JP2000136308A - Resin composite material and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composite material having high mechanical properties and a preparation process for resin composite materials wherein the deterioration of polymers composing the resin composite materials is prevented. SOLUTION: A resin composite material comprises a polymer and an organified clay, wherein an organic matter contained in the organified clay is linked to the clay at a part other than the terminal of its longest molecular chain. A preparation process of this material comprises an organification step wherein an organification agent possessing a reactive group at a part other than the terminal of its longest chain is prepared and a clay is organified using this organification agent, and a mixing/polymerization process wherein a polymer and/or monomer is added to the clay and the clay and the polymer and/or monomer are mixed and/or polymerized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composite material in which an organized clay is dispersed in a polymer and a method for producing the same.

[0002]

2. Description of the Related Art In order to enhance the mechanical properties of a resin material, it has been studied to add and mix an organic clay to the resin material. For example, for maleic acid-modified polypropylene,
Organized clay (stearyl ammonium [C18]
Montmorillonite, etc.), added and mixed. Thereby, the mechanical properties such as strength and elastic modulus of the maleic acid-modified polypropylene can be greatly improved.

[0003] Such a method of adding an organically modified clay to a resin material is effective even if the amount of the organically modified clay to be added is small. is there. The reason why the clay is added to the resin material after the organic treatment is that the clay is not easily blended with the resin material as it is, and the clay does not mix well with the resin material.

[0004]

However, simply adding and mixing the organic clay to the resin material may not be able to completely satisfy the above-described effect of the property improvement. Therefore, as a result of diligent efforts, the present inventors have found that it is effective to actively form a covalent bond between an organic agent of clay and a polymer constituting a resin material.

[0005] When an attempt is made to improve a resin material using a clay which has been conventionally used and which has been organically modified with an organic agent having a reactive group at a terminal, a very large shearing force is required to disperse the organically modified clay. Power is needed. For this reason, the shear force applied to disperse the organized clay
There has been a problem that the polymer constituting the resin material is decomposed.

SUMMARY OF THE INVENTION The present invention has been made in view of such conventional problems, and is a resin composite material having excellent mechanical properties. The resin composite material can prevent deterioration of a polymer constituting the resin composite material during manufacturing. It is intended to provide a method for producing the same.

[0007]

The invention according to claim 1 comprises a polymer and an organized clay, wherein an organic substance contained in the organized clay is bonded to the clay at a position other than the end of the longest molecular chain. Resin composite material.

The operation of the present invention will be described. The resin composite material according to the present invention is composed of a polymer and an organized clay, and the organic substance contained in the organized clay is free from the longest molecular chain terminal being not bonded to the clay, and is in the free state. It is considered that the terminal of the other molecular chain other than the molecular chain, or the part in the middle of the longest molecular chain is in a state of being bonded to the clay.

As described later, the clay is formed by laminating a plurality of sheets 15 and 95 and has a layered structure. Organized clay is shown in FIGS.
As shown in (a), an organic substance (here, the organic agent 16 and the organic agent 96) has entered between the sheets 15 and 95. Here, consider an organized clay in which the terminal of the longest molecular chain of an organic substance is bonded to a clay. In this one,
As shown in FIG. 4A, it is considered that the longest molecular chain of the organic substance strongly bonds between the adjacent sheets 95.

When the organic clay is mixed with a polymer, the organic substance is hardly reacted with the functional group of the polymer because the longest molecular chain is restricted by the sheet 95 and the degree of freedom is small, as shown in FIG. 4 (b). , The sheet 95 is bonded by the organic substance, and the resin composite material 9 is dispersed in the polymer while maintaining the layered structure. As a result, the reinforcement of the polymer by the clay becomes insufficient. Further, in order to sufficiently disperse such an organized clay in a polymer, it is necessary to apply a large shearing force to break the bond between the terminal of the longest molecular chain of the organic substance and the sheet 95. High shear forces will degrade the polymer.

On the other hand, as shown in FIG. 2, the organic matter in the organized clay according to the present invention has the longest molecular chain at the end of the sheet 1.
Not linked to 5. And the terminal of the longest molecular chain is in a free state. Therefore, as described later, by mixing the organically modified clay according to the present invention with the polymer,
The sheet 15 separates and enters the polymer (finely dispersed in the polymer), and the molecular chains constituting the polymer and the sheet 15 are covalently bonded to each other, whereby the bond between the molecular chains constituting the polymer is strengthened. (See FIG. 1).

As described above, in the composite resin material according to the present invention, since the sheet 15 forms a covalent bond with the polymer, larger and superior mechanical properties (such as strength and elastic modulus) can be obtained. (See Tables 1 and 2).

