WO1999010276A1

WO1999010276A1 - Silicate-containing composite material

Info

Publication number: WO1999010276A1
Application number: PCT/US1998/017421
Authority: WO
Inventors: Nobuhiro Takahashi; Shunichi Kobayashi; Tsunemi Kadoma; Takayuki Arai; Hideo Akimoto
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1997-08-25
Filing date: 1998-08-25
Publication date: 1999-03-04

Abstract

A composite material not containing water comprised of stratified silicates and an organic polymer material, which has thermal stability and in which dispersibility is improved so that the interlayer distances of the silicate layers are expanded and the interlayers are essentially not parallel, a method for its manufacture and a resin composition which contains such a composite material. A method of manufacture in which an aqueous dispersion of ethylene acid copolymer or ionomer is mixed with a stratified silicate and the mixture is dried resulting in the ethylene acrylic acid copolymer or isomer thereof being inserted between the silicate layers with the interlayers of which being essentially not parallel. An organic polymer resin composition containing such composite material.

Description

TITLE SILICATE-CONTAINING COMPOSITE MATERIAL

This patent application claims priority to Japanese Patent Application

No. 9-241700, filed 25 August 1997, which is incorporated herein by reference. FIELD OF THE INVENTION

The present invention relates to a composite material that is compounded in organic polymer materials for the purpose of improving the mechanical properties, gas barrier capacity, heat resistance or transparency of organic polymer materials and to a method for its manufacture. In greater detail, it relates to a composite material in which an ethylene α,β ethylenically unsaturated carboxylic acid copolymer or ionomer thereof, particularly an ethylene acrylic acid or ethylene methacrylic acid copolymer or ionomer thereof, is inserted into the silicate layer that forms a stratified silicate so that the interlayers are essentially not parallel and to a method for its manufacture. Further, this invention relates to an organic resin composition containing a composite material that contains an organic polymer material and the composite material that is obtained.

BACKGROUND OF THE INVENTION

Attempts have been made to obtain composite materials in which an organic polymer material is inserted into silicate layers that form stratified silicates. These attempts have been summarized in review articles by, for example, Chuzo Kato (Kobunshi [High Polymers], 1970, Vol. 19, No. 222, pp. 758-764) and Chuzo Kato and Kazuyuki Kuroda (Nendo Kagaku [Journal of the Clay Science Society of Japan], 1986, Vol. 26, No. 4, pp. 292-305). However, inserting the organic polymer material into the silicate layer to expand the interlayer distance decreases the parallel character of the interlayers and makes it difficult to disperse the clay mineral.

One composite material that was developed for the purpose of solving this problem was a clay mineral/polyamide resin composition characterized in that a swellable clay mineral is inserted onto the silicate layer, and, in that, as required, treatment is performed with an alkylamine swelling agent and a monomer is impregnated and polymerized (Japanese Patent Disclosure No. 58-35211 [1983] and Japanese Patent Disclosure No. 58-35542 [1983]).

A composite material in which a resin containing polyamide is admixed in a silicate layer in which the thickness of the silicate layer that forms the stratified silicate is from 7 to 12 angstrom and the interlayer distance is greater than 30 angstrom and in which a portion of the polyamide polymer chain is ionically bonded with the silicate layer has been reported as a composite material in which a portion of the polyamide chain is ionically bonded with the silicate layer (Japanese Patent Application Early Disclosure No. 62-74957 [1987]). The method of manufacture of this composite material is comprised of a contact process in which the stratified silicate and a swelling agent are brought into contact and a composite having the property of swelling is made by means of the polyamide in the monomer at a temperature above the fusion temperature of the monomer, a mixing process in which the composite that is obtained and the polyamide monomer are mixed and a polymerization process in which the mixture is heated to a specified temperature and is polymerized (Japanese Patent Application Early Disclosure No. 62-74957 [1987]). Because the polymerization process is included in the manufacturing process in this method, manufacture of the composite material is not always easy and it is difficult to use substances other than polyamides.

An organic resin composition containing a composite material has been reported for the purpose of solving the problems of the manufacturing process in which the interlayer distance is expanded to greater than 30 angstrom and in which the parallel character of the interlayer is decreased by fusing and kneading with the polyamide a stratified silicate/alkylamine swelling agent composite material obtained by dispersing a stratified silicate and an alkylamine swelling agent in water and drying the dispersion (U.S. Patent No. 5385776). However, with this method, an alkylamine swelling agent of low molecular weight is admixed with the final product, for which reason there is a problem of thermal stability. In addition, expanding the interlayer distance to greater than 30 angstrom using a resin other than a polyamide resin decreases the parallel character of the interlayers and makes it difficult to obtain a resin composition containing a composite material of improved dispersibility.

A composite material that is manufactured by extruding a mixture of phillosilicate, intercalated polymer and water through a die opening has been reported as a composite material that is an organic polymer material other than a polyamide, in which a stratified silicate is dispersed and that does not contain a polymerization process (Japanese Patent Application Early Disclosure No.9- 20514 [1997]). Although the interlayer of silicate in this composite material is expanded to 10 to 55 angstrom, it has a regular structure in which the parallel structure is essentially maintained. Moreover, it was difficult to handle because it contained at least approximately 10 wt % of water.

