JP3356026B2 - Resin composite - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composite for improving physical properties such as an elastic modulus.

[0002]

2. Description of the Related Art Conventionally, addition and mixing of clay have been studied in order to improve the mechanical properties of organic polymer materials. For example, there is a method of dispersing clay in a thermosetting polymer such as nylon, vinyl polymer, epoxy, or rubber (Japanese Patent Application Laid-Open No. 62-74957, Japanese Patent Application Laid-Open No.
198645, E.C. P. Giannelis et al. C
hem. Mater. 5,1694-1696 (199
3) etc.). These are a method of organizing clay with an organic onium ion and initiating polymerization of a monomer between clay layers, a method of incorporating clay into growing seeds, or a method of kneading clay with a polymer and inserting a polymer between layers.

[0003]

However, in the above-mentioned conventional clay composite materials, clay is not well compatible with non-polar polymers. Therefore, it is not easy to insert a non-polar polymer between clay layers to expand the layers. Therefore, it was difficult to uniformly disperse the clay in the non-polar polymer. Also, even when intercalating between clay layers, such as polystyrene, only about one layer can be intercalated, and there is a limit to interlayer swelling.

To cope with such a problem, as shown in FIG. 7 , we have organized clay 7 with organic onium ions 6 to form organized clay 3, which is converted to a polar group 910.
(Japanese Patent Application Laid-Open No. 8-333114).

An object of the present invention is to provide a resin composite material which can be easily compounded and which can produce a resin composite material having a wide range of application.

[0006] The first invention relates to two or more kinds of polymers and carbon.
More than 6 organic onium ions are on the surface of clay
By binding to consist the organized clay obtained by organizing, among the two or more polymers, at least one is intercalated clay layers of <br/> upper Symbol organoclay
And have a functional group capable of the organized clay
The amount of addition is 100 total weight of the above two or more polymers.
Relative to the amount unit, a 0.01 to 200 parts by weight, the
Two or more polymers are compatible with each other, and
A resin composite material that forms a lix (Claim 1) . In the second invention, two or more kinds of polymers and an organic onium ion having 6 or more carbon atoms are formed of clay.
Consists of a organophilic clay was organically modified by ionic bonding to the surface, among the two or more polymers, Intaka at least one is in the clay layers above Symbol organophilic clay
And have a functional group capable of rates, the organic
The amount of added clay is the sum of the above two or more polymers.
0.01 to 200 parts by weight based on 100 parts by weight , and the two or more polymers are incompatible and
A tree characterized by forming micelles with a matrix
It is a fat composite material (Claim 2).

In the resin composite materials of the first and second inventions, since at least one kind of polymer has a functional group, this functional group interacts with a hydrophilic organically modified clay to have a functional group. Organized clay is dispersed at the molecular level in the polymer.

[0008] The most characteristic feature of the first and second inventions is that the dispersion state of the organized clay changes depending on whether two or more polymers are compatible or incompatible with each other. It is in.

When two or more polymers are compatible as in the first invention, as shown in FIG. 1, a compatible matrix 81 in which these polymers A100 and B101 are compatible is formed. . In the compatible matrix 81, at least one kind of polymer has a functional group. Therefore, the functional group interacts with the hydrophilic organically-organized clay 3, and the organically-organized clay 3 is uniformly dispersed in the compatible matrix 81 at the molecular level.

On the other hand, when two or more types of polymers are incompatible as in the second invention, as shown in FIG.
Using one polymer A103 as matrix 821,
The other polymer B104 forms micelles 822 in the matrix 821. As a result, an incompatible matrix 82 composed of two or more incompatible polymers is formed. This state can be compared to a sea-island structure consisting of an "ocean" (matrix) and "islands" (micelles) floating within it.

In the incompatible matrix, at least one of the polymer forming the matrix and the polymer forming the micelle is
Having organophilic clay and the parent sum highly functional group. The functional group interacts with the organized clay, and the organized clay is dispersed at the molecular level in the polymer having the functional group.

Namely, as shown in FIG. 2 (A), when a polymer A103 constituting the matrix 821 in the incompatible matrix 82 has a functional group, wherein
As in the invention of Item 3 , the organized clay 3 is composed of a matrix 8
21.