As described above, according to the present invention, a resin composite material having excellent mechanical properties can be provided. Although the resin composite material according to the present invention is used, the sheet 15 is finely dispersed in the polymer, and a physical shielding effect can be imparted to the resin composite material. And high gas barrier properties can be obtained.

Next, the above-mentioned organized clay will be described. The organic clay according to the present invention is, as described later,
Using various organic agents such as onium ion,
Binding organic matter to clay (organizing clay)
It is a substance that can be obtained by using organic substances in its structure. And this organic matter is bonded to clay except at the end of the longest molecular chain. Here, clay (clay mineral) is a silicate mineral etc. having a layered structure. Many sheets (some are tetrahedral sheets made of silicic acid, some are octahedral sheets containing Al, Mg, etc.) Is a substance having a laminated layered structure. And the organic matter has entered between the sheets.

Examples of the clay which is a source of the organized clay in the present invention include montmorillonite, saponite, hectorite, beidellite, stevensite,
Examples include nontronite, vermiculite, halloysite, mica, fluorinated mica, kaolinite, and pyrophyllolite. Moreover, it may be a natural product or a synthetic product.

Next, specific examples of the above polymer will be described below. Polyester (for example, polybutylene terephthalate, polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate),
Polycarbonate, polyacetal, polyarylate, polyamide (nylon 6, nylon 11, nylon 12, nylon 66, nylon 46, aromatic nylon), polyamide imide, polyether imide, polyether ketone, polybutalamide, polyether nitrile, Examples include acrylic resins such as polybenzimidazole, polycarbodiimide, polysiloxane, polymethyl (meth) acrylate, and poly (meth) acrylamide, acrylic rubber, urea resin, diallyl phthalate resin, silicone resin, and urethane resin.

Further, a modified polymer or a copolymer may be used as the polymer. As shown in FIG. 6, the modified polymer is obtained by introducing a functional group 50 into a side chain and / or a main chain by modifying the polymer 502. Examples of the polymer 502 include polyethylene, polypropylene, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene copolymer, polybutadiene, polyisoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, and ethylene-propylene-diene copolymer. Polymer, ethylene-butene-diene copolymer, butyl rubber, polystyrene, styrene-butadiene copolymer, styrene-hydrogenated butadiene copolymer, polyamide, polycarbonate, polyacetal, polyester, polyphenylene ether, polyphenylene sulfide, polyether sulfone , Polyetherketone, polyarylate, polymethylpentene, polyphthalamide, polyethernitrile, polyethersulfone, polybenzimidazole, polycal Polymers such as diimide, polytetrafluoroethylene, fluororesin, polyamideimide, polyetherimide, liquid crystal polymer, epoxy resin, melamine resin, urea resin, diallyl phthalate resin, phenolic resin, polysilane, polysiloxane, silicone resin, urethane resin Can be used.

The functional group introduced by the modification may be any functional group capable of intercalating between the sheets constituting the clay. In order to determine whether or not intercalation can be performed between sheets, a compound having the functional group is mixed with the organized clay, and the interlayer distance of the organized clay may be measured by X-ray diffraction. Intercalation is preferred because the interlayer distance between the organized clays is increased and the organized clays are more easily dispersed.

The functional groups capable of intercalation include:
For example, there are (1) those having a polarization in a molecule, and (2) those having π electrons on an aromatic ring which can move relatively freely.
Examples of the functional group (1) having polarization include an acid anhydride group, a carboxylic acid group, a hydroxyl group, a thiol group, an epoxy group,
Functional groups such as halogen groups, ester groups, amide groups, urea groups, urethane groups, ether groups, thioether groups, sulfonic acid groups, phosphonic acid groups, nitro groups, amino groups, oxazoline groups, imide groups, and isocyanate groups. .

Examples of the functional group (2) having a π electron include aromatic rings such as a benzene ring, a pyridine ring, a pyrrole ring, a furan ring and a thiophene ring. The aromatic ring may have a substituent. The π electron on the aromatic ring is
When charged organically modified clay approaches, π
Electrons are biased and polarization is induced in the aromatic ring. Therefore, the aromatic ring acts as an effective functional group for intercalation between the clay sheets. In the case of a polymer having a functional group such as polystyrene, it is preferable to use a functional group to be introduced by modification that has a larger interaction with the sheet constituting the clay.

As shown in FIG. 7, the copolymer 5 having a functional group 50 is composed of a functional group monomer 51 having a functional group 50 and a monomer 52 copolymerizable with the functional group monomer 51.