In addition, a composite material not containing water and in which an ionomer is inserted into the silicate layer by dispersing, mixing, drying and pulverizing the ionomer in a stratified silicate and water has been disclosed

(Japanese Patent Application 8-302368 [1996]).

Problems the invention is intended to solve

The object of this invention is to provide a composite material not containing water that is comprised of a stratified silicate and an organic polymer material, that has thermal stability, in which the interlayer distance of the silicate layer is expanded and of which dispersibility is increased so that the interlayers are essentially not parallel and to provide a method for its manufacture.

Further, the object of this invention is to provide an organic resin composition that contains such a composite material. In detail, the object of this invention is to provide a composite material that is comprised of an ethylene α,β ethylenically unsaturated carboxylic acid copolymer or ionomer thereof, particularly an ethylene acrylic acid or ethylene methacrylic acid copolymer or ionomer thereof, and of a stratified silicate, a method for its manufacture and an organic resin composition that contains such a composite material.

SUMMARY OF THE INVENTION

This invention provides a composite material not containing water which is comprised of stratified silicates and an ethylene α,β ethylenically unsaturated carboxylic acid copolymer or ionomer thereof, particularly an ethylene acrylic acid or ethylene methacrylic acid copolymer or ionomer thereof, and in which dispersibility is improved so that the interlayer distances of the silicate layers are expanded and the interlayers are essentially not parallel and a method of manufacture whereby such a composite material can be manufactured.

The present invention is concerned with a method whereby composite materials not containing water in which the interlayers are essentially not parallel and which are of improved dispersibility are made by mixing an ethylene α,β ethylenically unsaturated carboxylic acid copolymer or ionomer thereof, particularly an ethylene acrylic acid or ethylene methacrylic acid copolymer or ionomer thereof, and the stratified silicate in water at a strong shear. Specifically, the composite material in accordance with the invention of this application first of all is characterized in that it contains an ethylene α,β ethylenically unsaturated carboxylic acid copolymer or ionomer thereof, particularly an ethylene acrylic acid or ethylene methacrylic acid copolymer or ionomer thereof, and a stratified silicate layer and in that the aforementioned ethylene acid copolymer or ionomer thereof is inserted between the silicate layers of the aforementioned stratified silicate.

The method of manufacture of the composite material in accordance with the invention of this application is characterized in that an ethylene α,β ethylenically unsaturated carboxylic acid copolymer or ionomer thereof, particularly an ethylene acrylic acid or ethylene methacrylic acid copolymer or ionomer thereof, dispersion is mixed with a stratified silicate and dried, by which means the aforementioned ethylene acid copolymer or ionomer thereof is inserted in the silicate layer of the aforementioned stratified silicate.

The method of manufacture of the composite material in accordance with another aspect of the invention of this application is characterized in that an ethylene α,β ethylenically unsaturated carboxylic acid copolymer or ionomer thereof, particularly an ethylene acrylic acid or ethylene methacrylic acid copolymer or ionomer thereof, and a stratified silicate are mixed, and, by rapid drying as shearing force was applied, the aforementioned ethylene acid copolymer or ionomer thereof is inserted into the silicate layer of the aforementioned stratified silicate.

The method of manufacture of the composite material in accordance with another aspect of the invention of this application is characterized in that the an ethylene α,β ethylenically unsaturated carboxylic acid copolymer or ionomer thereof, particularly an ethylene acrylic acid or ethylene methacrylic acid copolymer or ionomer thereof, and the stratified silicate are mixed using an homogenizer and the mixture is dried with a spray dryer, by which means the aforementioned ethylene acid copolymer or ionomer thereof is inserted into the aforementioned stratified silicate.

A resin composition containing composite material in accordance with still another aspect of the invention of this application is characterized in that it contains the composite material in accordance with the invention first of all specifically described above or a composite materials that is manufactured by any of the other aspects of the invention described above and an organic polymer material. A resin composition containing composite material in accordance with still another aspect of the invention of this application is characterized in that the aforementioned organic polymer material in the resin composition containing composite material of the aforementioned invention has affinity with the aforementioned ethylene acrylic acid copolymer or ionomer thereof.

BRIEF EXPLANATION OF THE FIGURES

Figure 1 is an X-ray chart of composite materials obtained in Example 2. Figure 2 is an X-ray chart of composite materials obtained in Example 3.

Figure 3 is an X-ray chart of composite materials obtained in Example 4.

Figure 4 is an X-ray chart of composite materials obtained in Example 5.

Figure 5 is an X-ray chart of composite materials obtained in Example 6.

Figure 6 is an X-ray chart of composite materials obtained in Example 7. Figure 7 is an X-ray chart of composite materials obtained in Example 8.

Figure 8 is an X-ray chart of composite materials obtained in

Comparative Example 1.

Figure 9 is an optical microscope photograph of the composite material obtained in Example 11. Figure 10 is an optical microscope photograph of the composite material obtained in Example 12.

Figure 11 is an optical microscope photograph of the composite material obtained in Example 13.

Figure 12 is an optical microscope photograph of the composite material obtained in Example 14.

Figure 13 is an optical microscope photograph of the composite material obtained in Example 15.

Figure 14 is an optical microscope photograph of the composite material obtained in Example 16. Figure 15 is an optical microscope photograph of the composite material obtained in Example 17.

Figure 16 is an optical microscope photograph of the composite material obtained in Example 18.

