JPH0822946B2 - Composite material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composite material having excellent mechanical strength and heat resistance, and more specifically, a resin composition containing polyamide and a silicate layer constituting a clay mineral. The present invention relates to a composite material in which and are bound to each other via an ionic bond, and they are uniformly mixed, and which has a mechanical strength superior to that of a molded product made of only a resin.

[Conventional technology]

Conventionally, the addition and mixing of inorganic materials such as calcium carbonate, clay minerals, and mica have been studied for the purpose of improving the mechanical properties of organic polymer materials.

However, when these inorganic materials are added and mixed, the bond between the organic polymer matrix and the organic polymer matrix is very weak, and therefore, there are many problems such as embrittlement due to addition, and However, there is a limit to the amount of addition of the inorganic material. For the purpose of strengthening the bond between the inorganic material and the polymer material, treatment of the inorganic material with a silane coupling agent is known. However, the bond between the organic polymer material and the inorganic material obtained by these methods is due to the Van der Waals bond, and is only to the extent that the compatibility between them is improved. Can't be enough.

In order to solve these problems, the present applicant has previously proposed that a “polyamide-containing resin composition” (a polyamide-containing resin composition) comprising a polyamide-containing resin and a vermiculite flakes having an average aspect ratio of 5 or more dispersed in the polyamide. JP-A-57-83551) has been proposed. This composition is intended to improve the mechanical strength of an organic polymer material by incorporating a vermiculite flakes having a large aspect ratio (particle size / thickness) into a resin.

[Problems to be Solved by the Invention]

However, although this resin composition certainly has improved mechanical strength as compared with the conventional one, it cannot be obtained with a sufficient aspect ratio because mechanical pulverization is required to obtain a vermiculite flakes. Moreover, since the bond strength between the mineral layer and the matrix phase is weak, it was necessary to increase the amount of addition at the expense of embrittlement in order to obtain the required strength.

Attempts have also been made to synthesize polymers such as polyamide and polystyrene between layers of clay minerals to obtain composite materials (“Polymer”, 19,759,1979; “Industrial material”, 2
5, "3", 58, 1977). However, in the methods so far, since the organic polymer chain does not sufficiently penetrate between the layers of the clay mineral, it is not possible to increase the distance between the layers, and the silicate layer and the organic polymer are evenly and further The constituent unit layer of the silicate was not dispersed in a molecular form. Further, in such a case, since the aspect ratio of the layered mineral is reduced, it has an adverse effect on improving the mechanical strength. Furthermore, since the bond between the polymer material as the matrix and the intercalation compound is not sufficient, a sufficient reinforcing effect cannot be obtained.

In addition, a "clay-polyamide composite" that polymerizes a lactam in the presence of a clay-organic composite in which an organic compound containing at least one amino group and having a catalytic activity for lactam polymerization is bound to clay by an ion exchange reaction Manufacturing method "(JP-A-51-109998). However, in the composite obtained by the method for producing a clay-polyamide composite, the clay in the resin is not separated for each crystal unit layer, and since the interlayer distance of the clay layer is small, the tensile strength is It is not more than the strength of the resin as the matrix. That is, for example, it is not more than the tensile strength of nylon 6 (the tensile strength disclosed in the examples of the above-mentioned publications is 30 to 80% of that of nylon 6). Therefore, the composite obtained by this method has a problem of insufficient mechanical strength and heat resistance.

In the first place, it is conventionally said that when clay is dispersed in polyamide to form a hybrid, the mechanical strength such as tensile strength is lower than that of the original resin. The composite obtained by the method disclosed in JP-A-51-109998 is intended to improve the strength reduction of this conventional composite and to approach the strength of the molded product obtained by the matrix resin alone. In other words, in other words, in each case, the mechanical strength is lower than that of the molded body obtained from the original resin alone by the compounding. As described above, the above method has a problem in that it is not possible to obtain a composite having strength characteristics superior to the strength of the molded body obtained from the matrix resin alone.

Therefore, the inventors of the present invention have earnestly studied in order to solve the above-mentioned problems of the prior art, and as a result of various systematic experiments, the present invention has been accomplished.