The form of distribution of the functional group monomer in the copolymer is not particularly limited. The form of the copolymer will be described below. As shown in FIG. 7A, a random copolymer in which functional group monomers 51 are randomly (randomly) distributed in the copolymer 5 can be mentioned. Further, as shown in FIG.
Are distributed continuously.
Further, as shown in FIG. 7C, an alternating copolymer in which a functional group monomer 51 and a copolymerizable monomer 52 are alternately bonded is exemplified. Further, the copolymer may have a branched structure due to the presence of a monomer having two or more polymerizable groups.

The functional group of the above copolymer may be any functional group capable of intercalating between clay sheets, similarly to the modified polymer.
Some have polarization in the molecule, and (2) have π electrons. Specific examples thereof are the same as those of the modified polymer.

The functional group monomer is not particularly limited as long as it is a polymerizable monomer having the functional group.
One or more functional groups may be present in the monomer. When two or more are present, they may be the same type of functional group or different.

For example, monomers having such functional groups include acrylic monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate, (meth) acrylamide, methyl (meth) acrylamide, and ethyl (meth) acrylate. ) Acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, etc., acrylamide, (meth) acrylic acid, maleic anhydride, maleimide, etc., compounds having unsaturated carbon, styrene, vinylpyridine, vinylthiophene, etc. Examples of such a monomer include a monomer having an aromatic ring such as a benzene ring, a pyridine ring, and a thiophene ring. Further, the functional group monomer may be a monomer having two or more polymerizable groups (for example, vinyl group) in one molecule.

The monomer copolymerizable with the functional group is, for example, a hydrocarbon compound having a double bond such as ethylene, propylene, butene or pentene, a hydrocarbon compound having a triple bond such as acetylene or propyne, or butadiene or isoprene. And the like, and may have a branched structure or a cyclic structure in their carbon chains.

The above monomers may be combined with a functional group monomer to form an acrylic monomer such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylamide, methyl (meth) acrylamide, Acrylamide such as ethyl (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, or a monomer having an aromatic ring such as styrene or methylstyrene may be used. In this case, an aromatic ring such as methylstyrene may contain a substituent. Further, it may be a monomer having two or more polymerizable groups in one molecule.

A monomer having a large interaction with the sheet constituting the clay is defined as a functional group monomer as a combination of monomers. For example, in the case of an ethylene-styrene copolymer, styrene having a large interaction with the sheet is the functional group monomer. In the case of a styrene-vinyl oxazoline copolymer, vinyl oxazoline having a larger interaction is the functional group monomer.

The number average molecular weight of the polymer according to the present invention is preferably 5,000 to 10,000,000. Thus, a material having excellent mechanical properties and excellent workability can be obtained. 10,
If it is larger than 1,000,000, the processability of the resin composite material may deteriorate. If it is less than 5,000, the mechanical properties of the resin composite material may be low.

The resin composite material according to the present invention preferably comprises 100 parts by weight of a polymer and 0.01 to 200 parts by weight of an organized clay. As a result, a resin composite material having excellent mechanical properties and gas barrier properties and excellent workability can be obtained.

When the amount of the organized clay is less than 0.01 part by weight, there is a possibility that sufficient improvement in mechanical properties cannot be obtained. If the amount of the organic clay exceeds 200 parts by weight, processability may be impaired. In addition, it is more preferable that the lower limit of the organically modified clay be 0.1 part by weight. The upper limit of the above-mentioned organic clay is 30.
It is more preferred to be parts by weight.

In the resin composite material, it is preferable that the organic clay is dispersed in the polymer in a size of 1 μm or less. Thereby, a high reinforcing effect and a high gas barrier property can be obtained. If the organized clay is dispersed in a state larger than 1 μm, the appearance of the resin composite material may be reduced, and the material may have poor appearance.

In the dispersion of the organic clay,
The polymer is preferably intercalated between the sheets constituting the organized clay. By this intercalation, the interface between the surface of the organized clay and the polymer is increased, and a large reinforcing effect on the polymer by the organized clay can be obtained.

The intercalation increases the distance (interlayer distance) between the sheets of the organized clay. Therefore,
The proportion of polymer bound by the organized clay increases,
The reinforcing effect of the organic clay can be further enhanced. Therefore, the effects of the present invention can be reliably obtained.

The term "intercalate" means that the distance between the sheets constituting the organized clay (interlayer distance) is larger than the interlayer distance in the original clay due to the composite of the polymer and the organized clay. Pointed out. This state can be confirmed by X-ray diffraction.
The increase in interlayer distance due to the above intercalation is 1
It is preferable that the distance be 0 ° or more and be wider than the original interlayer distance. Thereby, the effect of improving the mechanical properties of the polymer by the organized clay can be reliably obtained. Further, the expansion of the interlayer distance is preferably 30 ° or more, more preferably 100 ° or more.