Figure 17 is an optical microscope photograph of the composite material obtained in Example 19.

Figure 18 is an optical microscope photograph of the composite material obtained in Example 20.

Figure 19 is an optical microscope photograph of the composite material obtained in Comparative Example 3. Figure 20 is a transmission electron micrograph of the composite material obtained in Example 1. Figure 21 is a transmission electron micrograph of the composite material obtained in Example 2.

Figure 22 is a transmission electron micrograph of the composite material obtained in Example 3. Figure 23 is a transmission electron micrograph of the composite material obtained in Example 8.

Figure 24 is a transmission electron micrograph of the composite material obtained in Example 9.

Figure 25 is a transmission electron micrograph of the composite material obtained in Example 10.

DETAILED DESCRIPTION OF THE INVENTION

According to the present invention, ethylene α,β ethylenically unsaturated carboxylic acid copolymer or ionomer thereof, particularly an ethylene acrylic acid or ethylene methacrylic acid copolymer or ionomer thereof, is inserted between the silicate layers of the stratified silicate in the composite material of this invention. The ethylene acid copolymer or ionomer thereof in this inserted matter originates in the ionomer in the aqueous dispersion of the ethylene acid copolymer ionomer that is used in the method of the manufacture of the composite material. Ordinarily, the ionomer that is used is introduced in unaltered form into the composite material. When ammonia or an aqueous dispersion of an ionomer of a lower amine is used, some or all of these substances is lost by volatilization in the drying process. Therefore, it is introduced into the composite material as an ionomer of a decreased degree of neutralization or as an ethylene acid copolymer. Here, the ethylene acid copolymer is a copolymer of ethylene and α,β ethylenically unsaturated carboxylic acid, particularly acrylic acid or ethylene methacrylic acid, in which other monomers as desired may be copolymerized. These other monomers include olefins such as propylene, 1-butene and isobutylene, vinyl esters such as vinyl acetate and vinyl propionate, unsaturated monovalent carboxylic acid esters such as methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate and isobutyl methacrylate, unsaturated polyvalent carboxylic acids (anhydrides) such as fumaric acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, monomethyl maleate, monoethyl maleate and dimethyl maleate and esters thereof, carbon monoxide and sulfur dioxide. The ethylene acid copolymer described above should contain acid in an amount of 5 to 20 wt %, and, preferably, of 10 to 25 wt %. Specifically, when the acid content used is below the aforementioned range, the diameters of the dispersed particles in the aqueous dispersion when the composite material is manufactured become excessively great and it is difficult to obtain the desired composite material. When the acid content used is above the aforementioned range, moisture absorbing capacity is increased and there is a great deleterious effect on physical properties. The ionomer of the ethylene acid copolymer is a substance in which some or all of the carboxyl groups of said copolymer are neutralized by an alkali metal such as lithium, sodium or potassium, an alkaline earth metal such as calcium or magnesium, an organic amine such as an alkylamine or an alkanolamine or ammonia. As describe above, because a drying process is incorporated, ammonia and low boiling point amines are readily lost, for which reason it is difficult for a considerable quantity to remain in the composite material. In ionomers in which alkali metals and low boiling point amines are the ionic species, the degree of neutralization originating in the method of manufacture is generally 40 to 100%.

The ethylene acid copolymer that is used in this invention may be a random copolymer of ethylene and α,β ethylenically unsaturated carboxylic acid copolymer, particularly an ethylene acrylic acid or ethylene methacrylic acid, more particularly acrylic acid.

The stratified silicate is ordinarily 7 to 15 angstrom in thickness and is formed by a magnesium silicate and aluminum silicate layers. Specifically, it may be a natural or synthetic substance including smectite clay minerals such as montmorillonite, saponite, beidellite, nontronite, hectorite and stevensite and vermiculite, halloysite and mica. It can also be a swellable fluoromica. Of these, smectite stratified silicates are preferable.

The content of stratified silicate in the composite material should be 0.5 to 300 parts by weight, preferably, 1 to 100 parts by weight, and, more preferably, 20 to 50 parts by weight, per 100 parts by weight of ethylene acid copolymer. An aqueous dispersion of the ethylene acid copolymer or ionomer thereof can be used in the manufacture of the composite material as described above. This aqueous dispersion can be manufactured by a method in which ethylene acid copolymer is heated and stirred in an alkali aqueous solution at a temperature above its melting point or by a method in which an ionomer that has been manufactured in advance is heated and stirred in water at a temperature above its melting point. The ethylene acid copolymer that is used may be a substance obtained by radical polymerization or a substance that is obtained by thermal decomposition or hydrolysis of an ethylene acid ester copolymer. The alkali aqueous solution may consist of one or two or more of sodium hydroxide, potassium hydroxide, amines or ammonia. When the water dispersibility of the ionomer that is obtained is taken into consideration, it is desirable to prepare it so that the degree of neutralization in the aqueous dispersion is regulated to 40 to 100%.

Substances having a high concentration of solid matter can be manufactured as the aqueous dispersion of the ionomer. However, when they are mixed with the stratified silicate and the concentration is too high, there is the danger that the interlayers of silicate will not be sufficiently wide. When the concentration is excessively low, there is the danger that the aqueous dispersion will be unstable and that aggregation will occur. Therefore, ordinarily, a substance should be used in which the concentration of solid matter is on the order of 0.5 to 5 wt %, the pH of which is 8 to 12 and the number average molecular weight is 10 to 1000 nm..