(Object of the Invention) An object of the present invention is to provide a composite material having excellent mechanical strength and heat resistance.

Another object of the present invention is to provide a composite material having mechanical strength and heat resistance superior to those of a resin as a matrix.

The present inventors have focused on the following points regarding the above-mentioned problems of the conventional technology. That is, first, in the conventionally proposed clay-polyamide composite, when clay is dispersed in polyamide to form a hybrid, mechanical strength such as tensile strength is lower than that of the original resin. This is because the conventionally proposed clay-polyamide composite has a weak bond between the clay layer and the polyamide, and the dispersibility of the clay layer is not sufficient, so that the tensile strength is less than the strength of the resin as the matrix (for example, nylon 6 The tensile strength is less than or equal to). It was also found that the constituent units of the dispersed clay layer itself are large.

As a method of solving these problems, the present inventors
The silicate layer to be dispersed in the resin is the minimum of the constitutional unit, the silicate layer and the polyamide molecular chain are bonded by ionic bond, the silicate layer is uniformly dispersed in the resin, and the silicic acid is dispersed in the resin. We focused on setting the distance between salt layers to 100 Å or more.

As a method for achieving this, use a clay mineral having an appropriate cation exchange capacity (for example, 50 to 200 meq / 100 g), and have a function of incorporating polyamide monomer molecules between layers in addition to the polyamide monomer and the clay mineral. Coexistence of a substance that exerts a very strong catalytic action, coexistence of a substance that can appropriately increase the distance between clay layers before polymerization, and that allows the silicate layer and the polyamide molecular chain to be bonded by an ionic bond. I focused on ,. And
As a substance satisfying the above and, (a) a swelling agent composed of an inorganic cation such as a copper ion, a hydrogen ion or an aluminum ion, or (b) an organic cation having an alkylene group having 12 or more carbon atoms and a carboxyl group Attention was paid to a swelling agent composed of ions (organic ammonium ions).
Then, a clay mineral having the predetermined cation exchange capacity and the swelling agent are brought into contact with each other in advance to form an ionic bond between the two, thereby producing a composite having a property of being swollen by the monomer at a temperature equal to or higher than the melting temperature of the monomer. Then, the composite and the polyamide monomer are mixed, and the mixture is heated to a predetermined temperature to polymerize under the catalytic action of the swelling agent, whereby a composite material having excellent mechanical strength and heat resistance is obtained. It reached, and came to complete the present invention.

[Structure of Invention]

The composite material of the present invention is a composite material comprising a resin containing polyamide and a silicate layer uniformly dispersed in the resin in a unit of thickness at the molecular level, and the silicate layer has a thickness of Is 7 to 12Å, and the distance between the silicate layers is
100 Å or more, and the silicate layer is ionically bonded to a part of the polymer chain of the polyamide, the content of the silicate layer is 0.5 to 150 parts by weight with respect to 100 parts by weight of the resin, The composite material contains a clay mineral having a cation exchange capacity of 50 to 200 meq / 100 g and one or more inorganic cations of aluminum ion, hydrogen ion, copper ion or carbon number.
A composite material obtained by using a composite obtained by contacting a swelling agent composed of an organic cation having 12 or more alkylene groups and a carboxyl group, and having excellent mechanical strength and heat resistance. Characterize.

[Operation of the invention]

The mechanism by which the composite material of the present invention exhibits an excellent effect is not always clear, but it is considered as follows.

The composite material of the present invention has a structure in which the polyamide molecular chain is bridged by an ionic bond with the silicate layer, and therefore it is difficult to deform it thermally or mechanically.
Therefore, mechanical properties such as tensile strength and elastic modulus, and heat resistance characteristics such as softening temperature and high temperature strength are excellent. In addition, since the layered inorganic substance is uniformly dispersed, dimensional stability,
It has excellent wear resistance, surface lubricity, water permeability, and water resistance.
In addition, the silicate, which is an inorganic layered substance, is dispersed in a unit of a molecular level thickness of about 10Å, that is, a silicate having a molecular length of about 10Å is uniformly dispersed in the resin in a molecular state. Thus, in the present invention, the strength of the composite can be improved by uniformly dispersing the layered silicate in the resin containing polyamide at the molecular level, that is, in the state of being separated for each crystal unit layer. it can. Further, the silicate layer is strongly bonded to the organic molecular chain. That is, the silicate layer is
Since it is ionically bonded to a part of the polymer chain of the polyamide, it does not leave an adverse effect such as embrittlement as seen in the conventional inorganic composite materials. The distance between the layers of the silicate dispersed in the resin is 100Å or more. In this way, by using a composite material in which a layered silicate is dispersed in a resin containing polyamide with an interlayer distance of 100 Å or more, the mechanical strength and heat resistance of the composite are improved, and it is superior to ordinary nylon. Excellent strength and heat resistance can be obtained.