Further, in the dispersion of the organically modified clay,
It is preferable that the organic clay is molecularly dispersed in a polymer having a functional group in a state where the layer structure of the clay disappears and the sheet constituting the layer structure is separated (see FIG. 1). ).

By dispersing in such a state, the organized clay can be uniformly dispersed in the polymer.
The proportion of polymer constrained by the organized clay is very large. For this reason, since the reinforcing effect by the organically modified clay can be obtained to the maximum, the effect of the present invention can be reliably obtained. In the dispersion of the organized clay, the effect of the present invention can be obtained even if the layered structure partially remains, provided that the remaining layered structure is sufficiently small.

Next, as in the second aspect of the present invention, it is preferable that the above-mentioned organized clay is obtained by organizing clay with an organic agent having a reactive group other than the terminal of the longest molecular chain. An organic agent having the above reactive group at a position other than the terminal of the longest molecular chain will be described. As shown in FIG. 5 (a), this compound has a reactive group X inside the molecular chain constituting the organizing agent other than the terminal of the longest molecular chain, or FIG. 5 (b)
As shown in (1), an organic substance has a reactive group X at the end of the molecular chain, and a molecular chain longer than the molecular chain having the reactive group X exists in another place.

As used herein, the term "reactive group" refers to a portion which acts as a reaction point in a reaction (in the present invention, a reaction for bonding an organized clay and a polymer). It is a structure consisting of a functional group of

As shown in FIG. 4 (a), if the clay is organized by an organic agent 96 having a reactive group 960 at the end of the longest molecular chain, the molecular chains 96 constituting the organic agent 96
1 enters between the sheets 95 constituting the clay, and
The OH ^- groups and N ⁺ groups cause the sheets 95 to be strongly bonded to each other.

The organic agent having a reactive group other than the terminal of the longest molecular chain includes, for example, organic onium ions. The organic onium ion is an ion having one or two or more reactive groups inside other than the terminal of the longest molecular chain. Further, one or two or more branched molecular chains having a reactive group are present at portions other than the terminal of the longest molecular chain constituting the onium ion.

This branched molecular chain is shorter than the longest molecular chain constituting the organic onium ion. Therefore, when the organic onium ions enter between the sheets 95, the reactive groups in the branched molecular chains do not come into contact with the surface of the sheet constituting the clay. This is because longer molecular chains come into contact with the sheet. When the branched molecular chain has two or more reactive groups, these reactive groups may be the same or different.

It is preferable that at least one of the longest molecular chains in the organic onium ion has 4 or more carbon atoms. When the number of carbon atoms is less than 3, the organic agent cannot sufficiently hydrophobize the clay, so that the compatibility between the clay and the polymer is low and the clay and the polymer cannot be sufficiently mixed. There is a possibility that a resin composite material cannot be obtained. Specific examples of the organic onium ion include the following ammonium ions and phosphonium ions. Hereinafter, specific examples are listed.

Examples of the ammonium include hexyl hydroxyethyl ammonium, octyl hydroxyethyl ammonium, decyl hydroxyethyl ammonium, dodecyl hydroxyethyl ammonium, octadecyl hydroxyethyl ammonium, hexyl hydroxyethyl methyl ammonium, octyl hydroxyethyl methyl ammonium, and decyl hydroxyethyl. Methyl ammonium, dodecyl hydroxyethyl methyl ammonium, octadecyl hydroxyethyl methyl ammonium, hexyl hydroxyethyl dimethyl ammonium, octyl hydroxyethyl dimethyl ammonium, decyl hydroxyethyl dimethyl ammonium, dodecyl hydroxyethyl dimethyl ammonium, octadecyl hydroxy Le dimethyl ammonium, hexyl di (hydroxyethyl) methyl ammonium, octyl di (hydroxyethyl) methylammonium, Deshiruji (hydroxyethyl) methyl ammonium, dodecyl di (hydroxyethyl) methyl ammonium, octadecyl di (hydroxyethyl) methyl ammonium and the like.

Further, for example, hexylcarboxyethylammonium, octylcarboxyethylammonium, decylcarboxyethylammonium, dodecylcarboxyethylammonium, octadecylcarboxyethylammonium, hexylcarboxyethylmethylammonium, octylcarboxyethylmethylammonium, decylcarboxyethylmethylammonium,
Dodecylcarboxyethylmethylammonium, octadecylcarboxyethylmethylammonium, hexylhydroxyethyldimethylammonium, octylcarboxyethyldimethylammonium, decylcarboxyethyldimethylammonium, dodecylcarboxyethyldimethylammonium, octadecylcarboxyethyldimethylammonium, hexyldi (carboxyethyl) methylammonium, Octyldi (carboxyethyl) methylammonium, decyldi (carboxyethyl) methylammonium, dodecyldi (carboxyethyl) methylammonium, octadecyldi (carboxyethyl) methylammonium and the like can be mentioned.

