JP3368864B2 - Polymer composite materials - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer composite material containing clay.

[0002]

TECHNICAL FIELD Conventionally, addition and mixing of clay have been studied for the purpose of improving the properties of polymer materials. EPGi
Annelis et al., in Chem. Mater. 5, 1694-1696 (1993), compounded polystyrene and clay. However, polystyrene only intervenes between the clay layers and has not yet broken the clay layer structure or dispersed in a single clay layer.

Further, in Japanese Patent Laid-Open No. 8-333114, a device for introducing a polar group into a polymer to improve the dispersibility of clay is made. However, even in this case, the dispersibility of the clay was insufficient for the highly polar polymer.

[0004]

SUMMARY OF THE INVENTION In view of such conventional problems, the present invention is to provide a polymer composite material having excellent dispersibility of clay in a polymer having high polarity.

[0005]

According to the present invention, as described in claim 1,
A polymer having a nitrile group ranging solubility is a parameter of 8.8 or more 19 or less representative of the polarity of the polymer, organized organic clay with an organic agent fewer than 24 6 or more carbon atoms of the longest chain Do from the Ri and chromatic said nitrile group
The polymer has a nitrile group content of 5 to 50% by weight.
A polymer composite material, characterized by that.

The inventors of the present invention improve the dispersibility of clay in a high polarity polymer by matching the polarity of the polymer with the polarity of the organized clay for the high polarity polymer. I found that. That is, the polarity of the polymer changes depending on the type and content of the functional group. By varying the length of the carbon chain of the organizing agent, the fine dispersion of clay is achieved by using the organized clay adjusted to the polarity suitable for each polymer.

The polymer composite material of the present invention has a solubility of 8.8.
The content of the highly polar nitrile group of 19 or more and 19 or less is 5 to 50
An organically modified clay that is organically modified by an organic agent having 6 or more and less than 24 carbon atoms is added to a polymer in an amount of 7% to form a composite. The polarity of the organic agent having carbon number in the above range is
It is suitable for the polymer having the above-mentioned highly polar nitrile group .
Therefore, the compatibility of the organized clay with the polymer having high polarity is improved, and the clay dispersibility in the polymer is improved. Further, the fine dispersion of clay in the polymer improves the gas barrier property of the polymer composite material. Therefore, the polymer composite material of the present invention can be used as a film material having a high gas barrier property, for example, a packaging film.

Next, details of the present invention will be described. In the present invention, the solubility of the polymer is a parameter that represents the polarity of the polymer, and is described in Co., No. 193, p.
9-11 (1993) Defined by the numerical value calculated based on “Calculation of solubility parameter”. There are two methods for obtaining the solubility parameter, one is by measurement and the other is by calculation.

As a method of measurement, the latent heat of vaporization method,
There are vapor pressure method, dissolution method, swelling method, surface tension method, critical pressure method, thermal swelling coefficient method, and calculation method from refractive index. The method of, is a low molecular weight compound having a vapor pressure, and the method of is a useful means for polymers.

On the other hand, as a method by calculation, there is a method of determining the molecular cohesive energy and the molecular volume for each functional group constituting the compound and obtaining from the formula (1) of FIG. 5, which is the solubility of the compound having no vapor pressure. It is easy to obtain the parameter (SP) value. This method includes Small, Hoy, Rheine
There are constants proposed by ck et al. and Tortorello et al. They are,
There is a method of determining the molecular attraction constant G, which is the product of the cohesive energy and the molecular volume, by the equation (2) in FIG. 5, but it has the drawback that it cannot be calculated unless the density or molecular weight of the compound to be obtained is known.

On the other hand, the method proposed by Fedors is based on the cohesive energy Δe ₁ and the molecular volume Δv per each functional unit.
_This is a method in which ₁ is determined and the total sum is obtained by the equation (3) in FIG. In the present invention, the method proposed by the above Fedors is useful for determining the solubility of the polymer. The lower part of FIG. 5 shows the above Δe ₁
And an example of Δv ₁ is shown.