Here, the content of the silicate layer in the resin containing polyamide is 0.5 to 150 parts by weight with respect to 100 parts by weight of the resin. This is because if the content is less than 0.5 parts by weight, the silicate layer is too small and a sufficient reinforcing effect cannot be obtained. Further, when the content exceeds 150 parts by weight, the amount of the resin component is small and only the intercalation compound powder is obtained, and it is difficult to use this as a molded body.

From the above, it is considered that the composite material of the present invention could be made into a composite material excellent in mechanical strength and heat resistance.

〔The invention's effect〕

The composite material of the present invention is a composite material having excellent mechanical strength and heat resistance.

Further, the composite material of the present invention can obtain strength and heat resistance higher than that of ordinary nylon.

[Embodiment of the Invention]

The resin in the composite material of the present invention is a resin containing polyamide, and is a resin composed of polyamide or a mixture of polyamide and a polymer other than polyamide.

Here, polyamide is an acid amide bond (-CONH-).
Is a general term for polymers having, specifically, nylon 66, nylon 6, nylon 11 and the like.

This resin can exhibit the effect of the present invention remarkably as the proportion of the polyamide resin is increased, but the effect of the present invention can be exerted even when the content of the polyamide resin is 10% by weight (wt%). it can.

The silicate layer imparts mechanical properties and heat resistance to the polymer material, and is a layered phyllosilicate mineral formed from a magnesium silicate layer or an aluminum silicate layer having a thickness of 7 to 12Å. These silicate layers are negatively charged by isomorphic ion substitution or the like. The characteristics vary depending on the density and distribution of this negative charge, but in the present invention,
It is preferable that the silicate layer has an area occupied by the surface of the layer per negative charge of 25 to 200Å ² .

The composite material of the present invention comprises a resin containing the above-mentioned polyamide, and a silicate layer uniformly dispersed in the resin in a molecular form.

Here, the content of the silicate layer in the resin containing polyamide is preferably 0.5 to 25 parts by weight with respect to 100 parts by weight of the resin. Further, optimally, the content of the silicate layer is 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin. As a result, it is possible to obtain a composite material in which a silicate layer having a distance between layers of 100 Å or more is sufficiently dispersed in a resin containing polyamide in a more uniform and molecular form. It is possible to obtain a composite material having excellent mechanical properties and heat resistance characteristics such as softening temperature and high temperature strength.
This composite material has an unprecedented remarkable effect that strength and heat resistance can be remarkably improved as compared with conventional nylon.

This composite material forms an ionic bond with a silicate layer, which is a negatively charged constituent unit of clay mineral, and a group having a positive charge that a part of polyamide in a resin has. The positive charge includes ammonium ions (-NH
₃ ⁺ ) group or trimethylammonium ion (-N ⁺ (CH
₃ ) ₃ ) group or a cation group (-NX ⁺ group: X is hydrogen (H), methyl ((CH ₃ ) ₃ ), copper (Cu)) formed by the interaction between the monomer molecule and the inorganic molecule. , Made of at least one kind of aluminum (Al), etc.
It becomes trivalent).

The method for producing the composite material of the present invention will be described below.

First, a swelling agent composed of a clay mineral having a cation exchange capacity of 50 to 200 meq / 100 g and an inorganic cation such as copper ion, hydrogen ion or aluminum ion, or a carbon number of 12
The swelling agent composed of an organic cation having an alkylene group and a carboxyl group as described above is brought into contact with each other to form an ionic bond between the two, and a composite having a property of being swollen by the monomer at a temperature not lower than the melting temperature of the monomer ( Contact step). This allows the clay mineral to adsorb the swelling agent,
A composite having a property of being swollen by the monomer at a temperature equal to or higher than the melting temperature of the monomer is obtained.