Further, as shown in FIG. 2B, when both the polymer A103 constituting the matrix 821 and the polymer B104 constituting the micelle 822 have a functional group, the structure of claim 4 As in the invention, the organized clay 3 is dispersed in both the matrix 821 and the micelle 822.

As shown in FIG. 2C, when the polymer B104 forming the micelle 822 in the incompatible matrix 82 has a functional group ,
As in the invention, the organized clay 3 is dispersed in the micelle 822.

As described above, whether two or more kinds of polymers are compatible or incompatible, and in the latter case, the functional group is added to either the polymer constituting the matrix or the polymer constituting the micelle. The formation state changes the dispersion state (morphology) of the organized clay. Therefore, such a difference in the dispersion state greatly affects the physical properties of the resin composite material.

Next, the details of the resin composite material of the present invention will be described. As a polymer having a functional group, for example,
There are a copolymer having a functional group and a modified polymer obtained by introducing a functional group by modifying the polymer. First, a copolymer having a functional group will be described. As shown in FIG. 3, the copolymer having a functional group refers to a copolymer of a functional group monomer 11 having a functional group 10 and a monomer 12 copolymerizable with the functional group monomer 11.

Regarding the form of the copolymer, the form of distribution of the functional group monomer in the copolymer is not particularly limited.
As shown in FIG. 3, a random copolymer in which the functional group monomers 11 are distributed irregularly (randomly) (FIG. 3 (a))
Alternatively, the copolymer may be an alternating copolymer (FIG. 3 (c)) in which an oligomer comprising a functional group monomer and a copolymerizable oligomer are alternately bonded, and as shown in FIG. 3 (b). A plurality of functional group monomers 11 may be distributed continuously. Generally, as the amount of the functional group monomer in the copolymer increases, the blocking property necessarily increases. Also,
The copolymer may have a branched structure due to the presence of a monomer having two or more polymerizable groups.

The functional group may be any functional group capable of intercalating between clay layers. In order to determine whether intercalation can be performed between the clay layers, the functional group monomer and the organic clay are mixed, and the interlayer distance between the organic clays may be measured by X-ray diffraction. When intercalated, the interlayer distance of the organized clay increases.

For example, the functional groups capable of intercalating include acid anhydride groups, carboxylic acid groups, hydroxyl groups, thiol groups, epoxy groups, halogen groups, ester groups, amide groups,
Urea group, urethane group, ether group, thioether group,
Sulfonic acid group, phosphonic acid group, nitro group, amino group, urea group, ether group, thioether group, sulfonic acid group,
Phosphonic acid group, nitro group, amino group, oxazoline group,
Examples include functional groups such as imide groups, and aromatic rings such as benzene rings, pyridine rings, pyrrole rings, furan rings, and thiophene rings.

The functional group monomer is not particularly limited as long as it is a polymerizable monomer having the above functional group. The functional group is
One or more are present in the monomer. When two or more are present, the functional groups may be the same,
It may be different. For example, monomers having such a functional group include acrylic monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate, acrylic (meth) amide, methyl (meth) amide, and ethyl (meth) amide. Compounds having unsaturated carbon such as acrylamide, (meth) acrylic acid, maleic anhydride, maleimide, etc .; aromatic rings such as benzene, pyridine, thiophene, etc. such as styrene, vinylpyridine, vinylthiophene, etc. And the like. Further, the functional group monomer may be a monomer having two or more polymerizable groups (for example, vinyl group) in one molecule.

Examples of the monomer copolymerizable with the functional group monomer include a hydrocarbon compound having a double bond such as ethylene, propylene, butene and pentene, a hydrocarbon compound having a triple bond such as acetylene and propylene, or butadiene. It is a hydrocarbon compound having two or more conjugated unsaturated bonds such as isoprene, and may have a branched structure or a cyclic structure in these carbon chains.

