JPH11181309A - Resin composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composite material excellent in mechanical strength. SOLUTION: This material comprises an organically modified clay 70 desirably being a clay mineral (e.g. montmorillonite, vermiculite, or mica) to the surface of which 6C or higher organo onium ions (e.g. octylammonium ions or stearylammonium ions) are ionically bonded, a functional-group-containing polymer 1, another polymer 3, and a crosslinking agent 2. The functional-group- containing polymer has been crosslinked with a crosslinking agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composite material having excellent mechanical strength.

[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.
Chem. Mater. 5,1694-1696 (19
93) etc.). These are methods of organizing clay with organic onium ions to initiate polymerization of monomers between clay layers,
This is 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 poorly 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. Further, 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. 8, we have organized the clay 7 with an organic onium ion 6 to form an organized clay 3, which is converted into a polar group 910.
(JP-A-8-333114).

[0005]

However, in the above-mentioned conventional resin composite material, the organized clay in the polymer 9 may be a starting point for destruction. That is, when an external force is applied to the resin composite material, stress concentrates around the organized clay,
Cracks may occur at the interface between the organized clay and the polymer, or cracks may occur in the polymer around the organized clay, and in some cases, the resin composite may break. Therefore, it is necessary to strengthen the area around the organized clay, which is the starting point of fracture, and to improve the mechanical strength of the resin composite material.

The present invention has been made in view of the above problems, and has as its object to provide a resin composite material having excellent mechanical strength.

[0007]

According to the present invention, there is provided a functional group-containing polymer comprising an organic clay, two or more polymers, and a crosslinking agent, wherein at least one of the two or more polymers has a functional group. The functional group-containing polymer is a resin composite material which is crosslinked by the crosslinking agent.

The operation and effect of the present invention will be described.
The functional group-containing polymer has a functional group. This functional group has a higher affinity for the organized clay than the other polymer parts of the functional group-containing polymer. Due to the affinity between the functional group and the organized clay, the functional group-containing polymer intercalates between the clay layers of the organized clay.

Further, even when the clay is dispersed in the polymer, the functional group-containing polymer comes close to the organized clay due to the presence of the functional group having a high affinity for the organized clay. For this reason, the functional group-containing polymer surrounds the periphery of the organized clay in a state where the functional groups are brought close to the organized clay as described above.

Further, since the functional group-containing polymer in the vicinity of the organic clay is cross-linked by a cross-linking agent, the functional group-containing polymer has a high molecular weight and is strengthened. Therefore, even if stress is concentrated on the organized clay by applying an external force to the resin composite material, generation of cracks at the interface between the organized clay and the polymer and generation of cracks in the polymer around the organized clay can be prevented. In addition, destruction of the resin composite can be prevented. Therefore, a resin composite material having excellent mechanical strength can be obtained.

Next, the details of the present invention will be described. (Polymer) resin composite materials contain at least two or more polymers. At least one of them is a functional group-containing polymer containing a functional group.

(Functional Group-Containing Polymer) The functional group-containing polymer is a polymer having a functional group. Examples of the functional group-containing polymer include (1) a modified polymer (FIG. 1) and (2) a copolymer (FIG. 2).

(1) Modified Polymer As shown in FIG. 1, the modified polymer has a functional group 10 introduced into its side chain and / or main chain by modification of the polymer 102. 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,
Polyethersulfone, polyetherketone, polyarylate, polymethylpentene, polyphthalamide, polyethernitrile, polyethersulfone, polybenzimidazole, polycarbodiimide, polytetrafluoroethylene, fluororesin, polyamideimide, polyether Imide, liquid crystal polymer, epoxy resin, melamine resin,
Polymers such as urea resin, diallyl phthalate resin, phenol resin, polysilane, polysiloxane, 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 between the organized clays may be measured by X-ray diffraction. When intercalated, the interlayer distance of the organized clay increases.

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,
There are functional groups such as a halogen group, an ester group, an amide group, a urea group, a urethane group, an ether group, a thioether group, a sulfonic acid group, a phosphonic acid group, a nitro group, an amino group, an oxazoline group, an imide group, and an isocyanate group.

