KR20060049491A - Blocking Nanocomposite Compositions and Articles Using the Same - Google Patents

Abstract

The present invention relates to a barrier nanocomposite composition and an article prepared therefrom, wherein the composition characterized in that the melt mixture and the compatibilizer of the polyolefin resin, the barrier resin and the barrier nanocomposite are dry mixed, not only has excellent barrier properties, Its excellent moldability makes it useful for the production of barrier films, barrier films as well as airtight containers.

Description

Barrier nanocomposite composition and product using the same {Gas-barrier nanocomposite composition and product using the same}

1 is a photograph of a cross section of a hollow molding container prepared from a nanocomposite composition according to an embodiment of the present invention with an electron microscope (x200).

Figure 2 is a photograph of the cross-section of the hollow molded container prepared from the nanocomposite composition according to an embodiment of the present invention with an electron microscope (x5000).

The present invention relates to a barrier nanocomposite composition and an article prepared therefrom, and more particularly, to a nano-olefin having a melt mixture and a compatibilizer of a barrier resin / blocking nanocomposite dry mixed with a polyolefin resin and having excellent barrier properties and moldability. A composite composition and an article made therefrom.

General purpose resins such as polyethylene and polypropylene are used in various fields because of their excellent moldability, mechanical properties and moisture barrier properties. Although they have excellent barrier performance against gas, they have limitations in applications such as food packaging requiring oxygen barrier properties, pesticide containers and foods requiring chemical barrier properties.

On the other hand, ethylene-vinyl alcohol copolymer and polyamide-based resin has the advantage of providing excellent gas barrier properties and transparency, but the resin content is limited because the price is higher than the general purpose resin.

Therefore, in order to reduce costs, a method of kneading barrier resins such as ethylene-vinyl alcohol and polyamide-based resins with low-cost polyolefins has been proposed, but the barrier properties are not satisfactory.

In order to improve the barrier property, nanocomposites in which nanoscale layered clay compounds are dispersed in a fully exfoliated, partially exfoliated, intercalated, and partially intercalated polymer matrix are used. Doing.

When the molded article is manufactured using the nanocomposite as described above, the morphology exhibiting the barrier property is maintained even after molding, and it is required to be excellent in workability and easy to manufacture into a sheet or a film in addition to the container.

Accordingly, the first technical problem to be achieved by the present invention is to provide a barrier nanocomposite composition having excellent mechanical strength, excellent oxygen barrier properties, organic solvent barrier properties, and moisture barrier properties, as well as excellent moldability. .

It is a second object of the present invention to provide an article prepared from the barrier nanocomposite composition.

In order to achieve the first technical problem, the first aspect of the present invention

(a) 30 to 95 parts by weight of a polyolefin resin;

(b) at least one barrier resin selected from (i) ethylene-vinyl alcohol copolymers, polyamides, ionomers and polyvinyl alcohols, and (ii) ethylene-vinyl alcohol copolymers / layered clay compound nanocomposites, polyamides. 0.5 to 60 parts by weight of a melt mixture of at least one barrier nanocomposite selected from layered clay compound nanocomposites, ionomers / layered clay compound nanocomposites and polyvinyl alcohol / layered clay compound nanocomposites; And

(i) 1 to 30 parts by weight of a compatibilizer provides a dry-blended composition.

The weight ratio of the barrier resin and the layered clay compound in the barrier nanocomposite is 58.0: 42.0 to 99.9: 0.1, preferably 85.0: 15.0 to 99.0: 1.0. If the weight ratio of the barrier resin is less than 58.0, agglomeration of the layered clay compound occurs and dispersion is not properly performed. If the weight ratio of the barrier resin exceeds 99.9, the barrier property synergistic effect is insignificant, which is not preferable.

According to one embodiment of the composition of the present invention, (i) the barrier resin and (ii) the barrier nanocomposite may be melt mixed in a weight ratio of 25: 75 to 75: 25.

According to another embodiment of the composition of the present invention, (i) the barrier resin and (ii) the barrier nanocomposite may be melt mixed at a temperature above the melting point of the resin using a coaxial twin screw or single screw extruder.

In order to achieve the second technical problem of the present invention, the second aspect of the present invention provides an article prepared from the barrier nanocomposite composition.