When the ethylene acid copolymer or ionomer is mixed with a stratified silicate in water, mixing should be performed under strong shearing conditions so that the stratified silicate will be thoroughly mixed with the ethylene acid copolymer or ionomer. Mixing can be performed by any known method such as with an homogenizer or a propeller mixer. Mixing by means of a homogenizer is preferable in that strong shear can be applied.

Drying can be performed by any known method such as with a spray dryer or a box dryer. A desirable drying method is quick drying in which water is eliminated instantaneously as shearing is applied. Specifically, such drying can be performed with a spray dryer. Freeze-drying is also effective. After drying, the water content of the composite material should be less than 10%, and, preferably, less than 5%.

Evaluation of whether or not the ethylene acid copolymer or ionomer has been inserted into the silicate layer and whether the silicate has lost its parallel character in the composite material that is obtained is performed on the basis of the peak values and intensity of wide angle X-ray determination.

The composite material that is obtained and various organic polymer material are kneaded and an organic composition containing the composite material can be obtained. The organic polymer material that is kneaded can be, for example, a thermoplastic resin, a thermosetting resin or a rubber. The thermoplastic resin, thermosetting resin or rubber for use as an organic polymer material can be selected from an extremely wide range. Examples of useful thermoplastic resins, which can be used individually or in mixtures, include polylactones such as poly(pivalolactone) and poly(caprolactone), diisocyanates such as 1,5-naphthalene diisocyanate, p- phenylene diisocyanate, m-phenylene diisocyanate, 2,4-triethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 4,4'-diphenylisopropylidene diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy- 4,4'-biphenyl diisocyanate. dianisidine diisocyanate, toluidine diisocyanate, hexamethylene diisocyanate and 4,4'-diisocyanatodiphenylnethane, polyurethane derived from reactions between linear long chain diols such as poly(tetramethyleneadipate), poly(ethyleneadipate), poly(l ,4-butyelenadipate), poly(ethylenesuccinate), poly(2,3-butylenesuccinate) and polyether diols, polycarbonates such as poly[methane bis (4-phenyl) carbonate], poly[l,l '- ethylene bis (4-phenyl) carbonate], poly[diphenylmethane-bis (4-phenyl) carbonate] and poly[l,l-cyclohexanebis (4-phenyl) carbonate], polysolfones, polyethers, polyketones, polyamides such as poly(4-aminoacetic acid), poly(hexamethyleneadipamide), poly(6-aminohexanoic acid), poly(m-xylylene- adipamide), poly(p-xylylenesebacamide), poly(2,2,2- trimethylhexamethyleneterepht-thalamide), poly(methaphenyleneisophthalmide (NOMEX®) and poly(p-ethylene terephthalamide (KEVLAR®), polyesters such as poly(ethylene azelate), poly (ethylene- 1, 5 -naph-thalate), poly(l,4- cyclohexanedimethyleneterephthalate), poly(ethylene oxybenzoate) (A-TELL), poly(p-hydroxybenzoate) (EKONOL). Poly(l,4-cyclohexylideneterephthalate) (KODEL) (cis), poly(l,4-cyclohexylidenedimethyleneterephthlate) (KODEL) (trans), polyethylene terephthalate and polybutylene terephthalate, poly(arylene oxides) such as poly(2,6-dimethyl-l,4-phenyleneoxide) and poly(2,6-diphenyl- 1 ,4-phenyleneoxide), poly(arylene sulfides) such as poly(phenylene sulfide), polyether imides, vinyl polymers and vinyl copolymers such as poly vinyl acetates, polyvinyl alcohols and polyvinyl chlorides, polyacryls, polyacrylates and copolymers thereof such as polyvinyl butyral, polyvinylidene chloride, polyethyl acrylamide, poly(n-butylacrylate), polymethyl methacrylate, polyethyl methacrylate, poly(n-butylmethacrylate), poly(n-propyl-methacrylate), polyacrylamide, polyacrylonitrile, polyacrylic acid, ethylene-vinyl alcohol, acrylonitrile copolymers, methyl methacrylate-butylene copolymers and butadiene methacrylate-styrene copolymers, polyolefins such as low molecular weight polyethylenes, ethylene-vinyl acetate copolymers, ethylene acrylate or methacrylate copolymers, ethylene acrylic or methacrylic acid copolymers, ionomers, high density polyethylenes, polypropylenes, chlorinated low density polyethylenes, poly(4-methyl-l-pentene), polyethylenes and polystyrenes, poly(epichlorohydrins), polyurethanes that are polymerization products of one or more polydiols such as ethylene glycol and propylene glycol and or polydiols such as diethylene glycol and triethylene glycol and polyisocyanates such as 2,4- tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenyl-methane diisocyanate, 1,6-hexamethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate, polysulfones such as the reaction product of sodium salt of 2,2-bis (4-hydroxyphenyl) propane and 4,4'-dichlorodiphenyl sulfone, furan resins such as polyfurans, cellulose ether plastics such as cellulose acetate, cellulose acetate butyrate and cellulose propionate, silicones such as poly(dimethyl-siloxane) and poly(dimethyl-siloxane cophenylmethylsiloxane), protein plastics and mixtures of two or more of these substances.