Further, for example, hexylmercaptoethylammonium, octylmercaptoethylammonium, decylmercaptoethylammonium, dodecylmercaptoethylammonium, octadecylmercaptoethylammonium, hexylmercaptoethylmethylammonium, octylmercaptoethylmethylammonium, decylmercaptoethylmethylammonium,
Dodecylmercaptoethylmethylammonium, octadecylmercaptoethylmethylammonium, hexylhydroxyethyldimethylammonium, octylmercaptoethyldimethylammonium, decylmercaptoethyldimethylammonium, dodecylmercaptoethyldimethylammonium, octadecylmercaptoethyldimethylammonium, hexyldi (mercaptoethyl) methylammonium, Octyl di (mercaptoethyl) methylammonium, decyldi (mercaptoethyl) methylammonium, dodecyldi (mercaptoethyl) methylammonium, octadecyldi (mercaptoethyl) methylammonium and the like can be mentioned. The organic agent according to the present invention is not limited to the substances listed above.

Next, the reactive group of the above-mentioned organic agent will be described. Suitable reactive groups differ depending on the functional groups of the polymer combined with the organized clay. The combination of a reactive group and a functional group is important. For example, consider a case where polyester is used as a polymer having a functional group. The polyester has a hydroxyl group or a carboxyl group at the terminal of a molecular chain constituting the polyester. Accordingly, clay which has been organically treated with an organic agent having a hydroxyl group, a thiol group, or a carboxyl group, an acid anhydride group, an isocyanate group, or the like, capable of reacting with the above-mentioned carboxyl group as a reactive group. It is preferable to combine them.

In the case where maleic anhydride-modified polypropylene is used as the polymer having a functional group, a combination of an organically modified clay that has been organically treated with an organic agent having a hydroxyl group and a thiol group capable of reacting with maleic anhydride group is used. Is preferred. Furthermore, when polyphenylene ether is used as the polymer having a functional group, an organically modified clay that has been organically treated with an organic agent having a carboxyl group, an acid anhydride group, an isocyanate group, etc., which can react with a hydroxyl group, must be combined. Is preferred. In the case where polyphenylene sulfide is used, it is preferable to combine an organically modified clay that has been organically modified with an organic agent having a carboxyl group, an acid anhydride group, an isocyanate group, or the like that can react with a thiol group.

Next, according to the third aspect of the present invention, the polymer is preferably a modified polyolefin. This makes it possible to mix the polymer and the organized clay with a low shear force by using a shear force or the like, so that the deterioration of the polymer can be more reliably prevented. Therefore, a resin composite material having more excellent mechanical properties can be obtained.

Next, the invention according to claim 4 is to provide an organic agent having a reactive group at a position other than the terminal of the longest molecular chain, and to organize the clay with the organic agent. A method for producing a resin composite material, comprising adding a polymer and / or monomer to clay, and performing a mixing / polymerization step of mixing and / or polymerizing the clay and the polymer and / or monomer.

The above-mentioned organizing step is a step of reacting clay with an organic agent to make the clay organic by an ion exchange reaction. In this step, the clay is organized by an ion exchange reaction, and the ions in the organizing agent are bonded to the clay surface by ionic bonds, and the clay surface becomes an organized clay having a hydrophobic surface (see FIG. 2).

In the production method of the present invention, a mixing / polymerization step can be carried out separately from the above-mentioned organizing step, or can be carried out simultaneously with the organizing step. This mixture /
In the polymerization process, "polymer and / or monomer"
Is added. This means that "only the polymer can be added, the monomer can be added, or both can be added at the same time."

When this step is performed by adding a monomer, a polymer is formed by polymerizing the monomer in the mixing / polymerization step, and the polymer and the organic clay are mixed so as to be dispersed. When this step is performed by adding a polymer, the organic clay and the polymer are mixed so as to be dispersed.

The mixing / polymerization step is more preferably performed by melt-kneading under shearing with a twin-screw extruder, as shown in an embodiment example to be described later.
Thereby, the organic clay and the polymer can be sufficiently dispersed. As another method, the organic clay and the polymer can be mixed by dispersing and dissolving the organic clay and the polymer in a solvent, mixing the two, and removing only the solvent.