According to one embodiment of the article of the invention, the article can be made by blow molding, extrusion molding, press molding or injection molding.

According to another embodiment of the article of the present invention, the article may be a barrier container, barrier sheet, pipe or barrier film.

Hereinafter, the present invention will be described in more detail.

Korean Patent Application No. 2002-76575, filed by the present applicant, includes 1 to 97 parts by weight of polyolefin resin, ethylene-vinyl alcohol copolymer / lamellar clay compound nanocomposite, polyamide / lamellar clay compound nanocomposite; Nanocomposite blend composition comprising 1 to 95 parts by weight of at least one blocking nanocomposite selected from the group consisting of ionomer / layered clay compound nanocomposites and polyvinyl alcohol / layered clay compound nanocomposites and 1 to 95 parts by weight of a compatibilizer The present invention has been completed based on this.

The barrier nanocomposite composition of the present invention is characterized by dry mixing a polyolefin resin and a compatibilizer by melt-mixing the barrier nanocomposite with the barrier resin.

That is, (a) 30 to 95 parts by weight of a polyolefin resin; (b) at least one barrier resin selected from (i) ethylene-vinyl alcohol copolymers, polyamides, ionomers and polyvinyl alcohols, and (ii) ethylene-vinyl alcohol copolymers / layered clay compound nanocomposites, polyamides. 0.5 to 60 parts by weight of a melt mixture of at least one barrier nanocomposite selected from layered clay compound nanocomposite, ionomer / layered clay compound nanocomposite and polyvinyl alcohol / layered clay compound nanocomposite; And (c) 1 to 30 parts by weight of the compatibilizer is dry-blended.

The polyolefin resin used in the present invention is a high density polyethylene (HDPE, high density polyethylene), low density polyethylene (LDPE, low density polydethylene), linear low density polyethylene (LLDPE, linear low density polyethylene), ethylene-propylene copolymer, metallo One or more types selected from the group consisting of strong polyethylene and polypropylene can be used. The polypropylene is at least one selected from the group consisting of propylene homopolymers, copolymers, metallocene polypropylenes, and composite resins in which homopolymers or copolymers are added with talc and flame retardants to enhance the properties of general polypropylene. Can be used.

The polyolefin resin is preferably included in 30 to 95 parts by weight, more preferably 70 to 90 parts by weight. If the olefin resin is less than 30 parts by weight, the molding is not easy, and if it exceeds 95 parts by weight, the effect of improving barrier properties is poor, which is not preferable.

The barrier resin / blocking nanocomposite melt mixture used in the present invention is prepared by first forming a barrier nanocomposite in a peeled or partially peeled form from the barrier resin and the layered clay compound, and then melt-mixing the barrier resin with the barrier resin. Can be. Specifically, at least one barrier resin selected from nanocomposite ethylene-vinyl alcohol copolymer, polyamide, ionomer and polyvinyl alcohol, and (ii) ethylene-vinyl alcohol copolymer / layered clay compound nanocomposite, polyamide / One or more barrier nanocomposites selected from layered clay compound nanocomposites, ionomer / layered clay compound nanocomposites, and polyvinyl alcohol / layered clay compound nanocomposites may be prepared by melt mixing.

A barrier resin is added to the layered clay compound to prepare the nanocomposite by peeling or partially peeling the layered clay compound to a nano size to lengthen the gas and liquid permeation path inside the barrier resin so that the water barrier and the liquid barrier of the barrier resin itself are blocked. In addition to increasing the properties, the layered clay compound has a processing advantage of suppressing the sagging of the parison during blow molding by increasing the melt strength of the polyolefin in the continuous phase.

By using the molten mixture of the barrier nanocomposite and the barrier resin, the processing temperature range can be widened during molding. Specifically, it is possible to broaden moldability and molding use by selecting blend components and adjusting blend ratios in accordance with processing temperature conditions required for molding products.

In order to obtain a molten mixture of the barrier resin / blockable nanocomposite, melt kneading is preferably performed at a temperature of 175 to 270 ° C.