Useful rubbers that are vulcanizable and thermoplastic can also be used over a wide range as organic polymer materials. Examples of such rubbers include butyl bromide, butyl chloride, polyurethane elastomers, fluoroelastomers, polyester elastomers, butadiene/acrylonitrile elastomers, silicone elastomers, polybutadiene, poly(isobutadiene), ethylene-propylene copolymers, ethylene- propylene-diene terpolymers, sulfonated ethylene-propylene-diene terpolymers, poly(chloroprene), poly(2,3-dimethyl-butadiene), poly(butadiene-pentadiene, chlorosulfonated polyethylenes, polysulfide elastomers, polystyrenes, poly(vinyltoluene), poly(l-butylstyrene), glass or crystalline blocks such as polyesters and polybutadienes, poly(isoprene), ethylene-propylene copolymers, propylene copolymers, ethylene-butylene copolymers, block copolymers comprised of elastomer blocks such as polyethers and polystyrene-polybutadiene- polystyrene block copolymers such as, for example, KRATON®, which is manufactured by the Shell Chemical Company. Useful thermoplastic resins include urea resins obtained by condensation or urea and formaldehyde, melamine resins obtained by condensation of melamine and formaldehyde, phenol resins obtained by condensation of phenols such as phenol, cresol and xylylene and formaldehyde, epoxy resins that are obtained by hardening reaction condensates of epichlorohydrin and bisphenols or polyvalent alcohols (glycols such as ethylene glycol and propylene glycol, polyethylene glycol, polypropylene glycol, glycerol, pentaerythritol and sorbitol) by means of polyvalent amines or acid anhydrides such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, 2,2-dimethyl-l, 3- propanediamine, norbornanediamine, metaxylenediamine, melamine, diaminobenzene and triaminobenzene, unsaturated polyester resins comprised of unsaturated polybasic acids such as maleic anhydride, maleic acid and fumaric acid, saturated polybasic acids such as fumaric anhydride and adipic acid and polyvalent alcohols such as ethylene glycol and propylene glycol, alkyd resins comprised of polyvalent alcohols such as glycerol and ethylene glycol and polyvalent acids such as fumaric anhydride, maleic anhydride and rosin maleic anhydride additives and polyurethane resins hardened by diisocyanates such as toluene diisocyanate (TDI), polymeric diphenylmethane diisocyanate (MDI), metaxylene diisocyanate (MXDI), norbornane diisocyanate (NBDI) and isophorene diisocyanate (IPDI), polyvalent alcohols and polyvalent amines.

When the composite material of this invention is compounded with these thermosetting resins, it is desirable that they be dispersed in the monomer or prepolymer before the reaction and hardening and that heating and hardening be performed thereafter.

Useful and most desirable thermoplastic polymers as organic polymer materials include thermoplastic polymers such as polyamines, polyesters and α, β- unsaturated monomers and copolymers. The polyamides that can be used in this invention are synthetic straight chain polycarbonates characterized by the fact that repeating carbonamide groups are present in all parts of the polymers that are separated by each other by at least two carbon atoms. Polymers that are generally known as nylons in said technological field are contained in this type of polyamide. They have repeating units as indicated by the following general formula.

[Chemical Formula 1 ]

-NHCOR'COHNR² (Wherein, R¹ is an alkylene group having at least 2, and, preferably, from approximately 2 to approximately 11 carbon atoms or an arylene having at least approximately 6, and, preferably, approximately 6 to approximately 17 carbon atoms, and R2 indicates a group that is selected from R¹ and arylene groups.) They are obtained from diamines and dibasic acids. They include copolyamides and terpolyamides, and, preferably, poly-amides, that are obtained by known methods such as, for example, by concentration of mixtures of dibasic acids such as terephthalic acid and adipic acid with hexamethylene-diamine. The aforementioned polyamides are well known in said technological field and can include, for example, copolyamides comprised of 30% of hexamethylene- diammmonium isophthalate and 70% of hexamethylenediammonium adipate, poly(hexa-methyleneadipate) (nylon 6, 6), poly(hexa-methylenesebacate) (nylon 6, 10), poly (hexa-methyleneisophthalamide), poly(hexamethyleneterephthalamide), poly(heptamethylene-pimelide) (nylon 7, 7), poly(octamethylenesuberide) (nylon 8, 8), poly(nonamethylene-azelide) (nylon 9, 9), poly(decamethyleneazelide) (nylon 10, 9), poly(decamethylene-sebacamide) (nylon 10, 10), poly[bis(4-aminocyclohexyl)methane-l,0-decanecarboxa-mide)], poly(m-adipamide), poly(p-xylylenesebacamide), poly(2,2,2-trimethylhexa- methyleneterephthalamide), poly(piperazinesebacamide), poly(p-phenylenetereph- thalmide) and poly(m-phenyleneisophthalamide).

Other polyamides that are useful as organic polymer materials include amino acids and derivatives thereof, for example, substances that are formed by polymerization of lactams. Examples of these useful polyamides include poly(4- aminobutyric acid) (nylon 4), poly(6-aminohexanoic acid) (nylon 6), poly(7- aminoheptanoic acid (nylon 7), poly(8-aminoactanoic acid) (nylon (8), poly (p- aminononanoic acid) (nylon 9), poly (10-aminodecanoic acid) (nylon 10), poly(l 1-aminoundecanoic acid (nylon 11) and poly(12-aminodecanoic acid) (nylon 12).