The solubility of the polymer is 8.8 or more and 19 or less. If it is less than 8.8, the polarity is too low, and good dispersion of clay cannot be obtained. That is, since the polarities of the polymer and the organized clay do not match, they are not well compatible with each other and the clay is difficult to disperse in the polymer. If it exceeds 19, the polarity is too high and good dispersion of clay cannot be obtained.
In this case as well, the polarities of the polymer and the organized clay do not match, so the two are not well compatible and the clay is difficult to disperse in the polymer.

The polymer may be, for example, a resin or rubber as described in claim 3.
As the polymer containing a nitrile group having a solubility of 8.8 or more and 19 or less, a polymer such as polyether nitrile can be used.

Further, as the polymer having the above-mentioned solubility, there is a copolymer of two or more kinds of monomers. Examples of such copolymers include acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer.
Body, A acrylonitrile - butadiene copolymer, hydrogenated acrylonitrile - butadiene copolymer, A acrylonitrile <br/> - etc. acrylate copolymer can be used.

A copolymer composed of a polar monomer and a nonpolar monomer is particularly preferable. As such a copolymer,
Acrylonitrile - styrene copolymer, acrylonitrile - butadiene - styrene copolymer, A acrylonitrile <br/> - butadiene copolymer, hydrogenated acrylonitrile - have etc. butadiene copolymer.

Further, as a polymer having a nitrile group ,
Nitrile rubber or the like can be used. As the rubber, for example, there is one in which a crosslinking agent is added to the above polymer to form a crosslinking bond. The cross-linking includes, for example, sulfur cross-linking and peroxide cross-linking.

The above polymer has a nitrile group, which is a polar group ,
Have This improves the dispersibility due to the strong interaction with the organized clay surface.

In the present invention, the polar group of the above polymer is
Is a nitrile group . As the polymer having a nitrile group, e.g., A acrylonitrile - butadiene copolymer, hydrogenated acrylonitrile - butadiene copolymer, ethylene having a hydroxyl group - vinyl alcohol copolymer is preferred.

In the above polymer in which the polar group is a nitrile group,
There are, nitrile group content in the polymer, 5～50W
Ru t% der. If it is less than 5 wt%, sufficient mechanical properties and gas barrier properties may not be obtained. 50 wt
When it exceeds%, sufficient clay dispersibility may not be obtained. More preferably, two in the polymer
The tolyl group is 10 to 50 wt%. As a result, it is possible to obtain a polymer composite material in which the dispersibility of clay is good and various physical properties are well balanced. In particular, the nitrile group content in the acrylonitrile-butadiene copolymer or hydrogenated acrylonitrile-butadiene copolymer is preferably 5 to 50 wt%, more preferably 10 to 50 wt% as described above.

For reference, when the polar group of the polymer is a hydroxyl group, the hydroxyl group content in the polymer is
It is preferably 20 to 90 wt%. If it is less than 20 wt%, the physical property balance of the polymer composite material may be deteriorated. If it exceeds 90 wt%, good clay dispersibility may not be obtained. More preferably, the hydroxyl group in the polymer is 30 to 80 wt%. This makes it possible to provide a polymer composite material in which the dispersibility and physical properties of clay are well balanced. In particular, ethylene
As described above, the content of hydroxyl group in the vinyl alcohol copolymer is 20 to 90 wt%, and further 30 to 80 wt%.
Is desirable.

The number average molecular weight of the polymer is 5,0.
It is preferably from 00 to 10,000,000.
If it is less than 5,000, the mechanical properties may be insufficient. If it exceeds 10,000,000, there may be a problem in workability of the polymer composite material. More preferably, the number average molecular weight of the polymer is 10,
000 to 1,000,000, preferably 10
It is from 10,000 to 1,000,000. By this,
Both mechanical properties and workability are improved.