The layered clay compound used in the present invention is preferably an organic layered clay compound in which an organic material is interposed between layers of the layered clay compound. The organic content in the layered clay compound is preferably 1-45% by weight. If the organic content is less than 1% by weight, the compatibility between the layered clay compound and the polymer is inferior, and if the content exceeds 45% by weight, the intercalation of the polymer chain is not easy, which is not preferable.

The layered clay compound may include montmorillonite, bentonite, kaolinite, mica, hectorite, fluorohectorite, saponite, and vadell Beidelite, nontronite, stevensite, vermiculite, hallositd, volkonskoite, suconite, suconite, magadite, and At least one selected from the group consisting of kenyalite is preferable, and the organic material is 1 to 4 quaternary ammonium, phosphonium, maleate, succinate, acrylate, benzylic hydrogen, dimethyl distearyl ammonium, oxazoline It is preferable that it is an organic substance containing a functional group selected from the group consisting of.

The barrier resin and the barrier nanocomposite are preferably combined in a weight ratio of 25: 75 to 75: 25. Outside the above range, too much barrier resin is difficult to obtain a barrier synergistic effect by mixing with the barrier nanocomposite, too little barrier resin may cause a problem of lowering the impact strength of the final molded product.

It is preferable that the ethylene content of the ethylene-vinyl alcohol copolymer used for this invention is 10-50 mol%. If the content of the ethylene is less than 10 mol%, workability is lowered and melt molding is difficult. If the content of the ethylene is more than 50 mol%, oxygen barrier property and liquid barrier property are not sufficient.

Polyamides used in the present invention are 1) nylon 4.6, 2) nylon 6, 3) nylon 6.6, 4) nylon 6.10, 5) nylon 7, 6) nylon 8, 7) nylon 9, 8) nylon 11, 9) Nylon 12, 10) Nylon 46, 11) MXD6, 12) Amorphous polyamide, 13) Copolyamide having two or more components in 1) to 12), or 14) 1) to 12) Mixtures of two or more may be selected and used.

The amorphous polyamide refers to a polyamide that lacks crystallinity without an endothermic crystalline melting point peak as measured by differential scanning calorimetry (DSC) (ASTM D-3417, 10 ^° C./min).

Generally polyamides can be prepared from diamines and dicarboxylic acids. Examples of diamines include hexamethylenediamine, 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, bis (4-aminocyclohexyl) methane, 2,2 -Bis (4-aminocyclohexyl) isopropylidine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, meta-xylylenediamine, 1,5-diaminopentane, 1,4- Diaminobutane, 1,3-diaminopropane, 2-ethyldiaminobutane, 1,4-diaminomethylcyclohexane, methane-xylylenediamine, alkyl substituted or unsubstituted m-phenylenediamine and p-phenyl Rendiamine and the like. Examples of dicarboxylic acids include alkyl substituted or unsubstituted isophthalic acid, terephthalic acid, adipic acid, sebacic acid, butanedicarboxylic acid and the like.

Polyamides prepared from aliphatic diamines and aliphatic dicarboxylic acids are traditional semicrystalline polyamides (also referred to as crystalline nylon) and are not amorphous polyamides. Polyamides prepared from aromatic diamines and aromatic dicarboxylic acids are difficult to process under conventional melt processing conditions.

Thus, amorphous polyamide can be preferably prepared when either one of diamine and dicarboxylic acid is aromatic and the other is aliphatic. At this time, the aliphatic groups of the amorphous polyamide are preferably aliphatic having 1 to 15 carbon atoms or alicyclic alkyl having 4 to 8 carbon atoms. The aromatic groups of the amorphous polyamide are preferably mono or bicyclic aromatic groups having substituents of 1 to 6 carbon atoms. However, such amorphous polyamides are not necessarily suitable for the present invention, for example, metaxylenediamine adipamide is undesirable because it crystallizes easily under the heating conditions typical for thermoforming operations and also crystallizes when oriented.

Specific examples of amorphous polyamides suitable for the present invention include hexamethylenediamine isophthalamide, hexamethylene diamine isophthalamide / terephthalamide terpolymer having a ratio of isophthalic acid / terephthalic acid of 99/1 to 60/40, 2,2, Mixtures of 4- and 2,4,4, -trimethylhexamethylenediamine terephthalamide, isophthalic acid or terephthalic acid, or mixtures thereof and copolymers of hexamethylenediamine or 2-methylpentamethylenediamine. Polyamides based on hexamethylenediamine isophthalamide / terephthalamide with a high content of terephthalic acid may also be useful, but a second diamine such as 2-methyldiaminopentane must be mixed to produce a processable amorphous polyamide. do.