Desirable polyamides include poly(caprolactam), poly(12- aminododecanoic acid) and poly(hexamethyleneadipamide).

Other polymers that are useful as organic polymer materials include straight chain polyesters. The type of polyester does not control this invention. Specific polyesters that can be selected for use as organic polymer materials depend essentially on the physical properties and properties, i.e., tensile strength and tensile stress, that are desired in the final state. The presence of large numbers of straight chain thermoplastic polyesters having diverse physical characteristics is desirable in manufacturing the composite materials of this invention and for their use in mixtures with inserted matter.

The polyesters that are especially selected for use in this invention, as desired, may be homopolyesters, copolyesters or mixtures thereof. The polyesters are ordinarily prepared by concentration of a dicarboxylic acid and an organic diol. Because in situ polymerization of the polyester is effected during contact with the inserted matter, the reactants can be added to the stratified silicate in which the ethylene acid copolymer or ionomer thereof has been inserted. Desirable polyesters that can be used as organic polymer materials in this invention are obtained by concentration of aromatic, alicyclic and aliphatic diols with aliphatic, aromatic and alicyclic dicarboxylic acids. Therefore, they may be alicyclic, aliphatic or aromatic polyesters.

Examples of useful alicyclic, aliphatic and aromatic polyesters that can be used as organic polymer materials in executing this invention include poly(ethylene terephthalate), poly(cyclohexylene dimethylene terephthalate), poly(ethylene dodecate), poly(butylene terephthalate), poly[ethylene(2,7- naphthalate)], poly(m-phenylene isophthalate), poly(glycolic acid), poly(ethylene succinate), poly(ethylene adipate), poly(ethylene sebacate), poly(decamethylene azelate), poly(decamethylene adipate), poly(decamethylene sebacate), poly(dimethyl propiolactone), poly(p-hydroxybenzoate) (EKONOL), poly(ethylene oxybenzoate) (A-TELL), poly(ethylene isophthalate), poly(tetra- methylene terephthalate), poly(hexamethylene terephthalate), poly(decamethylene terephthalate), poly(l,4-cyclohexylene dimethylene terephthalate) (trans), poly(ethylene- 1 ,5-naphthalate), poly(ethylene-2,6-naphthalate), poly(l ,4- cyclohexulidene dimethylene terephthalate (KODEL) (cis) and (1 ,4- cyclohexylidene dimethylene terephthalate (KODEL).

The polyester compounds that are prepared by concentration of diols and aromatic dicarboxylic acids are particularly suited for use as organic polymer materials in this invention. Examples of aromatic carboxylic acids having such usefulness include terephthalic acid, isofumaric acid, o-phthalic acid, 1,3- naphthalenedicarboxylic acid, 1 ,4- naphthalenedicarboxylic acid, 2,6- naphthalenedicarboxylic acid, 2,7- naphthalene-dicarboxylic acid, 4,4'- diphenyldicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 1,1,3-trimethyl- 5-carboxy-30(p-carboxyphenyl) indane, diphenyl ether-4,4' -dicarboxylic acid and bis-p-(carboxyphenyl) methane. Of the aforementioned aromatic dicarboxylic acids, those having benzene rings (terephthalic acid, isophthalic acid, o-phthalic acid, etc.) are preferable for use in executing this invention. Of these desirable acid precursors, terephthalic acid is a particular desirable acid precursor.

In the most desirable mode of execution of this invention, the inserted matter is incorporated into an organic polymer material selected from a group comprised of polyethylene terephthalate), poly(butylene terephthalate), poly(l,4- cyclohexane dimethylene terephthalate), polyvinyl amines and mixtures thereof. Of the polyesters that can be selected, poly(ethylene terephthalate) and poly(butylene terephthalate) are the most desirable. Other useful thermoplastic homopolymers and copolymers for use as organic polymer materials in this invention can include , β unsaturated monomers and polymers that are formed by polymerization of monomers as indicated by the following formula. R³R⁴C=CH₂ (Wherein, R³ and R⁴, which may be the same or different, indicate cyano, phenyl, carboxy, alkyl ester, halo or alkyl groups, alkyl groups substituted by one or more chlorine or fluorine atoms or hydrogen atoms.) Example of such desirable homo-polymers or copolymers include homopolymers and copolymers of ethylene, propylene, vinyl alcohols, acrylonitrile, vinylidene chloride, acrylic acids and esters thereof, methacrylic acid and esters thereof, chlorotrifluoroethylene and vinyl chloride. Desirable substances include polypropylenes, propylene copolymers, polyethylenes and ethylene copolymers. Ethylene copolymers can include ethylene - vinyl acetate copolymers, ethylene - acrylic acid or methacrylic acid copolymers, ethylene - acrylate and methacrylate copolymers and ionomers. In a desirable mode of execution of this invention, the polymers that can be selected for use as organic polymer materials are polymers and copolymers olefins, polyesters, polyamides, polyvinyl imides and mixtures containing these polyesters. In a particularly desirable mode of execution of this invention, polymers and copolymers of ethylene, polyamides (preferably, nylon 6 and nylon 6, 6, and, more preferably, nylon 6) and mixtures thereof can be used as organic polymer materials.