Here, as the contacting method, after the clay mineral is immersed in an aqueous solution containing a desired swelling agent, the clay mineral is washed with water to remove excess ions, and it is replaced with a predetermined swelling agent in advance. There is a method in which a cation exchange resin and a water suspension of clay mineral are brought into contact with each other to perform ion exchange.

The clay mineral is a clay mineral having a large cation exchange capacity of 50 to 200 meq / 100 g and a large contact area with a monomer to be reacted. Specifically, montmorillonite,
There are smectite clay minerals such as saponite, hydelite, nontronite, hectorite, and stevensite, vermiculite, halloysite, and the like, which may be natural or synthetic.

Here, the cation exchange capacity of the clay mineral used in the present invention is set to 50 to 200 meq / 100 g, because when the capacity exceeds 200 meq / 100 g, the bonding force between layers of the mineral is strong. Therefore, it is difficult to obtain the complex intended by the present invention. Further, when the cation exchange capacity of the clay mineral is less than 50 meq / 100 g, the exchange adsorption of the swelling agent consisting of an organic cation or an inorganic cation, which is indispensable in the production method of the present invention, cannot be sufficiently performed. This is because it is difficult to synthesize the composite material targeted by the present invention. The clay mineral is preferably crushed using a mixer, a ball mill, a vibration mill, a pin mill, a jet mill, a beating machine, or the like to have a desired shape and size in advance.

Furthermore, the swelling agent has a role of expanding the layers of the clay mineral and a role of giving a force to take the interlayer polymer into the clay mineral, and (a) copper ion (Cu ²⁺ ), hydrogen ion (H ⁺ ), Swelling agent consisting of one or more inorganic cations such as aluminum ions (Al ³⁺ ) or (b) swelling consisting of one or more organic cations having an alkylene group having 12 or more carbon atoms and a carboxyl group. Use agents.

The organic cation (b) having an alkylene group having 12 or more carbon atoms and a carboxyl group has a polymerization promoting action on a lactam compound, has 12 or more carbon atoms, and has X ⁺ -R-
It is a cation represented by COOH, and X ⁺ is ammonium ion (−NH ₃ ⁺ ) or trimethylammonium ion (−N ⁺
(CH ₃ ) ₃ ), the R group is an alkylene group containing an alkyl chain represented by — (CH) n—, and a phenylene group is included in the middle thereof. And a bond such as a vinylene group (HC═CH—) containing is also included. Specifically, 12-aminododecanoate ion (NH
_{^{3 + · C 12 H 22 ·}} COOH), 14- tetraacetic decanoate ion _{^{(NH 3 + · C 13 H}} 26 · COOH), + · 16- amino hexadecanoic acid ion _{(NH 3 C 15 H 30 ·} COOH), 18 -Aminooctadecanoate ion (NH ₃ ⁺ · C ₁₇ H ₃₄ · COOH) and the like, and one or a mixture of two or more of them is used.

The above-mentioned adsorbed clay minerals have a catalytic action for ring-opening polymerization of lactam compounds such as ε-caprolactam. Not only that, it has the ability to incorporate the polyamide produced by ring-opening polymerization of lactam and dehydration condensation of amino acid or nylon salt into the layers of clay. Therefore,
The super-dispersed composite according to the present invention is synthesized by utilizing the clay mineral that adsorbs these ions.

In the initiation of this polymerization reaction or in the polymerization reaction, the inorganic cations are (Cu ・ NH ⁺ −) and ammonium ions (H
_It forms a cation group such as ₃ N ⁺ −) and forms an ionic bond with this cation clay layer.

Also, the organic cation is To the polymer chain through the amide group of. Therefore, in the case of ordinary surfactants used for lipophilicity of clay mineral surface,
It cannot be used because it has no polymerization initiation action, polyamide intercalation action, and binding ability with organic polymer chains.