The operation and effect of the present invention will be described. By utilizing the production method of the present invention comprising the above-mentioned organic treatment step and mixing / polymerization step, as shown in FIG. 1 described later, a resin in which the organic clay is dispersed and entered into a polymer having a functional group. A composite material can be obtained. This resin composite material has excellent mechanical properties because the sheet derived from the organized clay is bonded to the polymer having a functional group (see Tables 1 and 2). Further, in the production method of this example, in the mixing / polymerization step, the polymer having a functional group and the organized clay can be made into a resin composite material without applying an extremely high shearing force. Therefore, according to the present invention, it is possible to provide a method for producing a resin composite material that can prevent deterioration of a polymer constituting the resin composite material during production.

The resin composite material according to the present invention can be widely applied as various molding materials such as injection molding materials, extrusion molding materials, press molding materials, blow molding materials, and film molding materials. Further, since the resin composite material according to the present invention is a resin material having particularly excellent mechanical properties (see the embodiments), it can be widely used mainly for interior and exterior materials for automobiles, home electric appliances and the like.

[0057]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment A resin composite material and a method for manufacturing the same according to an embodiment of the present invention will be described with reference to FIGS. FIG.
As shown in (1), the resin composite material 1 of the present example is composed of a polymer and an organized clay, and an organic substance contained in the organized clay is bonded to the clay except at the terminal of the longest molecular chain.
In the resin composite material 1, the polymer forms a matrix 10 of the resin composite material 1, and the matrix 1
The sheets 15 constituting the above-mentioned organically modified clay are dispersed in the area 0. Further, the sheet 15 is composed of the molecular chains 1 constituting the organic matter (organizing agent 16 shown in FIG. 2) contained in the organized clay.
61 are connected.

As shown in FIG. 2, the above-mentioned organic clay is obtained by organizing clay, and the organic agent 16 is in a state of entering the sheet 15 constituting the layer structure of clay. Such an organized clay is dispersed in the matrix 10 composed of a polymer by using a manufacturing method described later, but at this time, the clay loses its layer structure, and the sheet 15 having the layer structure has disappeared. The molecules are dispersed in a state where they are separated (FIG. 1).

The outline of the method for producing the resin composite material of this embodiment will be described. First, the clay is organized using an organic agent. Thereby, as shown in FIG. 2, the molecular chains 161 of the organic agent 16 are interposed between the sheets 15 constituting the clay.
Penetrates and spreads between layers. In addition, reactive groups 160 are present at positions other than the end of the longest molecular chain in the molecular chain (-OH in the figure), but they do not interact with the sheet 15.

[0060] Such an organized clay and a polymer are
Melt and knead using a screw extruder or the like. As a result, as shown in FIG. 1 described above, the clay sheet 15 is separated and molecularly dispersed in the matrix 10 formed by the polymer, and the resin composite material 1 is obtained.

Next, the performance of the resin composite material according to the present invention will be described together with comparative samples. First, the resin composite material according to Sample 1 will be described. As the clay, Na-montmorillonite (Kunipia F) manufactured by Kunimine Industries, which is a layered clay mineral, was prepared. 80 g of this Na-montmorillonite was dispersed in 5000 ml of water at 80 ° C.

Next, octadecyldi (hydroxyethyl) methylammonium bromide was prepared as an organic agent. 43.1 g of this organic agent was dissolved in 2000 ml of water at 80 ° C., and this solution was added to the above dispersion of montmorillonite. Note that octadecyldi (hydroxyethyl) methylammonium bromide as the above-mentioned organicizing agent has a structure in which a reactive group having a structure as shown in FIG. 3 (the reactive group in this is a hydroxyl group) has a longest molecular chain (CH in this case). ₁₈ H ₃₇ N ⁺ -CH ₂ OH).

The precipitate obtained is filtered and
After washing three times with water at ℃ and freeze-drying, an organized montmorillonite was obtained. In addition, when the inorganic content in this organized montmorillonite was measured, it was 63%.
The interlayer distance in the layered structure of the organized montmorillonite determined by the X-ray diffraction method was 22 °. In addition,
The organic montmorillonite obtained here will be referred to as C
Abbreviated as 18 (OH) -Mt.

Next, maleic acid-modified polypropylene (P
O1015, Exxon) 400g and C18 (OH)-
13.1 g of Mt was melt-kneaded using a twin-screw extruder.
At this time, the kneading temperature was 200 ° C., and the twin-screw extruder had a shaft rotation speed of 200 rpm. The inorganic content of Sample 1 obtained by the above kneading was determined by a burning test to be 2.0% by weight.