The organized clay is obtained by adsorbing and binding an organizing agent on the surface of clay (clay mineral) by a physical or chemical method. Since clay is naturally hydrophilic, it is made hydrophobic by the adsorption and binding of organic agents. The polarity of the whole organized clay can be controlled by changing the type of organizing agent. In particular, it is preferable to use an organic onium ion salt as the organizing agent, and it is preferable to ionically bond the organic onium ion by ion exchange between the organic onium ion salt and the metal ion between the clay layers.
As the organic onium ion, organic ammonium ion, organic phosphonium ion or the like can be used. Among these, it is preferable to use organic ammonium ions.

Specific examples of the organic onium ion include, for example, hexyl ammonium ion, octyl ammonium ion, decyl ammonium ion, dodecyl ammonium ion, tetradecyl ammonium ion, hexadecyl ammonium ion, octadecyl ammonium ion, hexyl trimethyl ammonium ion,
Examples include octyl trimethyl ammonium ion, decyl trimethyl ammonium ion, dodecyl trimethyl ammonium ion, tetradecyl trimethyl ammonium ion, hexadecyl trimethyl ammonium ion, octadecyl trimethyl ammonium ion, dodecyl dimethyl ammonium ion, dodecyl methyl ammonium ion.

The polarity of the organized clay can be defined by the hydrophobization constant. Here, the hydrophobicity constant is
It refers to the ratio of the total number of carbon atoms in the organic agent to the total number of cations in the organized clay. Since the total number of cations in the organized clay is equal to the ion exchange capacity of the organized clay, the hydrophobization constant of the organized clay is the ratio of the total number of carbon atoms in the organizing agent to the ion exchange capacity of the organized clay. Can also be expressed as

For example, when the organic agent is hexyl ammonium having 6 carbon atoms and all the exchanged metal ions in the clay are ion-exchanged by the hexyl ammonium, the hydrophobization constant becomes 6. When the organic agent is dodecyl ammonium having 12 carbon atoms and all the exchanged metal ions in the clay are ion-exchanged with the dodecyl ammonium, the hydrophobization constant is 12.

The organizing agent has a structure in which one or two or more chains are extended from the bond atom centering on the bond atom that is bonded or adsorbed to the clay. The carbon number of the longest chain of the organic agent is 6 or more and less than 24. The longest chain refers to the longest chain of one or more chains extending from the bond atom. The carbon chain of the longest chain refers to the number of carbon atoms contained in the longest chain, and may be either the main chain or the side chain.

When the longest chain carbon number of the organic agent is less than 6, the hydrophobicity is insufficient and the dispersibility of the clay is insufficient. When it is 24 or more, there is a problem that the hydrophobicity is too high for the polymer having the solubility of 8 to 15. Preferably,
The carbon number of the longest chain of the organic agent is 6 or more and less than 18.

Examples of the clay include kaolinite,
Examples include, but are not limited to, kaolinites such as halosite, montmorillonite, beidellite, saponite, hectorite, smectites such as mica, and vermiculites. It may be derived from a natural product, a processed product of a natural product, or a synthetic product such as swelling mica.

Ion exchange amount of clay is 50 to 200 m
It is preferably eq / 100 g. 50 meq / 1
If the amount is less than 00 g, the cation of the clay may not be sufficiently exchanged with the onium ion of the organic agent. If it exceeds 200 meq / 100g,
The bonding force between the layers of the clay becomes strong, and it may be difficult to swell the clay layers.

The content of the organized clay is preferably 0.01 to 200 parts by weight based on 100 parts by weight of the polymer. If the amount is less than 0.01 part by weight, the effect of adding clay may not be sufficiently exhibited. If it exceeds 200 parts by weight, the content of the organized clay that may cause a problem in the processability of the polymer composite material is 10
It is 0.1 to 30 parts by weight with respect to 0 parts by weight. This improves the balance between the processability and the physical properties of the polymer composite material.

The composite method of the organized clay and the polymer is, firstly, a method of dispersing and dissolving in a solvent and then removing the solvent, and secondly, mixing the organized clay and the polymer, There is a method of heating these above the softening point or melting point of the polymer. In the second compounding method, it is preferable to apply a shearing force to the organized clay and the polymer during heating, so that the clay is uniformly dispersed in the polymer. In particular,
It is preferable to perform melt kneading while applying shearing force with an extruder. At this time, air, solvent, oil or the like may be added. When the polymer is rubber, the rubber may be crosslinked after the clay dispersion or at the same time as the clay dispersion process.