The above-mentioned monomer may be an acrylic monomer such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, acryl (meth) amide, methyl (meth) amide in combination with a functional group monomer. , Acrylamide such as ethyl (meth) amide, and monomers having an aromatic ring such as styrene and methylstyrene. 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 larger interaction with the clay layer 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 clay layer 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.

Next, the modified polymer will be described. The modified polymer is a polymer 10 shown in FIG.
As shown in FIG. 4 (b), the functional group 10 was introduced into the side chain or main chain by the modification of No. 2. Examples of the polymer include polyethylene, polypropylene, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene copolymer, polybutadiene, polyisoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, and ethylene-propylene-diene copolymer. , Ethylene-butene-diene copolymer, butyl rubber, polystyrene, styrene-butadiene copolymer, styrene-hydrogenated butadiene copolymer, polyamide, polycarbonate, polyacetal, polyester, polyphenylene ether, polyphenylene sulfide, polyether sulfone, poly Ether ketone, polyarylate, polymethylpentene, polyphthalamide, polyethernitrile,
Polyether sulfone, polybenzimidazole, polycarbodiimide, polytetrafluoroethylene, fluororesin, polyamideimide, polyetherimide, liquid crystal polymer, epoxy resin, melamine resin, urea resin, diallyl phthalate resin, phenol resin, polysilane, poly Polymers such as siloxane, silicone resin and urethane resin can be used.

The functional group introduced by the modification may be any functional group capable of intercalating between the clay layers. In order to determine whether or not intercalation can be performed between the clay layers, 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. When intercalated, the interlayer distance between the organized clays increases. Examples of the functional group include an acid anhydride group, a carboxylic acid group, a hydroxyl group, a thiol group,
Functional groups such as epoxy group, halogen group, ester group, amide group, urea group, urethane group, ether group, thioether group, sulfonic acid group, phosphonic acid group, nitro group, amino group, oxazoline group, or benzene ring, pyridine It is preferable to use an aromatic ring such as a ring, a pyrrole ring, a furan ring, and a thiophene ring, but it is not limited thereto. This further improves the dispersibility of the organized clay in the modified polymer. In the case of polymers having functional groups such as polystyrene, the functional groups introduced by modification are
It is preferable to use one having a greater interaction with the clay layer.

Next, the combination of two or more polymers will be described in detail for the case where the polymers are compatible and the case where the polymers are incompatible. When the polymers are compatible, the two or more polymers are not particularly limited as long as they are compatible with each other, and for example, the following combinations are available. First, the combination of the polymer having a functional group and the other polymer preferably has the same or similar main chain structure. Thereby, two or more kinds of polymers are easily compatible with each other. Specifically, a combination of the above modified polymer and an unmodified polymer can be considered. However, in this case, care must be taken because if the amount of modification of the modified polymer is too large, it becomes incompatible. Since the amount of modification of the modified polymer varies depending on the type of the polymer, it is not particularly limited. As a combination of an unmodified polymer and a modified polymer, for example, polyethylene (hereinafter, referred to as P)
E. ) And modified PE, polypropylene (hereinafter referred to as PP)
That. ), Modified PP, ethylene propylene rubber (hereinafter referred to as EPR), modified EPR, and the like, but are not limited thereto.

Second, as a combination of a polymer having a functional group and another polymer, one polymer is
There are combinations of the polymer with other polymers that have the same constituent parts. As this combination, there is a combination of a copolymer having the above functional group and a polymer compatible with the copolymer, and specific examples thereof include, for example, an ethylene-acrylic acid copolymer and PE, -But not limited to, methyl acrylate copolymer and PE. However, also in this case, it is necessary to be careful because if the amount of a different monomer such as acrylic acid or methyl acrylate is too large, it becomes incompatible. The amount of the different types of monomers is not particularly limited because there is a difference depending on the type of the polymer.

Third, there is no problem if the polymer having a functional group and the other polymer have compatibility even if the structure of the main chain is different. For example, polyphenylene oxide (hereinafter referred to as PPO) and polystyrene, polystyrene and polyvinyl methyl ether, polyvinyl chloride and polycaprolactone, PMMA (polymethyl methacrylate) and polyvinylidene fluoride, polycarbonate and MMA (methyl methacrylate) copolymer And so on.