Next, 400 g of maleic acid-modified polypropylene (PO1015, manufactured by Exxon) and the above C
It was prepared by melt-kneading 20 (g) of 18 (OH) -Mt using a twin screw extruder. The kneading temperature at this time is 20
The twin-screw extruder at 0 ° C. had a shaft rotation speed of 200 rpm. The inorganic content of Sample 2 obtained by the above kneading was determined by a scuffing method and found to be 3.0% by weight.

Next, a comparative sample C1 was prepared by the following method. As the clay, Na-montmorillonite (Kunipia F) manufactured by Kunimine Industries, which is a layered clay mineral, was prepared. 80 g of this Na-montmorillonite was dispersed in 5000 ml of water at 80 ° C. Next, octadecylamine was prepared as an organic agent. This organic agent 2
8.5 g of concentrated hydrochloric acid (11 ml) was added to 80 ° C. water (200).
The solution was dissolved in 0 ml, and the solution was added to the dispersion of montmorillonite. Note that octadecylamine as the above-mentioned organic agent is a compound having a structure of C ₁₈ H ₁₇ NH ₂ .

The resulting precipitate was filtered and
After washing three times with water at ℃ and freeze-drying, an organized montmorillonite was obtained. The inorganic content in this organized montmorillonite was 68%. The interlayer distance in the layered structure of the organized montmorillonite determined by the X-ray diffraction method was 22 °. The organically treated montmorillonite obtained here is hereinafter abbreviated as C18-Mt.

Next, maleic acid-modified polypropylene (P
O1015, Exxon) 100g and the above C18-Mt
11.8 g was melt-kneaded using a twin screw extruder. The kneading temperature at this time is 200 ° C.
It was set to 0 rpm.

A comparative sample C2 was prepared by melt-kneading 100 g of maleic acid-modified polypropylene (PO1015, manufactured by Exxon) and 1.8 g of C18-Mt using a twin-screw extruder. The kneading temperature at this time is 20
The twin-screw extruder at 0 ° C. had a shaft rotation speed of 200 rpm. The inorganic content of the comparative sample C2 obtained by the above-mentioned kneading was 2.0 wt% as determined by a burning test.

When these samples 1 and 2 and comparative samples C1 and C2 were observed with a transmission electron microscope, it was found that clay was dispersed in the polymer on the order of nanometers in each case. The samples 1, 2 and the comparative samples C1, C
2 was subjected to a tensile test based on ASTM-D638. The results are shown in Table 1. For reference, the results of tensile tests on maleic acid-modified polypropylene (described as modified PP in the same table) are also described. According to the table, it was found that the use of C18 (OH) -Mt improved the strength and elastic modulus as compared with the modified PP. It was also found that the strength was improved as compared with the comparative samples C1 and C2 using C18-Mt.

As a sample 3, polybutylene terephthalate (UBE PBT 1000 manufactured by Ube Industries) 4
It was produced by melt-kneading 00 g and the above C18 (OH) -Mt 20 g using a twin-screw extruder. The kneading temperature at this time is 250 ° C., and the number of rotations of the twin-screw extruder is 200 r.
pm. The inorganic content of Sample 3 obtained by the above kneading was determined by a shaving method and found to be 3.0% by weight.

As a comparative sample C3, 400 g of polybutylene terephthalate (UBE PBT1000 manufactured by Ube Industries) and 17.9 g of C18TM-Mt shown below were melt-kneaded using a twin-screw extruder. The kneading temperature at this time was 250 ° C., and the twin-screw extruder had a shaft rotation speed of 200 rpm.

The C18TM-Mt is manufactured as follows. As the clay, Na-montmorillonite (trade name: Kunivia F) manufactured by Kunimine Industries, which is a layered clay mineral, was prepared. This Na-montmorillonite 8
0 g was dispersed in 5000 ml of water at 80 ° C.
Next, octadecyltrimethylammonium bromide was prepared as an organic agent. 37.8 g of this organic agent was added to 8
The solution was dissolved in 2000 ml of water at 0 ° C., and the solution was added to the montmorillonite dispersion.

The precipitate thus obtained was filtered, and 80
After washing three times with water at ℃ and freeze-drying, an organized montmorillonite was obtained. The inorganic content in the organically treated montmorillonite was measured to be 67%. Also, X
The interlayer distance in the layered structure of the organized montmorillonite determined by the line diffraction method was 22 °. The organized montmorillonite obtained here is C18TM-Mt.

The inorganic content of the comparative sample C3 obtained by the above kneading was determined by a sharpening method to be 3.0% by weight. When these sample 3 and comparative sample C3 were observed with a transmission electron microscope, it was found that clay was dispersed in the polymer in the order of nanometer in all cases.