Here, as the organic cation having a carboxyl group, any one may be used as long as it satisfies the above conditions, but in order to draw the lactam compound into the interlayer or the like,
Alternatively, the projected area of the organic cations is preferably about 120 to 500Å ² in order to suppress the evaporation of lactam and to make the reinforcing effect of the clay mineral sufficient. For example, R groups are - if (CH ₂₎ a n- corresponds to 12 ≦ n ≦ 20. When n <12 or when the size of the ions is smaller than the corresponding size, the clay mineral is less likely to condense in the aqueous solution, which makes filtration and washing difficult, and the moisture absorption of the clay mineral. It becomes difficult to improve sex. In addition, the effect of promoting penetration of lactam molecules into the clay layer is small, which is not preferable. On the other hand, in the case of n> 20, it becomes insoluble and the ion exchange becomes difficult, which is not preferable. That is, by using a swelling agent having an organic cation of a carboxyl group having a carbon number within the above range, the swelling agent has a very strong action of incorporating polyamide monomer molecules between layers, and the clay interlayer distance is appropriately adjusted before polymerization. Since it can be expanded and, as a result, the cohesive force between layers is reduced, a composite material having excellent mechanical properties and heat resistance can be obtained. Furthermore, by using these swelling agents,
Since the clay mineral is hydrophobized in the aqueous solution and the particles are easily aggregated with each other, it is easy to filter and wash with water, and it is possible to exert a unique effect that the time required for the step is significantly shortened.

The inorganic cation or organic cation used as the swelling agent as described above has an action of incorporating polyamide monomer molecules between layers and an action of initiating ring-opening polymerization of a lactam compound. It also has the effect of being taken into The reason why only the above ions have a function of sufficiently incorporating the polymer between the layers, that is, a function of uniformly dispersing the silicate in the polymer in the polymer is not clear, but it is as follows. That is, in the case of an organic cation, the size of the molecule is considerably large, and the interlayer distance can be expanded to some extent in advance.
It is considered that the interaction between the carboxyl group and the amino group in the polyamide monomer has a strong force to take them in between the layers. Also, in the case of inorganic cations such as Cu ²⁺ , Al ²⁺ , and H ⁺ , the clay interlayer distance is expanded to some extent before polymerization due to the strong force of incorporating the above-mentioned monomer between layers, and as a result, the cohesive force between layers is It is thought that it is because it can be reduced. Thus, it is considered that the silicate can be uniformly and molecularly dispersed for the first time by reducing the cohesive force.

Next, the composite obtained in the contacting step and the polyamide monomer are mixed (mixing step).

Here, the polyamide monomer is a raw material that forms the base of the composite material and becomes a mixture of polyamide or polyamide and a polymer other than that after polymerization, and specifically, 6-amino-n-caproic acid. Amino acid compounds such as 12,12-aminododecanoic acid, nylon salt compounds such as hexamethylenediamine adipate, ε-caprolactam,
Lactam compounds such as valerolactam, capryllactam and α-pyrrolidinone.

The mixing of the composite and the polyamide monomer may be carried out by a conventional mixing method, specifically, mechanical mixing with an automatic mortar, a vibration mill or the like.

Next, the mixture obtained in the mixing step is heated to a predetermined temperature to polymerize under the catalytic action of the swelling agent (polymerization step). Here, this polymerization may be carried out by raising the temperature to a predetermined temperature immediately after mixing, but it is more effective if the polymer is once heated just above the melting point of the monomer and then the clay mineral is uniformly dispersed in the monomer.

The composite material obtained as described above may be used by molding by direct injection molding or heat / pressure molding, or may be mixed with a polymer such as another polyamide in advance so as to have a predetermined mixing ratio. Good. Further, the above-mentioned polymerization reaction may be advanced in a predetermined mold to obtain a molded product. Further, in the polyamide polymerization step, a polymerization catalyst such as phosphoric acid or syrup may be further added.

