JP2000273318A - Polymer composite materials - Google Patents

Abstract

(57) [Problem] To provide a polymer composite material excellent in dispersibility of clay in a highly polar polymer. SOLUTION: It is composed of a polymer having a solubility of 8.8 or more and 19 or less, and an organically modified clay organically treated with an organic agent having a longest chain having 6 or more and less than 24 carbon atoms. The polymer is a rubber and preferably has an acrylonitrile group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

BACKGROUND ART 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, 1994-1996 (1993) combined polystyrene and clay. However, polystyrene only intervenes between clay layers, and has not broken the clay layer structure or dispersed in a single clay layer.

In Japanese Patent Application Laid-Open No. 8-333114, a device has been devised to improve the dispersibility of clay by introducing a polar group into a polymer. However, also in this case, the dispersibility of the clay was insufficient for the highly polar polymer.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has as its object to provide a polymer composite material having excellent dispersibility of clay in a highly polar polymer.

[0005]

According to the present invention, as set forth in claim 1,
A polymer composite material comprising a polymer having a solubility of 8.8 or more and 19 or less, and an organically modified clay organically treated with an organic agent having a longest chain having 6 or more and less than 24 carbon atoms. .

The present inventors have found that, for a highly polar polymer, the dispersibility of the clay in the highly polar polymer is improved by matching the polarity of the polymer with the polarity of the organized clay. I found that. That is, the polarity of the polymer varies depending on the type and content of the functional group. Fine dispersion of the clay can be achieved by changing the length of the carbon chain of the organicizing agent and using the organically modified clay adjusted to have a polarity suitable for each polymer.

The polymer composite material of the present invention has a solubility of 8.8.
This is a compound obtained by adding an organically modified clay having a carbon number of 6 or more and less than 24 to an organic clay having an organic polarity of 19 or less and having a carbon number of less than 24. The polarity of the organic agent having a carbon number in the above range is suitable for the high-polarity polymer. Therefore, the compatibility of the organically modified clay with respect to the polymer having high polarity is improved, and the clay dispersibility with respect to the polymer is improved. In addition, the fine dispersion of the clay in the polymer improves the gas barrier properties 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, the details of the present invention will be described. In the present invention, the solubility of the polymer is a parameter indicating the polarity of the polymer, and is described in Coating Time Report No. 193, p.
(1993) Defined by numerical values calculated based on "Calculation of solubility parameter". In determining the solubility parameter value, there are a method by measurement and a method by calculation.

As methods by measurement, latent heat of evaporation 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 (1) is a low molecular compound having a vapor pressure, and the method of (2) is a useful means for polymers.

On the other hand, as a calculation method, there is a method in which the molecular cohesion energy and the molecular volume are determined for each functional group constituting the compound and the molecular cohesion energy and the molecular volume are determined from the equation (1) in FIG. It is simple to find 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, and calculating by the formula (2) in FIG. 5;

On the other hand, the method proposed by Fedors is based on the cohesive energy Δe ₁ and the molecular volume Δv per unit functional group.
_This is a method in which the density is unknown and the density can be calculated even if the density is unknown. This is a useful method when designing a polymer or the like. In the present invention, the method proposed by Fedors is useful for determining the solubility of a polymer. Incidentally, in the lower part of FIG. 5, the .DELTA.e ₁
And Δv ₁ are shown as examples.

The solubility of the polymer is from 8.8 to 19. If it is less than 8.8, the polarity is too low and good dispersion of the clay cannot be obtained. That is, since the polarities of the polymer and the organized clay do not match, the compatibility of the polymer and the clay is poor, and the clay is hardly dispersed in the polymer. If it exceeds 19, the polarity is too high and good dispersion of clay cannot be obtained.
Also in this case, the polarities of the polymer and the organized clay do not match, so that the compatibility between the two is poor and the clay is hardly dispersed in the polymer.

The polymer may be, for example, a resin or a rubber as described in claim 3.
As the polymer having a solubility of 8.8 or more and 19 or less, for example, polyamide, polycarbonate, polyacetal,
Polyester, polyphenylene ether, polyphenylene sulfide, polyether sulfone, polyether ketone, polyarylate, polymethylpentene, polyphthalamide, polyether nitrile, polyether sulfone, polybenzimidazole, polycarbodiimide,
Polymers such as polyamide imide, polyether imide, and polyurethane can be used.

Further, as the polymer having the solubility, there is a copolymer of two or more kinds of monomers. Such copolymers include, for example, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, hydrogenated Acrylonitrile-butadiene copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, acrylonitrile-acrylate copolymer, styrene-maleic anhydride Copolymer,
A styrene-maleimide copolymer or the like can be used.