Further, in manufacturing the polymer composite material, a master material is prepared in advance by preparing a composite material of the first polymer and the organized clay, adding the second polymer to the composite material, and thereafter molding. It is preferable to use a batch method. At this time, the second polymer added later may be the same as or different from the first polymer. It is preferable that the second polymer is the same polymer as the first polymer, or the second polymer is a polymer having a high compatibility with the first polymer. This further improves the dispersibility of clay in the polymer.

For example, after the organic clay is finely dispersed in an acrylonitrile-butadiene copolymer having a nitrile content of 34% by weight as the first polymer to form a composite material, the second polymer is added to the composite material. It is also possible to produce a polymer composite material by adding an acrylonitrile-butadiene copolymer having a nitrile content of 60% by weight as the above. The polymer composite material can be molded by injection molding, extrusion molding, or press molding.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described using Examples 1 to 11 and Comparative Examples 1 to 5. Example 1 The polymer composite material of this example has a polymer and a longest carbon chain of 1
2 and an organized clay that has been organized by an organizing agent of 2. The polymer is an acrylonitrile-butadiene copolymer with an acrylic amount of 10% by weight and has a solubility of 9.4. The organized clay is montmorillonite (C12-Mt) organized with dodecyl ammonium, and the crude water hydration constant is 12. The organic agent has 12 carbon atoms in the longest chain
Is dodecylammonium. The clay is Na-montmorillonite (Kunipia F manufactured by Kunimine Industries).

A method for manufacturing the polymer composite material of this example will be described. First, 80 g of Na montmorillonite was added to 10 parts of water.
Dispersed in liters. 2 liters of an aqueous solution containing 21.3 g of dodecylamine and 4.16 g of hydrochloric acid was added to the montmorillonite dispersion. Organized clay (C12-Mt) was prepared by filtering, washing and drying the deposit.

Next, 100 g of polymer and organized clay 1
3.9g and 12 using a closed mill (Laboplus mill)
The mixture was heated and kneaded at 0 ° C. for 2 minutes to form a composite. The content of clay in the composite material was 10% by weight. Composite material 10
To 0 parts by weight, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes.

As described above, the polymer composite material of this example was obtained. An X-ray diffraction pattern of the polymer composite material is shown in FIG. In FIGS. 1 to 4 and Table 1, “AN” means the amount of polymer acrylic.

Example 2 In this example, montmorillonite (C14-
Mt) was used. The crude water hydration constant of the organized clay is 14. The polymer is an acrylonitrile-butadiene copolymer having an acrylic amount of 10% by weight.

A method of manufacturing the polymer composite material of this example will be described. First, 80 g of Na montmorillonite was added to 10 parts of water.
Dispersed in liters. 2 liters of an aqueous solution containing 24.3 g of tetradecyl and 4.16 g of hydrochloric acid was added to the montmorillonite dispersion. Organized clay (C14-Mt) was prepared by filtering, washing and drying the deposit.

Next, 100 g of polymer and organized clay 1
4.5g and 12 using a closed mill (Laboplus mill)
The mixture was heated and kneaded at 0 ° C. for 2 minutes to form a composite. The content of clay in the composite material was 10% by weight. Composite material 10
To 0 parts by weight, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. As described above, the polymer composite material of this example was obtained. An X-ray diffraction pattern of the polymer composite material is shown in FIG. 1 (b).

Example 3 In this example, montmorillonite (C16-M) organized with hexadecyl ammonium as the organized clay was used.
t) was used. The crude water hydration constant of the organized clay is 16. The polymer is an acrylonitrile-butadiene copolymer having an acrylic amount of 10% by weight.