Further, with respect to Sample 3 and Comparative Sample C3,
A tensile test based on ASTM-D638 was performed. The results are shown in Table 2. For reference, the results of tensile tests on polybutylene terephthalate (described as PBT in the same table) are also described. According to the table, C
It was found that Sample 3 using 18 (OH) -Mt had improved strength and elastic modulus as compared with PBT. It was also found that the strength and the elastic modulus were improved compared to the comparative sample C3.

Next, the operation and effect according to this embodiment will be described. As shown in Samples 1 and 2, the resin composite material according to this example includes a maleic acid-modified polypropylene, which is a polymer having a functional group, and an octadecyldi (hydroxy), which is an organic agent having a reactive group at a position other than the end of the longest molecular chain. (Organized montmorillonite) which was organically treated with (ethyl) methylammonium bromide.

The montmorillonite is made organic by the above-mentioned organic oxidizing agent. As a result, the organic oxidizing agent enters between the sheets of silicic acid constituting the layered structure of montmorillonite.
Increase the interlayer distance between sheets.

The thus-organized montmorillonite is melt-kneaded with a maleic acid-modified polypropylene using a twin-screw extruder. In this kneading, the maleic anhydride of the maleic acid-modified polypropylene converts the hydroxyl groups and the ester in the organic agent into esters. Because of the formation, the sheets constituting the montmorillonite are separated and dispersed, and as a result, as shown in FIG. 1, a resin composite material in which the sheet derived from montmorillonite is dispersed in a polypropylene matrix is obtained.

Thus, since the sheet derived from montmorillonite restricts the movement of the molecular chain with respect to polypropylene, a resin composite material having high mechanical properties such as elasticity as described above can be obtained.

In the production method of the present embodiment, for example, for the samples 1 and 2, a resin composite material can be obtained by melt-kneading at a temperature of 200 ° C. and a shaft rotation speed of 200 rpm using a twin-screw extruder. For this reason, degradation of the polypropylene can be prevented from occurring, and a resin composite material having high mechanical properties can be reliably obtained.

As described above, according to this embodiment, it is possible to provide a method for producing a resin composite material which is excellent in mechanical properties and which can prevent deterioration of a polymer constituting the resin composite material during production.

[0083]

[Table 1]

[0084]

[Table 2]

[0085]

As described above, according to the present invention, a resin composite material having excellent mechanical properties can be provided. Further, it is possible to provide a method of manufacturing a resin composite material that can prevent deterioration of a polymer constituting the resin composite material during manufacturing.

[Brief description of the drawings]

FIG. 1 is a schematic view of a resin composite material according to an embodiment.

FIG. 2 is a schematic view of an organized clay in an embodiment.

FIG. 3 is an explanatory diagram showing a chemical formula of an organic agent used for producing the resin composite materials according to Samples 1 to 3 in the embodiment.

4A is a schematic diagram of an organized clay used in a conventional manufacturing method, and FIG. 4B is a schematic diagram of a resin composite material obtained by the conventional manufacturing method.

FIG. 5 is an explanatory view showing a structural example of an organic agent having a reactive group other than the terminal of the longest molecular chain according to the present invention.

FIG. 6 is an explanatory diagram showing a modified polymer which is an example of a polymer having a functional group according to the present invention.

FIG. 7 is an explanatory view showing a copolymer which is an example of a polymer having a functional group according to the present invention.

[Explanation of symbols]

 1. . . Resin composite materials,

Continued on the front page F-term (reference) 4J002 AC021 AC061 AC111 BB031 BB051 BB121 BB151 BB171 BB181 BB211 BC031 BC051 BF051 BG021 BG041 BG121 BN051 BN061 CB001 CC031 CC161 CC181 CD001 CF061 CL071 CL081 CF071 CF081 CF071 CP011 CP031 DJ006 EN137 EV087 FB086 GN00 GQ00

Claims (4)

[Claims] 1. A resin composite material comprising a polymer and an organized clay, wherein an organic substance contained in the organized clay is bonded to the clay other than at the end of the longest molecular chain. 2. The resin composite material according to claim 1, wherein the organized clay is obtained by organizing the clay with an organic agent having a reactive group other than the terminal of the longest molecular chain. 3. The resin composite material according to claim 1, wherein the polymer is a modified polyolefin. 4. An organic agent having a reactive group at a position other than the terminal of the longest molecular chain is prepared, and an organic compounding step of organically converting the clay with the organic agent, and adding a polymer and / or a monomer to the clay. Mixing and / or polymerizing the clay with the polymer and / or monomer /
A method for producing a resin composite material, comprising performing a polymerization step.