In particular, a copolymer comprising a polar monomer and a non-polar monomer is preferred. Such copolymers include:
Acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, hydrogenated acrylonitrile-butadiene copolymer, ethylene- Examples include a vinyl alcohol copolymer, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, and an ethylene-acrylate copolymer.

Further, as the polymer, chloroprene rubber,
Styrene rubber, nitrile rubber, styrene-butadiene rubber, epichlorohydrin rubber, acrylic rubber, urethane rubber, fluorine rubber, silicone rubber and the like can be used. As the rubber, for example,
In some cases, a crosslinking agent is added to form a crosslinking bond. Crosslinking includes, for example, sulfur crosslinking and peroxide crosslinking.

The polymer has a polar group. As described in claim 2, the polymer preferably has an acrylonitrile group. This improves the dispersibility due to strong interaction with the surface of the organized clay.

The polar group includes, in addition to the acrylonitrile group, a nitrile group, a hydroxyl group, an ester group, an amide group,
Ether and carboxyl groups are preferred. Preferred examples of the polymer having a polar group include an acrylonitrile-butadiene copolymer having a nitrile group, a hydrogenated acrylonitrile-butadiene copolymer; and an ethylene-vinyl alcohol copolymer having a hydroxyl group.

When the polar group of the polymer is a nitrile group, the content of the nitrile group in the polymer is 5 to 50 watts.
It is preferably t%. If less than 5 wt%,
Sufficient mechanical properties and gas barrier properties may not be obtained. If it exceeds 50% by weight, sufficient dispersibility of clay may not be obtained. More preferably, the acrylonitrile group in the polymer is 10 to 50% by weight.
It is. This makes it possible to obtain a polymer composite material having a good clay dispersibility and a balance of various physical properties. In particular, the content of the nitrile group in the acrylonitrile-butadiene copolymer and the hydrogenated acrylonitrile-butadiene copolymer is preferably 5 to 50 wt%, more preferably 10 to 50 wt%, as described above.

When the polar group of the polymer is a hydroxyl group, the content of the hydroxyl group in the polymer is preferably 20 to 90 wt%. If the amount is less than 20 wt%, the balance of physical properties of the polymer composite material may be deteriorated. 9
If it exceeds 0 wt%, good clay dispersibility may not be obtained. More preferably, the number of hydroxyl groups in the polymer is 30 to 80% by weight. Thereby, a polymer composite material having a good balance between the dispersibility and physical properties of clay can be provided. In particular, the nitrile group content in the ethylene-vinyl alcohol copolymer is 20
It is desirable that the content be 90 to 90 wt%, and more preferably 30 to 80 wt%.

The molecular weight of the polymer is 5,0 as a number average molecular weight.
It is preferably from 00 to 10,000,000.
If it is less than 5,000, mechanical properties may be insufficient. If it exceeds 10,000,000, a problem may occur in the processability 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 between 000 and 1,000,000. This gives
Both mechanical properties and workability are improved.

The organized clay is obtained by adsorbing and bonding an organic agent to the surface of a clay (clay mineral) by a physical or chemical method. Since clay has hydrophilicity by nature, it is hydrophobized by adsorption and binding of an organic agent. By changing the type of the organic agent, the polarity of the entire organic clay can be controlled. In particular, it is preferable to use an organic onium ion salt as the organic agent, and it is preferable that the organic onium ion is ion-bonded by ion exchange between the organic onium ion salt and a metal ion between the clay layers.
As the organic onium ion, an organic ammonium ion, an organic phosphonium ion, or the like can be used. Among these, it is preferable to use an organic ammonium ion.

Specific examples of the organic onium ion include 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, and the like.
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, and the like.

Further, the polarity of the organized clay can be defined by the hydrophobicity constant. Here, the hydrophobicity constant is
It refers to the ratio of the total number of carbon atoms in the organizing 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 organic agent to the ion exchange capacity of the organized clay. Can also be represented by

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

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

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

As clay, for example, kaolinite,
Examples include, but are not limited to, kaolinites such as halosites, montmorillonites, beidellite, saponites, hectorites, 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 swellable mica.

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

The content of the organized clay is preferably from 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 the amount exceeds 200 parts by weight, the content of the organized clay, which may cause a problem in the processability of the polymer composite material, is limited to the polymer 10
0.1 to 30 parts by weight with respect to 0 parts by weight. Thereby, the balance between the processability and the physical properties of the polymer composite material is improved.