A method of manufacturing the polymer composite material of this example will be described. First, 80 g of Na montmorillonite was added to 10 parts of water.
Dispersed in liters. 2 l of an aqueous solution consisting of 27.5 g of hexadecyl and 4.16 g of hydrochloric acid was added to the montmorillonite dispersion. Organized clay (C16-Mt) was prepared by filtering, washing and drying the deposit.

Next, 100 g of polymer and organic clay 1
5.4g and 12 using a closed mill (Laboplus mill)
The mixture was heated and kneaded at 0 ° C. for 2 minutes to form a composite. The content of clay in the composite material was 10% by weight. Composite material 10
To 0 parts by weight, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. As described above, the polymer composite material of this example was obtained. An X-ray diffraction pattern of the polymer composite material is shown in FIG. 1 (c).

Example 4 In this example, montmorillonite (C18-M) organized with octadecyl ammonium was used as the organized clay.
t) was used. The crude water hydration constant of the organized clay is 18. The polymer is an acrylonitrile-butadiene copolymer having an acrylic amount of 10% by weight.

A method of manufacturing the polymer composite material of this example will be described. First, 80 g of Na montmorillonite was added to 10 parts of water.
Dispersed in liters. 2 l of an aqueous solution consisting of 30.7 g of octadecyl and 4.16 g of hydrochloric acid was added to the montmorillonite dispersion. Organized clay (C18-Mt) was prepared by filtering, washing and drying the precipitate.

Next, 100 g of polymer and 1 of organized clay
12g with 6.7g using a closed mill (LaboPlus mill)
The mixture was heated and kneaded at 0 ° C. for 2 minutes to form a composite. The content of clay in the composite material was 10% by weight. Composite material 10
To 0 parts by weight, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. As described above, the polymer composite material of this example was obtained. An X-ray diffraction pattern of the polymer composite material is shown in FIG. 1 (d).

Example 5 In this example, montmorillonite (C10-Mt) organized with decyl ammonium was used as the organized clay. The crude water hydration constant of the organized clay is 10. The polymer is an acrylonitrile-butadiene copolymer (solubility 9.9) having an acrylic amount of 17% by weight.

A method for manufacturing the polymer composite material of this example will be described. First, 80 g of Na montmorillonite was added to 10 parts of water.
Dispersed in liters. 2 liters of an aqueous solution containing 17.9 g of decylamine and 4.16 g of hydrochloric acid was added to the montmorillonite dispersion. First, an organized clay (C10-Mt) was prepared by filtering, washing and drying the precipitate.

Next, 100 g of polymer and organic clay 1
3.5g and 12 using a closed mill (Laboplus mill)
The mixture was heated and kneaded at 0 ° C. for 2 minutes to form a composite. The content of clay in the composite material was 10% by weight. Composite material 10
To 0 parts by weight, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. As described above, the polymer composite material of this example was obtained. An X-ray diffraction pattern of the polymer composite material is shown in FIG.

Example 6 In this example, montmorillonite (C12-Mt) organized with dodecyl ammonium as the organized clay is used.
Was used. The crude water hydration constant of the organized clay is 12. The polymer is an acrylonitrile-butadiene copolymer having an acrylic amount of 17% by weight.

A method for manufacturing the polymer composite material of this example will be described. First, an organized clay (C12-Mt) was prepared in the same manner as in Example 1. Next, 100 g of the polymer and 13.9 g of the organized clay were heated and kneaded at 120 ° C. for 2 minutes using a closed mill (Laboplus mill) to form a composite. The content of clay in the composite material was 10% by weight. To 100 parts by weight of the composite material, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. As described above, the polymer composite material of this example was obtained. An X-ray diffraction pattern of the polymer composite material is shown in FIG. 2 (b).

Example 7 In this example, tetradecylammonium (C14-Mt) was used as the organized clay. The crude water hydration constant of the organized clay is 14. The polymer is an acrylonitrile-butadiene copolymer having an acrylic amount of 17% by weight.