It is desirable that the organic polymer material have an affinity with the ethylene acid copolymer. Here, the term affinity means complete compatibility, partial compatibility, or, in cases of incompatibility, good affinity at the interfaces. When affinity is absent, there is the possibility that there will be marked decreases in mechanical properties and gas barrier capacity when the silicate layers of the stratified silicate are completely dispersed in the final substance in the subsequent kneading process.

Specifically, they include polyesters such as polyolefins, polybutylene terephthalate and polyethylene terephthalate, polyamides such as nylon 6 and nylon 66, random copolymers of ethylene and methacrylic acid and ionomers of sodium salts, magnesium salts or zinc salts that have partially or completely neutralized ethylene and methacrylic acid. For example, when an ethylenic ionomer is used, the composite material of this invention is transparent, for which reason the conventional problem of loss of transparence of the ethylenic ionomer when an inorganic filler is added to the ethylenic ionomer to improve mechanical properties can be solved. The ethylene acid copolymer or ionomer thereof is combined with the organic polymer material and 0.5 parts by weight to 300 parts by weight of stratified silicate is dispersed and filled into it per 100 parts by weight. When the amount is less than 0.5 parts by weight, the effect due to filling is not sufficient. When it exceeds 300 parts by weight, poor dispersion occurs.

Fusion and kneading (compounding) of the composite material and the organic polymer material may be performed by any conventionally known method. It is desirable to use a kneading machine having strong fusion and kneading capacity so that the mechanical dispersing force is transmitted to the composite material and the stratified silicate will be even better dispersed as a result of the good affinity of the two substances, Specifically, biaxial (rotating in the same direction and rotating in different directions) kneading machine or a crushing kneader is preferable.

Whether the interlayer distance of the silicate layers in the resin composition containing composite material is expanded and whether a structure of composite material in which dispersibility is increased essentially without loss of the parallel character of the interlayers was evaluated by visual observation of the degree of transparency by means of an optical microscope, and, as required, by observation with a transmission electron microscope. EXAMPLES

The invention will now be described by way of Examples. However, this invention is not limited by these examples.

Reference Example 1

The following substances were introduced into an autoclave.

The mixture was heated to 130°C, stirring was performed for 30 minutes at 1000 revolutions/minute and an aqueous dispersion of potassium salt of ethylene acrylic acid copolymer (degree of neutralization, 90 mol %) was obtained. Its pH was 11.0 and its number average molecular weight was 20 nm. Reference Example 2

2.6 parts by weight of sodium hydroxide (purity, 97%) was used instead of the potassium hydroxide used in Reference Example 1 and an aqueous dispersion of sodium salt of ethylene acrylic acid copolymer (degree of neutralization, 90 mol %) was obtained. Its pH was 10 and its number average molecular weight was 40 nm.

Reference Example 3

3.3 parts by weight of ammonia water (concentration, 27%) was used instead of the potassium hydroxide used in Reference Example 1 and an aqueous dispersion of ammonium salt of ethylene acrylic acid copolymer (degree of neutralization, 75 mol %) was obtained. Its pH was 8.5 and its number average molecular weight was 70 nm.

Reference Example 4

2.5 parts by weight of metaxylenediamine (MXDA, manufactured by Mitsubishi Gas Chemical Company) was used in addition to the ammonia water in Reference Example 3 and an aqueous dispersion of ammonium/metaxylenediamine salt of ethylene acrylic acid copolymer (degree of neutralization, 100 mol %) was obtained. Its pH was 8.9 and its number average molecular weight was 130 nm. Examples 1 to 10 and Comparative Examples 1 and 2

1 wt % aqueous dispersions of ethylene acrylic acid copolymer and 1 wt % dispersions of powdered montmorillonite KUNIPIA F, manufactured by Kunimine Industrial Company, Ltd.; hereafter referred to as "silicate") were stirred for approximately 1 hour in an homogenizer, spray dry or magnetic stirrer so that the component ratios after drying and elimination of the water were in the proportions shown in Table 1. Following that, drying was effected by spray drying or box drying or on a hot plate.

The composite materials that were obtained were subjected to X-ray analysis. The results are summarized in Table 1. The baseline was 200. Table 1

The polymers in Table 1 are as follows.

EAA/K polymer originating from Reference Example 1

EAA/Na polymer originating from Reference Example 2 EAA/NH4 polymer originating from Reference Example 3

EAA/NH4/MXDA : polymer originating from Reference Example 4

The X-ray charts are presented in Figures 1 through 8. The determination conditions are presented below. Tube balls: Cu Tube voltage: 40 kilovolts Tube current: 30 milliamps Goniometer: wide angle goniometer Sampling angle: 0.010° Scanning speed: 1.00°/minute Scanning axis: 2Θ/Θ Offset angle: 0.000° Attachment: standard test material holder Monochromator: used Monochromator light reception slit: blank Divergence slit: 1° Scattering slit: 1° Light reception slit: 0.15 millimeters

When Figure 1 through Figure 7 (Examples 2 through 8) are compared with Figure 8 (Comparative Example 1), it can be seen that, in Example 1 of this invention, a composite material not containing water was made in which the peak of the (001) face was lost and in which the stratified structure of the silicate was no longer parallel.