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

In producing a polymer composite material, a composite material of a first polymer and an organized clay is prepared in advance, a second polymer is added to the composite material, and then a master is formed. It is preferable to use a batch method. At this time, the second polymer to be added later may be the same or different from the first polymer. Preferably, the second polymer is the same polymer as the first polymer, or the second polymer is a polymer having high compatibility with the first polymer. This further improves the dispersibility of the clay in the polymer.

For example, after the organically modified 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. The acrylonitrile-butadiene copolymer having a nitrile content of 60% by weight as the above may be added to produce a polymer composite material. The polymer composite material can be formed into a molded product by injection molding, extrusion molding, or press molding.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described with reference to Examples 1 to 11 and Comparative Examples 1 to 5. Example 1 The polymer composite material of this example has a polymer and one longest carbon chain.
And organically-organized clay organically treated with the organic-organizing agent. The polymer is an acrylonitrile butadiene copolymer having an acrylic content of 10% by weight, and has a solubility of 9.4. The organized clay is montmorillonite (C12-Mt) that has been organized with dodecylammonium, and the crude water conversion constant is 12. The organic agent has 12 carbon atoms in the longest chain.
Is dodecyl ammonium. Clay is Na-montmorillonite (Kunimine Kogni F).

The method for producing the polymer composite material of this embodiment will be described. First, 80 g of Na montmorillonite was added to water 10
Dispersed in liters. Two liters of an aqueous solution consisting of 21.3 g of dodecylamine and 4.16 g of hydrochloric acid was added to the montmorillonite dispersion. An organic clay (C12-Mt) was prepared by filtering, washing and drying the precipitate.

Next, 100 g of the polymer and the organic clay 1
3.9 g using a closed mill (Lab Plus Mill)
The mixture was heated and kneaded at 0 ° C. for 2 minutes to form a composite. The clay content in the composite 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 a vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes.

Thus, the polymer composite material of this example was obtained. The X-ray diffraction diagram of the polymer composite material is shown in FIG. In addition, in FIGS. 1-4 and Table 1, "AN" means the amount of high molecular acrylic.

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

A method for producing the polymer composite material of this example will be described. First, 80 g of Na montmorillonite was added to water 10
Dispersed in liters. Two liters of an aqueous solution consisting of 24.3 g of tetradecyl and 4.16 g of hydrochloric acid was added to the montmorillonite dispersion. An organic clay (C14-Mt) was prepared by filtering, washing, and drying the precipitate.

Next, 100 g of the polymer and the organic clay 1
4.5 g with a closed mill (Lab Plus Mill)
The mixture was heated and kneaded at 0 ° C. for 2 minutes to form a composite. The clay content in the composite 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 a vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. Thus, the polymer composite material of this example was obtained. The X-ray diffraction diagram of the polymer composite material is shown in FIG.

Example 3 In this example, montmorillonite (C16-M) organically treated with hexadecyl ammonium was used as the organic clay.
t) was used. The coarse wateration constant of the organized clay is 16. The polymer is an acrylonitrile butadiene copolymer having an acrylic content of 10% by weight.

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

Next, 100 g of the polymer and the organic clay 1
5.4 g and 12 using a closed mill (Lab Plus Mill)
The mixture was heated and kneaded at 0 ° C. for 2 minutes to form a composite. The clay content in the composite 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 a vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. Thus, the polymer composite material of this example was obtained. The X-ray diffraction diagram of the polymer composite material is shown in FIG.

Example 4 In this example, montmorillonite (C18-M) organically treated with octadecyl ammonium as an organic clay was used.
t) was used. The coarse wateration constant of the organized clay is 18. The polymer is an acrylonitrile-butadiene copolymer having an acrylic content of 10% by weight.

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

Next, 100 g of the polymer and the organic clay 1
6.7 g using a closed mill (Lab Plus Mill)
The mixture was heated and kneaded at 0 ° C. for 2 minutes to form a composite. The clay content in the composite 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 a vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. Thus, the polymer composite material of this example was obtained. The X-ray diffraction diagram of the polymer composite material is shown in FIG.

Example 5 In this example, montmorillonite (C10-Mt) organically treated with decyl ammonium was used as the organic clay. The coarse wateration constant of the organized clay is 10. The polymer is an acrylonitrile butadiene copolymer (solubility 9.9) with an acrylic content of 17% by weight.