According to the present invention, a resin containing polyamide and a silicate layer uniformly molecularly dispersed in the resin are formed by the above method, and the silicate layer has a thickness of 7 to 12Å It is possible to obtain a suitable composite material in which the distance is 100 Å or more and the silicate layer is ionically bonded to a part of the polymer chain of the polyamide. This makes it possible to obtain a composite material having excellent mechanical properties such as tensile strength and elastic modulus and heat resistance characteristics such as softening temperature and high temperature strength.
This composite material has an unprecedented remarkable effect that strength and heat resistance can be remarkably improved as compared with conventional nylon.

That is, in the composite obtained by the method for producing a clay / polyamide composite of the prior art, since the clay layer is not dispersed with a large interlayer distance as in the present invention,
The tensile strength is not more than the strength of the resin as the matrix (for example, not more than the tensile strength of nylon 6). In the first place, it is said that in the prior art, when clay is dispersed in polyamide to form a hybrid, the mechanical strength such as tensile strength is lower than that of the original resin. The present invention
This is not based on the concept of the prior art, but is intended for the purpose of improving the mechanical strength and heat resistance of the molded product obtained from the original resin alone. It has excellent mechanical properties and heat resistance such as softening temperature and high temperature strength. As a result, the present invention can exert a remarkable effect which has not been obtained in the past, that mechanical strength and heat resistance can be remarkably improved as compared with conventional nylon.

〔Example〕

 Examples of the present invention will be described below.

(Example 1) As a clay mineral, a montmorillonite produced in Yamagata Prefecture (cation exchange capacity: 100 meq / 100 g) was used as a swelling agent as shown in Table 1 to prepare a complex, and a lactam compound was polymerized. It was

First, an inorganic cation and an organic cation shown in Table 1 as swelling agents were adsorbed on montmorillonite.
In this case, the adsorbed cations are aluminum ions (Al ³⁺ ).
In the case of 1, the ion-exchange resin was adsorbed in advance, and the column filled with the resin was adsorbed by circulating an aqueous suspension of montmorillonite.

In the case of other cations, 10 g of montmorillonite was immersed in an aqueous chloride solution (concentration 1 N) 1 containing ions to be adsorbed, and then filtration-washing with a Buchner funnel was repeated. .

The ion-exchanged montmorillonite and ε-caprolactam were mixed in a predetermined ratio using a mortar, placed in an aluminum container, dried at 80 ° C. for 3 hours, and ε.
-Aiming for homogeneity by melting caprolactam. The obtained product was placed in a stainless steel hermetic container and heat-treated at 250 ° C. for 5 hours to obtain a product. This was heated at 2 ° C./min using a DSC (Differential Scanning Calorimeter), the heat of fusion of the product was measured, and the conversion rate of the polyamide in the product was estimated.
The degree of dispersion was determined by measuring the distance between silicate layers by X-ray diffraction. The results obtained are shown in Table 1.

Next, the composite material of sample number 7 was molded by an injection molding machine to obtain a test piece. Using this test piece, a tensile test (JIS K7113) and a heat distortion temperature were measured. The results are shown in Table 2.

For comparison, sodium ion (Na ⁺ ), magnesium ion (Mg ²⁺ ), and surfactant (NH ₃ ⁺ (CH ₂ ) ₁₇ CH ₃ ) were used instead of the swelling agent described above, A comparative composite was obtained in the same manner as in Example 1 above (Sample No. C
1 to C3), the conversion of polyamide was estimated and the distance between silicate layers was measured. The obtained results are also shown in Table 1.

In addition, a sample (sample number: C4) in which montmorillonite treated with aminosilane was kneaded in the same ratio (montmorillonite: 10 g, nylon 6: 100 g) and nylon 6 (sample number: C5) were molded in the same manner as above, Similarly, a tensile test and a heat distortion temperature measurement were performed. The obtained results are also shown in Table 2.

As is clear from Tables 1 and 2, it can be seen that the composite material of this example according to the present invention is a material having excellent mechanical strength and heat resistance as compared with the comparative material.

That is, it can be seen that the composite material obtained in this example has improved mechanical strength and heat resistance of the composite, and has strength and heat resistance higher than that of ordinary nylon (Comparative Example: C5).

Further, instead of the swelling agent as in Comparative Examples C1 to C3, Na
^{In the case of using +} , Mg ²⁺ , NH ₃ ⁺ (CH ₂ ) ₁₇ CH ₃ , since the clay layer is not dispersed with a large interlayer distance as in this example, the tensile strength of the matrix is It was confirmed that the strength was lower than that of the resin (nylon 6).