A method for manufacturing the polymer composite material of this example will be described. First, an organized clay (C14-Mt) was prepared in the same manner as in Example 2. Next, 100 g of the polymer and 14.5 g of organized clay were heated and kneaded for 2 minutes at 120 ° C. in a closed mill (Labo plus mill) to form a composite. The content of clay in the composite material was 10% by weight. To 100 parts by weight of the composite material, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. As described above, the polymer composite material of this example was obtained. An X-ray diffraction pattern of the polymer composite material is shown in FIG. 2 (c).

Example 8 In this example, montmorillonite (C10-Mt) organized with decyl ammonium was used as the organized clay. The crude water hydration constant of the organized clay is 10. The polymer is an acrylonitrile-butadiene copolymer (solubility 10.9) having an acrylic amount of 34% by weight.

A method of manufacturing the polymer composite material of this example will be described. First, an organized clay (C10-Mt) was prepared in the same manner as in Example 5. Next, 100 g of the polymer and 13.5 g of the organized clay were heated and kneaded at 120 ° C. for 2 minutes using a closed mill (Labo plus mill) to form a composite. The content of clay in the composite material was 10% by weight. To 100 parts by weight of the composite material, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. As described above, the polymer composite material of this example was obtained. An X-ray diffraction pattern of the polymer composite material is shown in FIG.

Example 9 In this example, montmorillonite (C12-Mt) organized with dodecyl ammonium as the organized clay was used.
Was used. The crude water hydration constant of the organized clay is 12. The polymer is a hydrogenated acrylonitrile-butadiene copolymer (hydrogenated NBR) with an acrylic amount of 34% by weight.

A method of manufacturing the polymer composite material of this example will be described. First, an organized clay (C12-Mt) was prepared in the same manner as in Example 1. Next, 100 g of the polymer and 13.9 g of the organized clay were heated and kneaded at 120 ° C. for 2 minutes using a closed mill (Laboplus mill) to form a composite. The content of clay in the composite material was 10% by weight. To 100 parts by weight of the composite material, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. As described above, the polymer composite material of this example was obtained. An X-ray diffraction pattern of the polymer composite material is shown in FIG. 3 (b).

Example 10 In this example, a polymer composite material was manufactured by the masterbatch method. First, an organized clay (C10-Mt) was prepared in the same manner as in Example 5. The crude water hydration constant of this organized clay is 10. Next, organized clay (C1
0-Mt) 55.5 g and acrylic amount as polymer 3
4% by weight of acrylonitrile-butadiene copolymer 10
0g and 12 using a closed mill (Laboplast mill)
A masterbatch was prepared by heating and kneading at 0 ° C. for 2 minutes.
The content of clay in the masterbatch was 30% by weight.

Next, 100 g of the above masterbatch and 200 g of an acrylonitrile-butadiene copolymer (acrylic amount 44% by weight) were heated and kneaded at 120 ° C. for 2 minutes using a closed mill (Laboplast mill). The amount of clay added was 10% by weight. To 100 parts by weight of the composite material, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes.
As described above, the polymer composite material of this example was obtained. An X-ray diffraction pattern of the polymer composite material is shown in FIG.

Example 11 In this example, a polymer composite material was produced by the masterbatch method. First, an organized clay (C10-Mt) was prepared in the same manner as in Example 5. This organized clay has a crude water hydration constant of 10 and is montmorillonite (C10-Mt) organized with decyl ammonium.

Next, organized clay (C10-Mt) 3
1.5 g and 100 g of an acrylonitrile-butadiene copolymer having an acrylic amount of 34% by weight as a polymer were heated and kneaded at 120 ° C. for 2 minutes using a closed mill (Laboplast mill) to prepare a masterbatch. The content of clay in the masterbatch was 20% by weight.

Next, 150 g of the above masterbatch and 150 g of an acrylonitrile-butadiene copolymer (acryl amount 60% by weight) were heated and kneaded at 120 ° C. for 2 minutes using a closed mill (Laboplast mill). The amount of clay added was 10% by weight. To 100 parts by weight of the composite material, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes.
As described above, the polymer composite material of this example was obtained. An X-ray diffraction pattern of the polymer composite material is shown in FIG.