When the polymers are incompatible, the two or more polymers are not particularly limited as long as they are not compatible with each other. For example, there are the following combinations. As a combination of a polymer having a functional group and another polymer, for example, one of the above-mentioned copolymer or the above-mentioned modified polymer having a functional group and the other is a combination of a polymer which is not compatible with these polymers. is there.

Examples of the polymer incompatible with the above-mentioned copolymer and the modified polymer include polyethylene, polypropylene, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene copolymer, polybutadiene, polyisoprene, and the like. Hydrogenated polybutadiene, hydrogenated polyisoprene, ethylene-propylene-diene copolymer, ethylene-butene-diene copolymer, butyl rubber, polystyrene, styrene-butadiene copolymer, styrene-hydrogenated butadiene copolymer, polyamide,
Polycarbonate, polyacetal, polyester, polyphenylene ether, polyphenylene sulfide,
Polyethersulfone, polyetherketone, polyarylate, polymethylpentene, polyphthalamide, polyethernitrile, polyethersulfone, polybenzimidazole, polycarbodiimide, polytetrafluorinated ethylene, fluororesin, polyamideimide, polyether Imide, liquid crystal polymer, epoxy resin, melamine resin,
Examples include, but are not limited to, polymers such as urea resins, diallyl phthalate resins, phenolic resins, polysilanes, polysiloxanes, silicone resins, urethane resins, and the like.

In both cases of compatibility and incompatibility,
The functional group may be formed on any of the two or more polymers. In the case of compatibility and incompatibility, the number average molecular weight of the polymer is between 5,000 and 10,000,000.
It is preferable that If it is less than 5,000, the mechanical properties of the resin composite material may be reduced. Also,
If it exceeds 10,000,000, a problem may occur in the workability of the resin composite material. More preferably,
The number average molecular weight of the polymer is between 10,000 and 1,000.
It is 0000. Thereby, the mechanical properties and workability of the resin composite material are further improved.

As shown in FIG. 5, the organized clay 3 is
The clay is organized by the organic onium ions 6 ion-bonding to the surface of the clay 7. Clay is organically formed by ionic bonding with an organic onium ion having 6 or more carbon atoms . When the number of carbon atoms is less than 6, the hydrophilicity of the organic onium ion is increased, and the compatibility with the polymer may be reduced. Examples of the organic onium ion include hexyl ammonium ion, octyl ammonium ion, 2-ethylhexylammonium ion, dodecyl ammonium ion, lauryl ammonium ion, octadecyl ammonium ion,
Stearyl ammonium ion, dioctyl dimethyl ammonium ion, trioctyl ammonium ion,
Distearyl dimethyl ammonium ion or ammonium laurate ion can be used.

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

Examples of the clay include smectite clays such as montmorillonite, saponite, hectorite, beidellite, stevensite, and nontronite, vermiculite, halloysite, and mica. It may be natural or synthetic.

It is preferable that the organic onium ion is used in an amount of 0.3 to 3 equivalents of the ion exchange capacity of the clay. 0.3
If it is less than the equivalent, it may be difficult to swell between the clay layers, and if it exceeds 3 equivalents, it may cause deterioration of the polymer and cause coloring of the resin composite material.
More preferably, the organic onium ion is used in an amount of 0.5 to 2 equivalents of the ion exchange capacity of the clay. Thereby, the clay layers can be further swollen, and the deterioration and discoloration of the resin composite material can be further prevented.

The added amount of the organized clay is 0.01 to 200 parts by weight based on 100 parts by weight of the total amount of two or more polymers.
Parts by weight . Thereby, the mechanical strength of the resin composite material is improved. On the other hand, when the amount is less than 0.01 part by weight, there is a possibility that the mechanical strength is not improved by the addition of the organized clay. If it exceeds 200 parts by weight,
There is a possibility that the viscosity of the resin composite material becomes too high and the moldability decreases.

Further, the amount is preferably 0.1 to 100 parts by weight. Thereby, a resin composite material having a balance between mechanical properties and moldability can be obtained. In particular, it is preferably 0.1 to 30 parts by weight.

