with a third guest molecule having a polar group and an unsaturated group in the molecule and having a molecular length equal to or larger than the organic onium ion to form an interlayer of the clay mineral; And at least a part of the third guest molecule is made to enter therein to form a hydrogen bond with the clay mineral to obtain a second clay composite material, and the second clay composite material is kneaded with a rubber material. A method for producing a clay composite rubber material, wherein a cross-linking is formed between an unsaturated group of the third guest molecule and a molecule of the rubber material. 10. The method according to claim 8 , wherein the first guest molecule and / or the second guest molecule or the third guest molecule is brought into contact with the organic clay mineral while being dissolved in a solvent. A method for producing a clay composite rubber material, comprising: 11. The organic or mineral clay mineral according to claim 8 , wherein the first guest molecule and / or the second guest molecule or the third guest molecule is in a state of being softened or melted by heat and being in contact with the organized clay mineral. A method for producing a clay composite rubber material.