COMPARATIVE EXAMPLE 1 In this example, montmorillonite (C24-M) organically modified with aminotetraeicosane was used as the organically modified clay.
t) was used. The crude water hydration constant of the organized clay is 24. The polymer is an acrylonitrile-butadiene copolymer having an acrylic amount of 17% by weight.

A method for manufacturing the polymer composite material of this example will be described. First, 80 g of Na montmorillonite was added to 10 parts of water.
Dispersed in liters. Amino tetraeicosan 40.
2 l of an aqueous solution consisting of 3 g and 4.16 g of hydrochloric acid was added to the montmorillonite dispersion. The precipitate is filtered, washed,
First, an organized clay (C24-Mt) was prepared by drying.

Next, 100 g of polymer and 1 of organized clay
8.9g and 12 using a closed mill (Labo plus mill)
The mixture was heated and kneaded at 0 ° C. for 2 minutes to form a composite. The content of clay in the composite material was 10% by weight. Composite material 10
To 0 parts by weight, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. As described above, the polymer composite material of this example was obtained. An X-ray diffraction pattern of the polymer composite material is shown in FIG.

Comparative Example 2 In this example, the same organized clay (C24-Mt) as in Comparative Example 1 was used as the organized clay. The crude water hydration constant of the organized clay is 24. Polymer is acrylic amount 34
It is a wt% acrylonitrile-butadiene copolymer (solubility 10.9).

A method of manufacturing the polymer composite material of this example will be described. First, an organized clay (C24-Mt) is prepared in the same manner as in Comparative Example 1. Next, 100 g of the polymer and 18.9 g of the organized clay were heated and kneaded at 120 ° C. for 2 minutes using a closed mill (Labo plus mill) to form a composite. The content of clay in the composite material was 10% by weight. To 100 parts by weight of the composite material, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. As described above, the polymer composite material of this example was obtained. An X-ray diffraction pattern of the polymer composite material is shown in FIG. 4 (b).

Comparative Example 3 This example is a polymer material composed of a polymer, and organic clay was not added. Polymer is 10% by weight of acrylic
Is an acrylonitrile-butadiene copolymer.

A method for manufacturing the polymer composite material of this example will be described. Next, to 100 parts by weight of the polymer, 5 parts by weight of zinc oxide, 1.5 parts by weight of sulfur, 1 part by weight of stearic acid, and 1 part by weight of vulcanization accelerator were added and kneaded with a roll.
It was vulcanized by press heating at 150 ° C. for 10 minutes. In this way, the polymer material of this example was obtained. As a result of X-ray diffraction, no peak was observed. This is because no clay was added.

Comparative Example 4 This example is a polymer material composed of an acrylonitrile-butadiene copolymer having an acrylic amount of 17% by weight. The others are the same as in Comparative Example 3. When this polymer material was also subjected to X-ray diffraction, no peak derived from clay was observed.

Comparative Example 5 This example is a polymer material composed of an acrylonitrile-butadiene copolymer having an acrylic amount of 34% by weight. The others are the same as in Comparative Example 3. When this polymer material was also subjected to X-ray diffraction, no peak derived from clay was observed.

Next, the above Examples 1 to 11 and Comparative Examples 1 to 1
The dispersibility of clay was evaluated from the X-ray diffraction result of No. 5, and the evaluation criteria were ○ when the clay layer structure disappeared, Δ when the clay layer structure almost disappeared, and when the clay layer structure remained. It was set to x. The evaluation results are shown in Table 1. In the table, "-" means that measurement is impossible.

[0073]

[Table 1]

Next, the X-ray diffraction result and the clay dispersibility evaluation result will be considered. 1 (a) to 1 (d)
Is the longest chain carbon number of the organic agent is 12, 14, 16, 1
8 is a measurement result when the amount of acrylic polymer is constant at 10% by weight (solubility 9.4). From these results, the peak derived from clay was low when the carbon number was 12-18. Also, it can be seen that the smaller the number of carbon atoms in the longest chain of the organizing agent, the smaller the peak intensity derived from clay.