Organized clay is one of the copolymers.
It is preferable that the particles are dispersed in a size of μm or less. Thereby, the mechanical properties of the resin composite material are improved. Further, it is preferable that the polymer intervenes (intercalates) between the clay layers. This increases the interface between the clay surface and the polymer, increasing the effect of the clay reinforcing the polymer. The term “intercalate” refers to a state in which the interlaminar distance between the organized clay and the polymer is larger than the interlaminar distance between the organized clays before the complexation. This state can be observed by, for example, X-ray diffraction.

It is preferable that the interlaminar distance between the organic clay is increased by 10 ° or more after the composite with the polymer than before the composite. More preferably, the interlayer distance is increased by 30 ° or more. Particularly preferably, it is enlarged by 100 ° or more. Thereby, the ratio of the polymer restricted by the organized clay is increased, and the reinforcing effect of the organized clay is increased.

It is particularly preferable that the layer structure of the organic clay is lost and the molecule is dispersed in a single layer. Thereby, the ratio of the polymer restricted by the organized clay is further increased, and the reinforcing effect of the organized clay is increased. However, even in this case, the physical properties of the resin composite material do not deteriorate.
In the range, several layers may be present in a laminated state.

Next, as a method for producing the above resin composite material, for example, there is a method of mixing two or more kinds of polymers with an organized clay. The order of mixing may be such that the organically modified clay and two or more polymers are simultaneously mixed, or the polymer and the organically modified clay may be mixed in any order.

This mixing is performed, for example, in a solvent such as an organic solvent or oil, and then by removing the solvent. Thereby, the dispersibility of the organized clay is improved.
Further, the above mixing is performed by heating the copolymer and the organized clay above the softening point and melting point of the polymer. More preferably, a shear force is applied at this time. Thereby, the organized clay can be uniformly dispersed in the polymer. In particular, it is preferable to perform melt-kneading while applying a shearing force using an extruder.

By carrying out this production method, the organized clay is finely dispersed in the polymer having a functional group. Further, a resin composite material having excellent mechanical strength, particularly mechanical properties such as elastic modulus can be obtained.

The reason is considered as follows. That is, the polymer having a functional group enters between the layers of the organized clay by adding and mixing the organized clay having the layer structure. Since the functional groups of the polymer have a high affinity for the clay surface, the polymer remains stably between the layers of the organized clay. As a result, an interlayer compound in which the polymer intervenes between the layers of the organized clay is obtained. In addition, the organized clay is dispersed at the molecular level due to the shearing force applied during melt-kneading.

Examples of uses of the resin composite material of the present invention include an injection molded product, an extruded product, and a film material.

[0046]

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiment 1 FIG. 2 shows a resin composite material according to an embodiment of the present invention.
This will be described with reference to FIG. The resin composite of this example is composed of two or more polymers and an organized clay. One of the two polymers is a polymer having a functional group and the other is a polymer having no functional group, and both polymers are incompatible.

Next, the resin composite of this embodiment will be described. Preparation of Organized Clay First, Na-montmorillonite (trade name: Knipia F) manufactured by Kunimine Industries was prepared as a layered clay mineral. Na
-80 g of montmorillonite, 5000 ml of water at 80 ° C.
Was dispersed. 28.5 g of stearylamine and 11 ml of concentrated hydrochloric acid were dissolved in 2000 ml of water at 80 ° C., and this solution was added to the above Na-montmorillonite dispersion.
The resulting precipitate was filtered, washed three times with water at 80 ° C., and freeze-dried to obtain montmorillonite organically treated with stearyl ammonium. Hereinafter, this is abbreviated as C18-Mt. C18-M determined by the scuffing method
The inorganic content in t was 68%. The C18-Mt interlayer distance determined by the X-ray diffraction method was 22 °.

Preparation of Polymer Next, as a polymer having a functional group, modified EPR
(Mitsui Petrochemical Co., Ltd., trade name: Tuffmer MP0610,
Hereinafter, this is referred to as modified EPR. ) Was prepared. Modified EP
The amount of modification of R with maleic anhydride is 0.04 mmol
/ G. On the other hand, as a polymer having no functional group, homo PP (trade name: MA2, manufactured by Mitsubishi Chemical Corporation, hereinafter referred to as homo PP) was prepared.