Figure 20 through Figure 22 show transmission electron micrographs of the composite materials that were obtained in Examples 1 through 3.

Examples 11 to 20 and Comparative Example 3 Composite materials that were obtained in the same way as in Examples

1 to 10 and Comparative Example 1 and blends of poly(ethylene methacrylic acid) zinc salt (HYMILAN®1706, manufactured by the Mitsui- Du Pont Poly chemical Company) were dry blended and the blends were fused and kneaded in a unidirectional biaxial kneading machine (TEM35, manufactured by Toshiba Machinery) and the products of Examples 11 to 20 were compared with that of Comparative Example 3. When the compositions had been prepared, the fused strands at the die outlet of the biaxial extruding machine were observed visually and records were made of whether or not they were transparent. The results are shown in Table 2 (a). Injection molded test pieces (3.2 mm in thickness, 2 cm in width and 18 cm in length) were observed visually and records were made of whether there were granular masses. The results are shown in Table 2 (b). Amounts of approximately 0.03 g of pellets of the compositions that were obtained were hot pressed to make thin sheets (less than 0.5 mm in thickness and 7 to 8 cm in diameter) and observations were made to determine whether there were granular masses by the optical microscope at a magnification of 400 times. The results are shown in Table 2 (c) and in Figure 9 to Figure 19. Figure 23 to Figure 25 show the transmission electron micrographs of the composite materials obtained in Examples 8 to 10. Table 2

From the results presented above, if the molar ratio is 1 : 1, it can be seen that better dispersion of silicate can be achieved when mixing is performed with an homogenizer and drying is effected by spray drying (Example 14) than when mixing is performed with an homogenizer and box drying is performed (Example 15) or propeller mixing and spray drying are performed (Example 16).

Examples 21 to 26 and Comparative Examples 4 to 7

Composite materials that were obtained in the same way as in Example 1 were dry blended with pellets of poly(ethylene methacrylic acid) zinc salt

(HYMILAN®1706, manufactured by Mitsui-Du Pont Poly chemical Company) so that so that the quantities of composite material compounded in the composition were 4 wt %, 12 wt % and 20 wt %, the materials were fused in kneaded in a unidirectional biaxial kneading machine (TEM35, manufactured by Toshiba Machinery) and pellets of the compositions were obtained. The pellets that were obtained were pressed at 180°C to make sheet-like test material strips. They were designated as Examples 21 to 23. Composite materials that were obtained in the same way as in Example 1 were dry blended with pellets of poly(ethylene methacrylic acid) sodium salt (HYMILAN®1707, manufactured by Mitsui-Du Pont Polychemical Company), pellets of poly(ethylene methacrylic acid) magnesium salt (HYMILAN®AM 7311 manufactured by Mitsui-Du Pont Polychemical Company) or pellets of polyethylene methacrylic acid (NUCREL®N1560, manufactured by Mitsui- Du Pont Polychemical Company) so that the quantity of composite material compounded in the composition was 20 wt % and the materials were fused in kneaded in a unidirectional biaxial kneading machine (TEM35, manufactured by Toshiba Machinery) and pellets of the compositions were obtained. The pellets that were obtained were pressed at 180°C to make sheet-like test strips. They were designated as Examples 24 to 26. As comparative examples, test strips not containing composite materials were made. Determinations were made of tensile stress (in accordance with JIS K 6760) and of flexural rigidity (in accordance with JIS K 7106) using the test strips that were obtained.

Table 3 shows the results of the determinations. The transparency of the test strips was observed visually and was found to be excellent in all cases.

Table 3

The polymers in the table are as follows. E/MAA Zn : poly(ethylene methacrylic acid) zinc salt E/MAA Na : poly(ethylene methacrylic acid) sodium salt E/MAA Mg : poly(ethylene methacrylic acid) magnesium salt E/15MAA : polyethylene methacrylic acid From the results described above, it can be seen that the resin compositions containing the composite materials of this invention were transparent and that they had improved flexural rigidity.

Claims

WHAT IS CLAIMED IS:

1. A composite material characterized in that it contains an ethylene ╬▒,╬▓ ethylenically unsaturated carboxylic acid copolymer or ionomer thereof, and a stratified silicate layer and in that the ethylene acid copolymer or ionomer thereof is inserted between the silicate layers of the aforementioned stratified silicate.

2. The composite material of claim 1 wherein the ethylene acid copolymer is ethylene acrylic acid or ethylene methacrylic acid copolymer.

3. A method for the manufacture of a composite material characterized in that an ethylene ╬▒,╬▓ ethylenically unsaturated carboxylic acid copolymer or ionomer dispersion is mixed with a stratified silicate and dried, by which means the ethylene acid copolymer or ionomer thereof is inserted in the silicate layers of the aforementioned stratified silicate.

4. The method for the manufacture of a composite material as described in Claim 3 in which the drying is performed as shear is being applied.

5. The method for the manufacture of a composite material as described in Claim 3 in which the mixing is performed using an homogenizer and in which the drying is performed by a spray dryer.

6. An organic resin composition containing the composite material characterized in that it contains the composite material of Claim 1 or the composite material manufactured by the method of Claims 3, 4 or 5 and an organic polymeric material.

7. The organic resin composition containing a composite material of Claim 6 characterized in that the organic polymeric material has an affinity with the ethylene acid copolymer or ionomer thereof.