The functional group (2) having π electrons includes, for example, 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. When the charged organically modified clay approaches the π electrons on the aromatic ring, the π electrons are biased due to the charge, and polarization is induced in the aromatic ring. for that reason,
The aromatic ring serves as a functional group effective for intercalation between the clay layers. In the case of a polymer having a functional group such as polystyrene, it is preferable to use a functional group having a larger interaction with the clay layer as the functional group introduced by modification.

The amount of the functional group introduced into the polymer is 0.0
It is preferably from 0.01 to 1 mmol / g (equivalent to 0.01 to 10% by weight when the functional group is converted to maleic anhydride). This makes it possible to finely disperse the organized clay while maintaining the physical properties of the polymer. on the other hand,
If the amount is less than 0.001 mmol / g, the polymer cannot intervene between the clay layers, and the organic clay may not be finely dispersed. If it exceeds 1 mmol / g,
When the polymer is modified, the polymer chain may be cut or cross-linked, so that the physical properties of the polymer may not be maintained.

More preferably, for the same reason as above, the amount of the functional group introduced into the polymer is 0.005 to 0.005.
0.5 mmol / g (corresponding to 0.05 to 5% by weight when the functional group is converted to maleic anhydride). However,
If the polymer is a less polar polyolefin,
If the amount of the functional group is too large, the compatibility with the polymer having no functional group may decrease.

The number average molecular weight of the polymer is from 5,000 to
Preferably it is 10,000,000. 5,000
If it is less than 0, the mechanical properties of the resin composite material may be reduced. If it exceeds 10,000,000, a problem may occur in the workability of the resin composite material.

More preferably, for the same reason as above, the number average molecular weight of the polymer is from 10,000 to 1,0.
00,000. Particularly preferably, the number average molecular weight of the polymer is between 100,000 and 1,000,000. Thereby, the mechanical properties and workability of the resin composite material can be further improved.

[0021]

As a method for modifying the polymer, a known method can be used and is not particularly limited. For example, a polymer is dissolved in a solvent, and a functional group is introduced into the polymer by a reaction with a reactant (modifier). At this time, a method using a radical initiator such as a peroxide can be used.

Alternatively, the polymer is melted by a kneader, an extruder, or the like, a compound having a functional group is added, and the functional group is introduced into the polymer. At this time, if a radical initiator such as a peroxide coexists, it can be efficiently introduced. At this time, the amount of the modifier not bound to the polymer is preferably smaller.

(2) Copolymer As shown in FIG. 2, the copolymer 1 having the functional group 10 is
It 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.

With respect to the form of the copolymer, there is no particular limitation on the form of distribution of the functional group monomer in the copolymer. As shown in FIG. 2, a random copolymer in which the functional group monomers 11 are randomly (randomly) distributed in the copolymer 1 (FIG. 2).
(A)), or a plurality of functional group monomers 11 may be distributed in a row as shown in FIG. 2 (b), and furthermore, an alternating copolymer in which functional group monomers and copolymerizable monomers are alternately bonded. It may be united (FIG. 2C). Generally, as the amount of the functional group monomer in the copolymer increases, the blocking property necessarily increases. 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 copolymer may be any functional group capable of intercalating between the clay layers, similarly to the modified polymer. ) Some have π electrons. Specific examples thereof include those similar to the above-mentioned modified polymers.

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, propyl (meth) acrylate, (meth) acrylamide, methyl (meth) acrylamide, ethyl (meth) acrylamide, Acrylamides such as dimethyl (meth) acrylamide and diethyl (meth) acrylamide; compounds having an unsaturated carbon such as (meth) acrylic acid, maleic anhydride, and maleimide; styrene, vinylpyridine,
Benzene ring, pyridine ring,
Examples include monomers having an aromatic ring such as 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 content of the functional group monomer is preferably 0.01 to 50 mol% in the copolymer. Thereby, the organized clay can be finely dispersed in the copolymer. When the amount is less than 0.01 mol%, the organic clay may not be finely dispersed. In addition, 50mol%
If it exceeds 3, the organic clay may not be finely dispersed.

More preferably, the content of the functional group monomer is 0.05 to 50 mol% in the copolymer.
Particularly preferably, it is 0.05 to 40 mol%, particularly preferably 0.05 to 30 mol%. Thereby, the organic clay can be more finely dispersed.

Examples of the monomer copolymerizable with the functional group 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 propyne; 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 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 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.