Preparation of Resin Composite Material Next, homo PP (700 g), modified EPR (300
g) and C18-Mt (15 g) were melt-kneaded at 200 ° C. using a twin-screw extruder. Thus, a resin composite material of this example was obtained.

Next, regarding the obtained resin composite material, C1
The dispersion state of 8-Mt was observed. As the observation method, the resin composite material of this example was molded, a test piece was formed, and the dispersed state of clay (montmorillonite) was observed using visual observation, an optical microscope, and a transmission electron microscope.

As a result, as shown in FIG. 2C, one polymer, homo-PP, constituted the matrix 821 and the other polymer, modified EPR, formed micelles 822 in the matrix 821. . The state consists of the "sea" (matrix) and the "island" floating in it.
It can be compared to the sea-island structure consisting of (micelles).
This sea-island structure is formed because homo-PP and denatured EPR are incompatible, and congruent with each other.

The organic clay 3 was dispersed in the micelles 822 in the incompatible matrix 82. This is because the polymer (modified EP)
R) has an organically modified clay and a highly hydrophilic functional group (maleic anhydride group). Therefore, it is considered that this functional group interacts with the organized clay and the organized clay (C18-Mt) is dispersed in the micelle formed of the polymer having the functional group.

Embodiment 2 The resin composite material of this example is a polymer having no functional group, which is a butyl rubber (Nippon Synthetic Rubber Co., trade name; Butyl).
268). That is, this butyl rubber (600 g) was melt-kneaded at 120 ° C. using a biaxial kneader with the modified EPR (400 g) and C18-Mt (15 g) used in Example 1. The amount of the modified EPR modified with maleic anhydride was 0.04 mm.
ol / g. Thus, a resin composite material of this example was obtained.

The dispersion state of C18-Mt in the obtained resin composite material was observed in the same manner as in Example 1. Also,
FIG. 6 shows an SEM (Electron Scanning Microscope) photograph of the resin composite material. As can be seen from this photograph, butyl rubber and modified EPR are incompatible and have a sea-island structure. Only in the modified EPR corresponding to the island (micelle), C
18-Mt was dispersed on the order of nanometer (see FIG. 2 (C)). The black part is denatured E in the same photograph.
The PR phase.

Embodiment 3 The resin composite material of this embodiment was prepared using maleic anhydride-modified PP and EPR as two incompatible polymers. As the maleic anhydride-modified PP, PO1015 manufactured by Exxon was used. Hereinafter, this is referred to as modified PP. The amount of the modified PP modified with maleic anhydride was 0.02 mmol / g. In addition, EPR
Was used as Sumitomo Chemical V0131.

In producing the resin composite material, the modified PP (700 g) and EPR (300 g) were added together with C18-Mt (35 g) used in the first embodiment,
Melt kneading was performed at 200 ° C. using a biaxial kneader.

The dispersion state of C18-Mt in the obtained resin composite material was observed in the same manner as in Example 1. As a result, the resin composite material formed the incompatible matrix 82 shown in FIG. The modified PP is a matrix 82
1 and the EPR formed micelles 822. And
C18-Mt, which is the organized clay 3, is composed of matrix 8
No. 21 was dispersed in the modified PP phase in the order of nanometer.

Embodiment 4 The resin composite material of this embodiment is manufactured by using modified PP and modified EPR as two kinds of incompatible polymers. As the modified PP, the modified PP used in Example 3 was used.
(Trade name: PO1015 manufactured by Exxon) was used. As the modified EPR, the modified EPR used in Example 1 (trade name: Tuffmer MP0610, manufactured by Mitsui Petrochemical Co., Ltd.) was used. Both the modified PP and the modified EPR have a maleic anhydride group. Maleic anhydride modification amount is modified PP
Is 0.02 mmol / g and the modified EPR is 0.04 mmol / g.
mmol / g.