As a result, in this example, a composite material having excellent mechanical properties such as tensile strength and elastic modulus, and excellent heat resistance characteristics such as softening temperature and high temperature strength was obtained. It can be seen that can be significantly improved over conventional nylon.

(Example 2) Chinese vermiculite (cation exchange capacity: 180 meq / 100 g) was pulverized by a vibrating ball mill using steel balls, and then 12-aminododecane was prepared in the same manner as in Example 1 above. Acid ions (NH ₃ ⁺ (CH ₂ ) ₁₁ COOH) were adsorbed as a swelling agent. This vermiculite powder 25
Hexamethylenediamine salt (6.6 salt) of adipic acid 20 g
0 g was mixed, and this was treated in a nitrogen (N ₂ ) stream at 230 ° C. for 5 hours to obtain a composite material of this example according to the present invention.

In the obtained composite material, a peak corresponding to the interlayer distance was not observed by the usual X-ray diffraction method (the interlayer distance was 100 Å or more), and it was confirmed that the vermiculite layer was uniformly dispersed.

(Example 3) A montmorillonite (Cation exchange capacity: 80 meq / 100 g) powder from Gunma prefecture was prepared in the same manner as in Example 1 above.
- amino dodecanoic acid ion ^{_{(NH 3 + (CH 2)}} 11 COOH) is ion adsorbed as swelling agent. This powder (50 g) was mixed with 12-aminododecanoate ion (NH ₃ ⁺ (CH ₂ ) ₁₁ COOH) (50 g), and then heat-treated in a nitrogen (N ₂ ) stream at 240 ° C. for 10 hours to give the present example. A composite material of When the interlayer distance of the obtained composite material was confirmed in the same manner as in Example 2, it was 100 Å or more.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Shigeri Sugiyama Inventor Shigeru Sugiyama 1 41st Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture 1st panel of Toyota Central Research Institute Co., Ltd. Mikami Kawakami (56) Reference JP-A-51-109998 (JP, A)

Claims (7)

[Claims] 1. A composite material comprising a resin containing polyamide and a silicate layer uniformly dispersed in the resin in a unit of thickness at a molecular level, wherein the silicate layer has a thickness of 7 ~ 12Å, the distance between silicate layers is 10
0 Å or more, and the silicate layer is ionically bonded to a part of the polymer chain of the polyamide, the content of the silicate layer is 0.5 to 150 parts by weight with respect to 100 parts by weight of the resin, The composite material has a cation exchange capacity of 50-200 meq /
100g of clay mineral, aluminum ion, hydrogen ion,
A composite material obtained by using a composite obtained by contacting a swelling agent composed of one or more inorganic cations of copper ions or an organic cation having an alkylene group having 12 or more carbon atoms and a carboxyl group. And is a composite material characterized by excellent mechanical strength and heat resistance. 2. The composite material according to claim 1, wherein the content of the silicate layer is 0.5 to 25 parts by weight with respect to 100 parts by weight of the resin. 3. The silicate layer has a negative charge and forms an ionic bond with a group having a positive charge that a part of the polyamide in the resin has, and the area per valence of the negative charge is 25 to 50. 200Å ²
The composite material according to claim (1), characterized in that 4. The composite material according to claim 2, wherein the content of the silicate layer is 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin. 5. The composite material according to claim 1, wherein the silicate layer is an aluminum silicate phyllosilicate or a magnesium silicate phyllosilicate. 6. The polyamide in the resin partially has a cation group (—NX ⁺ group), and X is hydrogen (H) or methyl ((CH ₃ )).
₃ ), one kind or two or more kinds of elements of copper (Cu) and aluminum (Al), The composite material according to claim (1). 7. The polyamide in the resin partially has a cation group (-R ⁺ group), and the R ⁺ group has an ammonium ion (-N ⁺ group).
H ₃ ⁺ ) group or trimethylammonium ion (−N ⁺ (C
The composite material according to claim (1), characterized in that it is a H ₃ ) ₃ ) group.