As the method for producing the copolymer, an existing method can be used, and there is no particular limitation. For example, when a vinyl monomer is used, a desired copolymer can be obtained by radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, or the like.
When radical polymerization is used, there are methods such as bulk polymerization, emulsion polymerization, suspension polymerization, and high-pressure polymerization. In coordination polymerization, for example, a copolymer of a functional group monomer and a non-polar monomer is obtained by a method as described in WO 96/23010.

The copolymer has a number average molecular weight of 5,
It is preferably from 000 to 10,000,000.
This facilitates the processing of the composite resin material and improves the mechanical properties. On the other hand, 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 molecular weight of the copolymer is 10,000 to 1,000,000 in number average molecular weight, and particularly preferably 100,000 to 1,000,000.
0. This further improves the workability and mechanical properties of the resin composite.

The compounding ratio of the functional group-containing polymer is preferably 50 parts by weight or more based on 100 parts by weight of the organized clay. Thereby, the protection effect of the organically modified clay by the functional group-containing polymer is enhanced, and the mechanical strength of the resin composite material is increased. If the amount is less than 50 parts by weight, the protective effect of the above-mentioned organized clay may be reduced.

(Other Polymers) The polymer other than the functional group polymer is not particularly limited, but is preferably compatible with the functional group polymer. In this case, a completely compatible system or a partially compatible system may be used.

(Crosslinking Agent) The crosslinking agent is a compound having two or more reaction points capable of reacting with a functional group of a functional group-containing polymer or other reactive groups. The term "having two or more reaction points" refers to a compound having two or more groups 20 capable of reacting with a functional group-containing polymer as shown in FIG.
(A)) or a compound having a group capable of reacting two or more times with one group. As an example of the latter, as shown in FIG. 3 (b), when the functional group-containing polymer is a halogen compound, there is a case where an amine which is a group capable of reacting with the halogen group more than once is used as a crosslinking agent. .

Suitable types of the cross-linking agent vary depending on the type of the functional group in the functional group-containing polymer or other types of reactive groups, and cannot be determined unequivocally, and their combination is important. For example, when the functional group in the functional group-containing polymer is an acid anhydride group, a carboxylic acid, or an ester group, two or more groups such as a hydroxyl group, a thiol group, and an amino group that can react with these groups are used as the crosslinking agent. Compounds. When the functional group in the functional group-containing polymer is a hydroxyl group or a thiol group, examples of the crosslinking agent include compounds having two or more groups such as an acid anhydride group, a carboxylic acid group, and an isocyanate group capable of reacting with these groups. Can be The reactive groups in the crosslinking agent may be the same or different.

Examples of the compound having two or more hydroxyl groups include ethylene glycol, glycerin, and di (hydroxymethyl) benzene, and a phenolic compound directly substituted on a benzene ring may be used. Examples of the compound having two or more thiol groups include 1,
Examples thereof include 2-ethylenedithiol and 1,3-prodithiol, and those directly substituted on a benzene ring may also be used.

Examples of the compound having two or more aminos include 1,2-diaminoethane, 1,3-diaminopropane and di (aminomethyl) benzene, and those directly substituted on the benzene ring. Is also good.

Examples of the compound having two or more acid anhydride groups include pyromellitic dianhydride.
As the compound having two or more carboxylic acids,
Examples thereof include 1,2-ethylenedicarboxylic acid, 1,3-prodicarboxylic acid, phthalic acid, trimesic acid, and pyromellitic acid.

Examples of the compound having two or more isocyanate groups include 1,2-ethylene isocyanate,
Examples include 1,3-prodiisocyanate, di (isocyanomethyl) benzene, diisocyanobenzene, tri (isocyanomethyl) benzene, and triisocyanobenzene. The various compounds described above are examples, and the present invention is not limited to these.

The molecular weight of the crosslinking agent is not particularly limited. The crosslinker may be an oligomer or polymer having two or more reactive sites capable of reacting with functional groups or other groups in the functional group-containing polymer. Of course, it may be a low molecular weight compound.

The crosslinking agent is preferably used in a molar ratio of 0.01 to 10.0 with respect to the amount of the functional group in the functional group-containing polymer. As a result, the functional group-containing polymer can be efficiently cross-linked, and the effect of protecting the organically modified clay by the functional group-containing polymer is enhanced. On the other hand, if it is less than 0.01%, the amount of the non-crosslinked functional group-containing polymer increases, and the effect of suppressing the destruction around the organized clay may be reduced. On the other hand, if it exceeds 10.0, the viscosity may be excessively increased and workability may be deteriorated.