In manufacturing the resin composite material, the above-mentioned modified PP (700 g) and modified EPR (300 g) were used.
The mixture was melt-kneaded with C18-Mt (35 g) used in the first embodiment at 200 ° C. using a biaxial kneader.

The dispersion state of C18-Mt in the obtained resin composite material was observed in the same manner as in Example 1. As a result, as shown in FIG. 2 (B), the two types of polymers composed of the modified PP and the modified EPR are incompatible with each other.
Had formed. The modified PP formed the matrix 821, and the modified EPR formed the micelle 822. Then, C18-Mt as the organized clay 3 is added to the matrix 82
1 and a modified EP as micelle 822
Both of the R phases were dispersed on the order of nanometers.

Embodiment 5 The resin composite material of this embodiment is produced using polystyrene and styrene copolymer as compatible polymers. Polystyrene is a polymer without functional groups,
Topolene (trade name, manufactured by Mitsui Toatsu) was used. As the styrene copolymer, a styrene-vinyloxazoline copolymer manufactured by Nippon Shokubai (trade name: Epicross RPS-1005) was used. Oxazoline (functional group) of this styrene copolymer
The content is 5% by weight.

As the organic clay, montmorillonite organically treated with trimethylstearylamine as an organic agent was used. The details of the production method are as follows. First, as a layered clay mineral, Kunimine Industries Na
-Montmorillonite (trade name: Knipia F) was prepared. 80 g of Na-montmorillonite is added to 50 ° C. of water at 80 ° C.
Dispersed in 00 ml. 36.8 g of trimethylstearyl ammonium chloride was added to 2000 ml of water at 80 ° C.
And this solution was added to the above Na-montmorillonite dispersion. The resulting precipitate is filtered,
The resultant was washed three times with water at 80 ° C. and freeze-dried to obtain montmorillonite organically treated with trimethylstearylamine. Hereinafter, it is abbreviated as C18TM-Mt. The inorganic content in C18TM-Mt determined by the scuffing method was 66%. The interlayer distance of C18TM-Mt determined by the X-ray diffraction method was 22 °.

In producing the resin composite material of this example, the polystyrene (600 g) and the styrene copolymer (400 g) were melt-kneaded at 150 ° C. using a biaxial kneader together with the C18TM-Mt.

The dispersion state of C18TM-Mt in the obtained resin composite material was observed in the same manner as in Example 1. As a result, as shown in FIG. 1, two kinds of polymers 100 and 101 composed of polystyrene and styrene copolymer were obtained.
Were co-solved to form a compatible matrix 81. C18TM-Mt, which is the organized clay 3, was uniformly dispersed in the compatible matrix 81 on the order of nanometers.

Embodiment 6 The resin composite of this embodiment is manufactured using PPO and a styrene copolymer as compatible polymers. PP
O is a polymer having a functional group, and PPO5 manufactured by GE
34 was used. As the styrene copolymer, a styrene-vinyl oxazoline copolymer having a functional group (manufactured by Nippon Shokubai, trade name; Epicross RPS-1005, oxazoline (functional group) content; 5% by weight) was used.

In manufacturing the resin composite material of this example, the PPO (850 g) and the styrene copolymer (150 g) were used in the C18TM-M
Along with t (35 g), the mixture was melt-kneaded at 150 ° C. using a biaxial kneader.

The dispersion state of C18TM-Mt was observed for the obtained resin composite in the same manner as in Example 1. As a result, as shown in FIG. 1, the PPO and the styrene copolymer were co-dissolved to form a compatible matrix 81. C18TM-Mt, which is the organized clay 3, was uniformly dispersed in the compatible matrix 81 on the order of nanometers.

Comparative Example 1 The resin composite material of this example was produced using two types of polymers each having no functional group. The two types of polymers are homo PP (trade name; MA2, manufactured by Mitsubishi Chemical Corporation) and EP
R (Sumitomo Chemical, trade name: V0131). In manufacturing the resin composite material of this example, homo PP (700
g) and EPR (300 g) were melt-kneaded with C18-Mt (35 g) used in Embodiment 1 at 200 ° C. using a biaxial kneader.