A method for producing the polymer composite material of this example will be described. First, 80 g of Na montmorillonite was added to water 10
Dispersed in liters. Two liters of an aqueous solution consisting of 17.9 g of decylamine and 4.16 g of hydrochloric acid was added to the montmorillonite dispersion. The precipitate was filtered, washed, and dried to prepare an organized clay (C10-Mt).

Next, 100 g of the polymer and the organic clay 1
3.5 g with a closed mill (Lab Plus Mill)
The mixture was heated and kneaded at 0 ° C. for 2 minutes to form a composite. The clay content in the composite 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 a vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. Thus, the polymer composite material of this example was obtained. The X-ray diffraction diagram of the polymer composite material is shown in FIG.

Example 6 In this example, montmorillonite (C12-Mt) organically treated with dodecyl ammonium as an organic clay was used.
Was used. The coarse wateration constant of the organized clay is 12. The polymer is an acrylonitrile-butadiene copolymer having an acrylic content of 17% by weight.

A method for producing 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 (Lab Plus Mill) to form a composite. The clay content in the composite was 10% 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 a vulcanization accelerator were added to 100 parts by weight of the composite material, and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. Thus, the polymer composite material of this example was obtained. The X-ray diffraction diagram of the polymer composite material is shown in FIG.

Example 7 In this example, tetradecyl ammonium (C14-Mt) was used as an organized clay. The coarse wateration constant of the organized clay is 14. The polymer is an acrylonitrile-butadiene copolymer having an acrylic content of 17% by weight.

A method for producing 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 the organized clay were heated and kneaded at 120 ° C. for 2 minutes using a closed mill (Lab Plus Mill) to form a composite. The clay content in the composite was 10% 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 a vulcanization accelerator were added to 100 parts by weight of the composite material, and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. Thus, the polymer composite material of this example was obtained. The X-ray diffraction diagram of the polymer composite material is shown in FIG.

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

A method for producing 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 (Lab Plus Mill) to form a composite. The clay content in the composite was 10% 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 a vulcanization accelerator were added to 100 parts by weight of the composite material, and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. Thus, the polymer composite material of this example was obtained. The X-ray diffraction diagram of the polymer composite material is shown in FIG.

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

A method for producing 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 (Lab Plus Mill) to form a composite. The clay content in the composite was 10% 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 a vulcanization accelerator were added to 100 parts by weight of the composite material, and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. Thus, the polymer composite material of this example was obtained. FIG. 3B shows an X-ray diffraction diagram of the polymer composite material.

Example 10 In this example, a polymer composite material was manufactured by a master batch method. First, an organized clay (C10-Mt) was prepared in the same manner as in Example 5. The roughening constant of this organically modified clay is 10. Next, the organic clay (C1
0-Mt) 55.5 g, and acrylic amount 3 as a polymer
4% by weight of acrylonitrile butadiene copolymer 10
0 g using a closed mill (Laboplast mill).
The mixture was heated and kneaded at 0 ° C. for 2 minutes to prepare a master batch.
The clay content in the masterbatch was 30% by weight.

Next, 100 g of the above master batch and 200 g of an acrylonitrile-butadiene copolymer (acrylic content: 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. 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 a vulcanization accelerator were added to 100 parts by weight of the composite material, and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes.
Thus, the polymer composite material of this example was obtained. The X-ray diffraction diagram of the polymer composite material is shown in FIG.

Example 11 In this example, a polymer composite material was manufactured by a master batch method. First, an organized clay (C10-Mt) was prepared in the same manner as in Example 5. This organic clay has a roughening constant of 10, and is montmorillonite (C10-Mt) organically treated with decyl ammonium.

Next, the organized clay (C10-Mt) 3
1.5 g and 100 g of an acrylonitrile-butadiene copolymer having an acrylic content 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 master batch. The clay content in the masterbatch was 20% by weight.

Next, 150 g of the above-mentioned master batch and 150 g of an acrylonitrile-butadiene copolymer (acryl content: 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. 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 a vulcanization accelerator were added to 100 parts by weight of the composite material, and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes.
Thus, the polymer composite material of this example was obtained. FIG. 3D shows an X-ray diffraction diagram of the polymer composite material.

Comparative Example 1 In this example, montmorillonite (C24-M) organically treated with aminotetraeicosane as an organic clay was used.
t) was used. The coarse wateration constant of the organized clay is 24. The polymer is an acrylonitrile-butadiene copolymer having an acrylic content of 17% by weight.

A method for producing the polymer composite material of this example will be described. First, 80 g of Na montmorillonite was added to water 10
Dispersed in liters. Aminotetraeicosane 40.
2 liters 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,
By drying, first, an organized clay (C24-Mt) was prepared.