More preferably, the crosslinking agent is used in a molar ratio of 0.1 to 5.0 with respect to the amount of the functional group in the functional group-containing polymer.
It is preferred that Thereby, the functional group-containing polymer can be crosslinked more efficiently, and the effect of suppressing destruction around the organized clay can be further enhanced.

(Crosslinking) The functional group-containing polymer is crosslinked by a crosslinking agent. Here, "crosslinking" refers to crosslinking a functional group-containing polymer to increase the molecular weight. Although the functional group-containing polymer has a functional group, the functional group-containing polymer may have a group other than the functional group, which can react with a crosslinking agent, in a main chain or a side chain. Also, when the functional group is a group having low reactivity (for example, polystyrene), the cross-linking agent mainly reacts with the functional group, but sometimes reacts with other reactable groups side by side. Therefore, as shown in FIGS. 4A to 4C, the crosslinking of the functional group-containing polymer 1 by the crosslinking agent 2 can take the following various forms, for example.

(1) Functional group 10 of functional group-containing polymer 1
And the functional groups 10 of the other functional group-containing polymer 1 are crosslinked. (2) When the functional group 10 of the functional group-containing polymer 1 and the reactive group 19 of another functional group-containing polymer 1 are crosslinked. (3) A case where the reactive group 19 of the functional group-containing polymer 1 and the reactive group 19 of another functional group-containing polymer 1 are crosslinked.

Among the above (1) to (3), (1) is a cross-linked form when the functional group-containing polymer has no group other than the functional group that reacts with the cross-linking agent. On the other hand, when the functional group-containing polymer has a group that reacts with the cross-linking agent in addition to the functional group, the cross-linking forms (1) to (3) can be taken.

When the functional group-containing polymer is the above-mentioned modified polymer, it is preferable that the functional groups are crosslinked.
When reacted with other reactive groups of the modified polymer,
This is because the molecular weight of the polymer may decrease or excessive crosslinking may occur.

As will be described later, a polymer other than the functional group-containing polymer may be added to the resin composite of the present invention. In this case, as shown in FIGS. 4 (4) and (5), the polymer 3 is a reactive group 3 other than a reactive group.
When it has 9, the polymer 3 may be crosslinked by the crosslinking agent 2 to increase the molecular weight. The crosslinking of the polymer in this case can take the following various forms, for example.

(4) The reactive group 39 of the polymer 3
When the functional groups 10 of the functional group-containing polymer 1 are crosslinked. (5) The case where the reactive group 39 of the polymer 3 and the reactive group 19 of the functional group-containing polymer 1 are crosslinked.

When such cross-linking with another polymer occurs, the molecular weight of the polymer may decrease, or excessive cross-linking may cause a problem in the flowability of the entire resin composite material and in the processability. When such a problem may occur, the amount of the crosslinking agent may have to be adjusted.

(Organized Clay) As shown in FIG. 5, the organized clay 70 is composed of the organic onium ion 6 and the clay 7.
(Clay mineral) This refers to clay that has been organized by ionic bonding to the surface of the clay. It is preferable that the 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 functional group-containing 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, and trioctyl ammonium ion. , Distearyl dimethyl ammonium ion, stearyl trimethyl ammonium ion, ammonium laurate ion or the like can be used.

As the clay, those having a large contact area with the functional group-containing polymer are preferably used. Thereby, the interlayer between the clays can be largely swollen.
Specifically, the cation exchange capacity of the clay is 50 to 2
It is preferably 00 milliequivalents / 100 g. If the amount is less than 50 milliequivalents / 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 strength between the clay layers becomes strong,
It may be difficult to swell between the layers of the clay.

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.

The organic onium ion is preferably 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 functional group-containing 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 was 100
It is preferably 0.01 to 200 parts by weight based on 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. On the other hand, when the amount exceeds 200 parts by weight, the viscosity of the resin composite material becomes too high, and the moldability may be deteriorated.

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

It is preferable that the organic clay is dispersed in the functional group-containing polymer in a size of 1 μm or less.
Thereby, the mechanical properties of the resin composite and the fluid barrier properties of the resin composite are improved.