The dispersion state of C18-Mt in the obtained resin composite material was observed in the same manner as in Example 1. As a result, the homo PP and the EPR formed an incompatible matrix. Among the incompatible matrices, C18-M
t was not finely dispersed. Between the layers of C18-Mt,
Neither homo-PP nor EPR was intercalated.

[0070]

According to the present invention, it is possible to provide a resin composite material which can be easily formed into a composite and which can produce a resin composite material having a wide range of application.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing compatible polymers A and B in the present invention (FIG. 1 (a)), and an explanatory view showing a dispersed state of an organized clay in a compatible matrix (FIG. 1).
(B)).

FIG. 2 is an explanatory view showing incompatible polymers A and B (FIG. 2 (O)), and an explanatory view showing a dispersed state of an organized clay in an incompatible matrix (FIG. 2).
(A, B, C)).

FIG. 3 is an explanatory view of a random copolymer (FIG. 3 (a)) and an explanatory view of an alternating copolymer (FIG. 3) in the present invention.
(B)).

FIG. 4 is an explanatory view of a polymer according to the present invention (FIG. 4).
(A)) and an explanatory view of a modified polymer (FIG. 4 (b)).

FIG. 5 is an explanatory view of an organized clay in the present invention.

FIG. 6 is a drawing substitute photograph (magnification: 30,0) composed of a microscopic photograph of the structure of the resin composite material showing the dispersion state of the organized clay in the incompatible matrix in Embodiment 2.
00 times).

FIG. 7 is an explanatory view of a resin composite material in a conventional example.

[Explanation of symbols]

 10. . . Functional group, 11. . . 11. functional group monomers, . . Monomer, 100, 103. . . Polymer A, 101, 104. . . 2. polymer B, . . 5. Organized clay, . . 6. organic onium ions, . . Clay, 81. . . 82. compatible matrix, . . Incompatible matrix, 821. . . Matrix, 822. . . Micelle,

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yumitsu Usuki 41-1, Oku-cho, Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture Inside Toyota Central Research Laboratory Co., Ltd. (56) References JP-A-8-134155 JP-A-3-62846 (JP, A) WO 97/31057 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00 -13/08

Claims (5)

(57) [Claims] Claims: 1. A polymer comprising two or more polymers.With 6 or more carbon atoms
Of onium ions on the surface of clay
Organized byConsisting of organically modified clay, at least one of the above two or more polymersRecord
Intercalating between clay layers of organic clay
CanHas functional groupAnd The added amount of the above-mentioned organically modified clay should be
0.01 to 200 weight per 100 parts by weight of total
Quantity AndThe two or more polymers are compatible with each other,
Resin composite characterized by forming a matrix
Wood. 2. A polymer comprising two or more polymersWith 6 or more carbon atoms
Of onium ions on the surface of clay
Organized byConsisting of organically modified clay, at least one of the above two or more polymersRecord
Intercalating between clay layers of organic clay
CanHas functional groupAnd The added amount of the above-mentioned organically modified clay should be
0.01 to 200 weight per 100 parts by weight of total
Quantity AndThe above two or more polymers are incompatible and
Resin composite characterized by forming micelles with micelles
Wood. 3. The method according to claim 2, wherein the matrix is
The formed polymer has affinity with the above-mentioned organic clay.
It has high functional groups, and the functional groups interact with the organic clay.
The polymer forming the matrix
The above-mentioned organic clay is dispersed at the molecular level.
It is characterized by the fact that clay is not dispersed in the micelle
Resin composite. 4. The method according to claim 2, wherein the matrix is
The polymer forming and the polymer forming the micelle
The rimer has a functional group with high affinity to the above-mentioned organized clay.
And the functional group interacts with the organized clay,
The polymer forming the matrix and the micelles
Organized clay is at the molecular level in the polymer being formed
Resin composite material characterized by being dispersed in. 5. The method according to claim 2, wherein the micelle is formed.
The polymer that is used has a high affinity with the above-mentioned organic clay.
Functional group, and the functional group interacts with the
The polymer forming the micelles
Rays are dispersed at the molecular level, while the matrix
Resin is characterized in that clay is not dispersed in
Mixture.