Next, 100 g of the polymer and the organic clay 1
8.9 g with a closed mill (Lab Plus Mill)
The mixture was heated and kneaded at 0 ° C. for 2 minutes to form a composite. The clay content in the composite 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 a vulcanization accelerator were added and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. Thus, the polymer composite material of this example was obtained. The X-ray diffraction diagram 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 coarse wateration constant of the organized clay is 24. The polymer has an acrylic amount of 34
% By weight of an acrylonitrile-butadiene copolymer (solubility: 10.9).

A method for producing 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 (Lab Plus Mill) to form a composite. The clay content in the composite was 10% 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 a vulcanization accelerator were added to 100 parts by weight of the composite material, and kneaded with a roll. It was vulcanized by press heating at 150 ° C. for 10 minutes. Thus, the polymer composite material of this example was obtained. The X-ray diffraction diagram of the polymer composite material is shown in FIG.

Comparative Example 3 In this example, a polymer material composed of a polymer was used, and no organic clay was added. Polymer is acrylic content 10% by weight
Is an acrylonitrile butadiene copolymer.

A method for producing the polymer composite material of this example will be described. Next, 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 a vulcanization accelerator were added to 100 parts by weight of the polymer, and kneaded with a roll.
It was vulcanized by press heating at 150 ° C. for 10 minutes. Thus, 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. Others are the same as Comparative Example 3. This polymer material was also subjected to X-ray diffraction. As a result, no peak derived from clay was observed.

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

Next, the above Examples 1 to 11 and Comparative Examples 1 to
The dispersibility of the clay was evaluated from the X-ray diffraction results of Example 5. The evaluation criteria were as follows: ○ when the clay layer structure disappeared, Δ when the clay layer structure almost disappeared, and when the clay layer structure remained. X. Table 1 shows the evaluation results. In the table, "-" means that measurement is not possible.

[0073]

[Table 1]

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

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

FIGS. 3 (a) and 4 (b) show the results when the longest chain of the organicizing agent has a carbon number of 10,24 and the acrylic amount of the polymer is 34% by weight (solubility 10.9). It is a measurement result. When the number of carbon atoms is 10 (FIG. 3A), the number of carbon atoms is 2
4 (FIG. 4B), the peak intensity derived from clay was lower.

FIG. 3B shows an example in which a hydrogenated acrylonitrile-butadiene copolymer is used as a polymer. Although this hydrogenated product has a higher polarity than the acrylonitrile-butadiene copolymer, it does not contain the organically modified clay (C12-
The dispersibility of Mt) was good, and the peak intensity derived from clay was weak.

FIGS. 3C and 3D are examples in which a polymer material is manufactured by a master batch method. In each case, the amount of polymer acrylic was 44,60% by weight.
However, no peak derived from clay was observed. This indicates that the clay is finely dispersed in the polymer by adding and kneading the previously prepared master batch to the polymer having a high polarity. Further, from Table 1, it can be seen that in Examples 1 to 11, the clay was finely dispersed in the polymer, and in Comparative Examples 1 and 2, the dispersibility of the clay was low.

Next, the gas permeability coefficients of the above Examples and Comparative Examples were measured. The measurement was performed at 80 ° C. using a Yanaco gas permeation measuring device. Table 1 shows the measurement results.
From the same table, the gas permeability coefficients of Examples 1 to 11 are shown in Comparative Example 1.
Lower than ~ 5. This indicates that the polymer composite materials of Examples 1 to 11 according to the present invention have excellent gas barrier properties.

As described above, a polymer composite material comprising a polymer having a solubility in the range of 8.8 to 19 and an organically modified clay organically treated with an organic agent having a longest chain having 6 to less than 24 carbon atoms is obtained. It can be seen that the clay has high dispersibility and gas barrier properties. In addition, the longest chain of the organic agent has 6 or more carbon atoms.
When it is less than 4, it can be seen that clay dispersibility and gas barrier property are particularly improved.

[0081]

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

[Brief description of the 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 shows X-ray diffraction diagrams (a) and (b) of Comparative Examples 1 and 2.

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

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Claims (3)

[Claims] 1. A high-molecular-weight composition comprising a polymer having a solubility of 8.8 or more and 19 or less and an organically modified clay organically modified with an organic agent having a longest chain having 6 or more and less than 24 carbon atoms. Molecular composites. 2. The polymer composite material according to claim 1, wherein the polymer has an acrylonitrile group. 3. The polymer composite material according to claim 1, wherein the polymer is rubber.