The reason is presumed as follows. That is, the functional group-containing polymer has a functional group. Therefore, the interaction between the functional group and the highly polar organically treated clay results in a matrix consisting of the functional group-containing polymer,
Organized clay disperses at the molecular level. In addition, the molecular motion of the functional group-containing polymer is hindered by the organized clay. Therefore, a resin composite having excellent mechanical strength can be obtained.

It is preferable that the functional group-containing polymer intervenes (intercalates) between the clay layers. As a result, the interface between the clay surface and the polymer is increased, and the effect of the clay reinforcing the functional group-containing polymer is increased. The above-mentioned intercalation refers to a state in which the interlaminar distance between the organically modified clay and the functionalized polymer is larger than the interlaminar distance between the organically modified clay before the composited clay. This state can be observed by, for example, X-ray diffraction.

More preferably, after compounding with the functional group-containing polymer, the interlayer distance of the organized clay is increased by 10 ° or more than before compounding. More preferably, 3
0 ° or more. Particularly preferably, the interlayer distance is increased by 100 ° or more. As a result, the proportion of the functional group-containing polymer bound by the organized clay is increased,
The reinforcing effect of the organized clay is increased.

Particularly preferably, the layer structure of the organized clay is lost, and the clay is dispersed in a single layer. As a result, the ratio of the functional group-containing polymer restricted by the organized clay is further increased, and the reinforcing effect of the organized clay is increased. However, even in this case, there may be a layered state of about several layers as long as the physical properties of the resin composite are not reduced.

(Addition of Polymer Other than Functional Group-Containing Polymer) In addition to the above-mentioned functional group-containing polymer, a polymer can be added to the resin composite material of the present invention. Such a polymer is preferably compatible with the functional group-containing polymer in order to finely disperse the organized clay.

The functional group-containing polymer and the polymer are not particularly limited as long as they are compatible with each other. For example, the following combinations are available. First, the combination of the functional group-containing polymer and the other polymer preferably has the same or similar main chain structure. Thereby, the functional group-containing polymer and the polymer 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.
Examples of the combination of the unmodified polymer and the modified polymer include polyethylene (hereinafter, referred to as PE) and modified PE, polypropylene (hereinafter, referred to as PP), modified PP, and ethylene propylene rubber (hereinafter, referred to as EPR). EPR and the like, but are not limited to these.

Second, as a combination of a functional group-containing polymer and another polymer, there is a combination of one polymer and the other polymer having the same constituent portion as that of the polymer. 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 functional group-containing polymer and the other polymer have compatibility even if the main chain structure 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.

(Method of Manufacturing Resin Composite) As a method of manufacturing the resin composite, first, after dispersing and dissolving the organic clay, the crosslinking agent, the functional group-containing polymer and the other polymer in a solvent, There is a method of removing the solvent and combining them.

Secondly, there is a method of mixing an organic clay, a crosslinking agent, a functional group-containing polymer and another polymer, and heating the mixture to a temperature higher than the softening point or higher than the melting point of the functional group-containing polymer.
At the time of this heating, it is preferable to apply a shear. This makes it possible to disperse the organic clay more uniformly. In particular, it is preferable to perform melt-kneading while giving shear using an extruder. At this time, an organic solvent, oil or the like may be added.

The organic clay, the functional group-containing polymer, the cross-linking agent, and the polymer may be mixed at the same time by, for example, charging them into an extruder or the like as raw materials, or may be mixed over time in an arbitrary order. . In the case of mixing over time in an arbitrary order, mixing may be performed over time in one mixing process, or raw materials may be taken out each time and mixed in several mixing processes.

The order of mixing is, for example, when (1) the functional group-containing polymer and the crosslinking agent are mixed first, and then the organic clay and the polymer are mixed, (2) the functional group-containing polymer and the crosslinking agent are required. It is conceivable to mix the organic polymer first and then the organic clay.

The resin composite material of the present invention is used, for example, in injection-molded products, extruded products, and film materials.

[0075]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The resin composite of the present invention will be described with reference to Examples 1 to 3 and Comparative Examples 1 and 2. (Example 1) As shown in FIG. 6, a resin composite material 8 of this example is composed of an organized clay 70, a functional group-containing polymer 1, another polymer 3, and a crosslinking agent 2. The functional group-containing polymer 1 is cross-linked by a cross-linking agent 2.