Further, FIGS. 2 (a) to 2 (c) and FIG.
(A) shows that the longest chain carbon number of the organic agent is 10, 12, 1
4, 24, which is the measurement result when the amount of acrylic polymer is constant at 17% by weight (solubility 9.9). From this result, when the carbon number is 10 or more and less than 24 (see FIG.
In (a) to FIG. 2 (d), the peak was low. Also,
It can be seen that the smaller the number of carbon atoms in the longest chain of the organic agent, the smaller the peak intensity derived from clay.

FIGS. 3 (a) and 4 (b) show the case where the longest chain carbon number of the organic agent is 10, 24 and the amount of acrylic polymer is 34% by weight (solubility 10.9). It is a measurement result. When the carbon number is 10 (Fig. 3 (a)), the carbon number is 2
The peak intensity derived from clay was lower than in the case of No. 4 (FIG. 4 (b)).

FIG. 3B shows an example using a hydrogenated acrylonitrile-butadiene copolymer as the polymer. Although this hydrogenated product is more polar than the acrylonitrile-butadiene copolymer,
The dispersibility of Mt) was good, and the peak intensity derived from clay was weak.

Further, FIGS. 3 (c) and 3 (d) are examples in which a polymer material is manufactured by the masterbatch method. In both cases, the amount of polymer acrylic is 44, 60% by weight
However, no peak derived from clay was observed. From this, it is understood that the clay is finely dispersed in the polymer by adding and kneading the previously prepared masterbatch to the polymer having high polarity. Further, from Table 1, it is understood that in Examples 1 to 11, clay is finely dispersed in the polymer, and in Comparative Examples 1 and 2, the dispersibility of clay is low.

Next, the gas permeation coefficient was measured for the above Examples and Comparative Examples. The measurement was performed at 80 ° C. using a Yanaco gas permeation measuring device. The measurement results are shown in Table 1.
From the table, the gas permeability coefficients of Examples 1 to 11 are shown in Comparative Example 1
It was lower than ~ 5. From this, it is understood that the polymer composite materials of Examples 1 to 11 according to the present invention have excellent gas barrier properties.

From the above, a polymer composite material comprising a polymer having a solubility in the range of 8.8 or more and 19 or less, and an organized clay which is organized by an organizing agent having 6 or more and less than 24 carbon atoms in the longest chain is , The clay has high dispersibility and gas barrier property. In addition, the carbon number of the longest chain of the organic agent is 6 or more 2
It can be seen that when it is less than 4, especially the clay dispersibility and the gas barrier property are improved.

[0081]

According to the present invention, it is possible to provide a polymer composite material having excellent dispersibility of clay in a polymer having high polarity.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction diagram (a) of Examples 1 to 4.
(D).

FIG. 2 is an X-ray diffraction diagram (a) of Examples 5 to 7.
(C).

FIG. 3 is an X-ray diffraction diagram (a) of Examples 8 to 11;
(D).

FIG. 4 is X-ray diffraction diagrams (a) and (b) of Comparative Examples 1 and 2.

FIG. 5 is an explanatory diagram of polymer solubility in the present invention.

Continuation of the front page (56) Reference JP-A-10-245453 (JP, A) JP-A-9-87432 (JP, A) JP-A-62-209148 (JP, A) JP-A-61-213231 (JP , A) JP-A-11-159667 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (3)

(57) [Claims] And <br/> polymer soluble <br/> Kaido has 8.8 or more 19 or less in the range of nitrile groups is 1. A parameter representing the polarity of the polymer, the longest chain carbons 6 Do Ri, and the from the organized organic clay by fewer than 24 of the organic agent or
A polymer having a nitrile group has a nitrile group content of 5 to
A polymer composite material characterized by being 50% by weight . 2. The organized clay according to claim 1,
Is a polymer composite material having the above carbon number of 6 or more and less than 18 . 3. An apparatus according to claim 1 or 2, the nitrilase
A polymer composite material characterized in that the polymer having a rubber group is rubber.