As the organic clay 70, montmorillonite organically treated with stearyl ammonium was used.
Hereinafter, this is referred to as C18-Mt. As the functional group-containing polymer 1, maleic anhydride-modified polypropylene (manufactured by Sanyo Chemical Industries, trade name: Umex 1001) was used. Hereinafter, this is referred to as Umex 1001. As the crosslinking agent 2, ethylene glycol was used. As the polymer 3, polypropylene MA2 manufactured by Mitsubishi Chemical Corporation was used. Less than,
This is called MA2.

Hereinafter, a method of manufacturing the resin composite material of this example will be described. (1) 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 °.

(2) Crosslinking of Functional Group-Containing Polymer Eumex 1001 (500 parts by weight) was mixed with ethylene glycol (3 parts by weight), and mixed with a twin screw extruder.
It was melt-kneaded at 0 ° C. The melt viscosity of EUMEX 1001 before kneading is 160 cps, and the melt viscosity after kneading is 220 cps.
ps, and crosslinked with ethylene glycol to obtain a high molecular weight.

(3) Complexing The above-mentioned cross-linked Eumex 1001 (21.4 parts by weight), MA2 (71.5 parts by weight), C18-Mt (7.
1 part by weight) and melt-kneaded at 200 ° C. using a twin-screw extruder. Thus, a resin composite material of this example was obtained.

(Evaluation) The dispersion state of clay (montmorillonite) in the obtained resin composite material was observed with a transmission electron microscope (TEM). As a result, the clay was dispersed on the order of nanometers.

Next, as shown in Tables 1 and 2, when a tensile test was performed on the resin composite material of this example, the elastic modulus and strength at 25 ° C. and 80 ° C. were higher than those of Comparative Example 1 described later. Was. When dynamic viscoelasticity was measured,
The storage modulus at 100 ° C. was also higher than Comparative Example 1 described later.

The reason is considered as follows. As shown in FIG. 6, the functional group 10 of the functional group-containing polymer 1
Has a higher affinity for the organized clay 70 than other polymer portions of the functional group-containing polymer. Due to the affinity between the functional group 10 and the organized clay 70, the functional group-containing polymer 1 is intercalated between the clay layers.

Even if the clay is dispersed in the polymer 3, the functional group-containing polymer 1 comes close to the organized clay 70 due to the presence of the functional group having a high affinity for the organized clay. Therefore, as shown in FIG. 7, the functional group-containing polymer 1 surrounds the periphery of the organized clay in a state where the functional groups 10 are brought close to the organized clay 70 as described above.

Further, since the functional group-containing polymer 1 that has been cut by the organized clay 70 is cross-linked by a cross-linking agent, the functional group-containing polymer 1 is increased in molecular weight and reinforced.
Therefore, even if stress is concentrated on the organized clay 70 by applying an external force to the resin composite material 8, the organized clay 70
Cracking at the interface between the polymer and the polymer 3 and cracking at the polymer 3 around the organized clay can be prevented. Further, the destruction of the resin composite material 8 can be prevented. Therefore, it is considered that the resin composite material 8 having excellent mechanical strength can be obtained.

(Example 2) The resin composite material of this example is different from that of Example 1 in that each raw material was kneaded at the same time. That is, Umex 1001 (21.4 parts by weight), MA2 (7
(1.5 parts by weight), C18-Mt (7.1 parts by weight), and ethylene glycol (0.13 parts by weight) were mixed and melt-kneaded at 200 ° C. using a twin-screw extruder. Otherwise, a resin composite material was manufactured in the same manner as in Example 1.

(Evaluation) The dispersion state of clay (montmorillonite) in the obtained resin composite material was observed with a transmission microscope. As a result, the clay was dispersed on the order of nanometers. Next, as shown in Tables 1 and 2,
When the tensile test of the resin composite material of this example was performed,
Both the elastic modulus and strength at 80 ° C. were higher than Comparative Example 1 described later. When dynamic viscoelasticity was measured,
The storage elastic modulus at 20 ° C. and 100 ° C. was also determined in Comparative Example 1 described later.
Than was higher.

(Comparative Example 1) The resin composite material of this example differs from that of Example 1 in that it does not contain a crosslinking agent. That is, EUMEX 1001 (21.4 parts by weight), MA2 (71.5 parts by weight) and C18-Mt (7.1 parts by weight) were mixed and melt-kneaded at 200 ° C. using a twin-screw extruder. A resin composite of this example was obtained.

(Evaluation) The dispersion state of clay (montmorillonite) in the obtained resin composite material was observed by TEM. As a result, the clay was dispersed on the order of nanometers. Next, as shown in Tables 1 and 2, when a tensile test was performed on the resin composite material of this example, the elastic modulus and strength at 25 ° C. were 1.18 GPa and 33.0 MPa.
The elastic modulus and strength at 0 ° C. are 0.401 GPa and 12.8.
MPa. When dynamic viscoelasticity was measured, the storage elastic modulus at 20 ° C. and 100 ° C. was 3.2 GP.
a, 0.90 GPa.

Example 3 As a functional group-containing polymer, a styrene-vinyl oxazoline copolymer (Nippon Shokubai Co., Ltd., trade name: Epicross RPS-1005) was used. Hereinafter, this is referred to as epicross. Terephthalic acid was used as a crosslinking agent.

As the organic clay, montmorillonite organically treated with trimethylstearylamine was used. Hereinafter, this is referred to as C18TM-Mt. To explain the details of the production method, first, Na-montmorillonite (trade name: Knipia F) manufactured by Kunimine Kogyo was prepared as a layered clay mineral. 80 g of Na-montmorillonite,
It was dispersed in 5000 ml of water at 80 ° C. 36.8 g of trimethylstearyl ammonium chloride was 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 trimethylstearylamine. Hereinafter, it is abbreviated as C18TM-Mt. The inorganic content in C18TM-Mt determined by the scuffing method was 66%. C18T determined by X-ray diffraction method
The interlayer distance of M-Mt was 22 °.

As the polymer, polystyrene (trade name: Toporex 525, manufactured by Mitsui Toatsu) was used. Hereinafter, this is called Toporex.

The above epicloth (21.4 parts by weight), Toporex (71.5 parts by weight), C18TM-Mt
(7.1 parts by weight) and terephthalic acid (0.1 parts by weight) were mixed and melt-kneaded at 170 ° C. using a twin-screw extruder.
A resin composite was obtained.

(Evaluation) The dispersion state of clay (montmorillonite) in the obtained resin composite material was observed by TEM. As a result, the clay was dispersed on the order of nanometers. Next, as shown in Tables 1 and 2, when a tensile test was performed on the resin composite material of this example, the elastic modulus and strength at 25 ° C. were higher than those of Comparative Example 2 described later.

(Comparative Example 2) The resin composite material of this example differs from Example 1 in that it does not contain a crosslinking agent. That is, Epicross (21.4 parts by weight), Toporex (71.5 parts by weight) and C18TM-Mt (7.1 parts by weight) were mixed,
The mixture was melt-kneaded at 170 ° C. using a twin-screw extruder to obtain a resin composite material of this example.

(Evaluation) The dispersion state of clay (montmorillonite) in the obtained resin composite was observed with a transmission microscope. As a result, the clay was dispersed on the order of nanometers. Next, as shown in Tables 1 and 2, when a tensile test was performed on the resin composite material, the elastic modulus and strength at 25 ° C. were 1.9 GPa and 40 MPa.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

According to the present invention, a resin composite material having excellent mechanical strength can be provided.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a modified polymer in the present invention.

FIG. 2 is an explanatory diagram of a copolymer in the present invention.

FIG. 3 is a cross-linking agent according to the present invention wherein
FIG. 4 is an explanatory diagram of the case of a compound having the above (a) and the case of a compound having a group capable of reacting two or more times with one group (b).

FIG. 4 is an explanatory view (1) to (3) showing a crosslinked form of a functional group-containing polymer and explanatory views (4) to (5) showing a crosslinked form of a polymer in the present invention.

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

FIG. 6 is an explanatory diagram of the resin composite material of Example 1.

FIG. 7 is an explanatory diagram showing the operation and effects of the first embodiment.

FIG. 8 is an explanatory view of a conventional resin composite material.

[Explanation of symbols]

 1. . . 9. functional group-containing polymer, . . Functional group, 2. . . 2. a cross-linking agent; . . Polymer, 70. . . 7. Organized clay, . . Resin composite,

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Claims (1)

[Claims] 1. A functional group-containing polymer comprising an organized clay, two or more polymers, and a crosslinking agent, wherein at least one of the two or more polymers is a functional group-containing polymer having a functional group. A resin composite, wherein the polymer is cross-linked by the cross-linking agent.