The amorphous polyamide may be a polymer based solely on the monomers containing small amounts of lactam species as comonomers such as caprolactam or lauryl lactam. It is important that the polyamide be amorphous as a whole. Therefore, small amounts of the comonomers can be incorporated as long as they do not impart crystallinity to the polyamide. Liquid or solid plasticizers such as glycerol, sorbitol or toluenesulfonamide (Santicizer 8 Monsanto) may also be included together in the amorphous polyamide at up to about 10% by weight. For most applications the Tg of the amorphous polyamide (measured in a dry state, i.e. containing up to about 0.12% by weight of moisture) is from about 70 ^o C to about 170 ^o C, preferably from about 80 ^o C to 160 ^o must be in the C range. As such, certain unblended amorphous polyamides have a Tg of approximately 125 ^° C. upon drying. The lower limit of Tg is not clear and 70 ^O C is an approximate lower limit. The upper limit of Tg is also not clear. However, using polyamides above about 170 ^o C is not easily thermoformed. Therefore, polyamides having aromatic groups in both the acid and amine moieties cannot be thermoformed due to too high Tg and are therefore generally unsuitable for the purposes of the present invention.

The polyamide component of b) also comprises at least one semicrystalline polyamide. The term refers to traditional semicrystalline polyamides, which are generally made of lactams or amino acids, such as nylon 6 or nylon 11, or diamines such as hexametalenediamine, dibasic acids such as succinic acid, adipic acid, or sebacic acid. It is prepared by condensation. Copolymers of such polyamides and terpolymers, such as those of hexamethylenediamine / adipic acid and caprolactam (nylon 6,66), are included. Mixtures of two or more crystalline polyamides may also be used. Both semi-crystalline and amorphous polyamides are prepared by condensation polymerization well known to those skilled in the art. The ionomer used in the present invention is preferably a copolymer of acrylic acid and ethylene, and has a melt index of 0.1 to 10 g / 10 min ( Preferably at 190 ° C and 2160 g).

The molten mixture of the barrier resin / blocking nanocomposite is preferably included in an amount of 0.5 to 60 parts by weight, and more preferably 8 to 30 parts by weight, based on 100 parts by weight of the nanocomposite composition. If the molten mixture of the barrier resin / blocking nanocomposite is less than 0.5 part by weight, the effect of improving barrier properties is small, and if it exceeds 60 parts by weight, the processing is not easy, which is not preferable.

The compatibilizer used in the present invention functions to improve the compatibility between the polyolefin resin and the barrier resin / blocking nanocomposite to form a composition having a stable structure.

It is preferable to use the hydrocarbon type polymer containing a polar group as said compatibilizer. In the case of using a hydrocarbon-based polymer containing a polar group, the affinity between the compatibilizer and the polyolefin resin and the compatibilizer with the blocking resin / blocking nanocomposite becomes good due to the hydrocarbon polymer portion composed of the polymer base. A stable structure is formed in the resin composition obtained.

The compatibilizer is an epoxy modified polystyrene copolymer, an ethylene-ethylene anhydride-acrylic acid copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-alkyl acrylate-acrylic acid copolymer, maleic anhydride modified (graft) high density polyethylene, maleic anhydride Modified (grafted) linear low density polyethylene, ethylene-alkyl methacrylate-methacrylic acid copolymer, ethylene-butylacrylate copolymer, ethylene-vinylacetate copolymer, and maleic anhydride modified (graft) ethylene-vinylacetate copolymer It is possible to use a mixture of one or more selected from the group consisting of or a modified product thereof.

The compatibilizer used in the present invention is preferably included in 1 to 30 parts by weight, more preferably 2 to 20 parts by weight. If the compatibilizer is less than 1 part by weight, the mechanical properties of the molded product are bad at the time of molding the composition, and if it exceeds 30 parts by weight, product molding processing of the composition is not easy, which is not preferable.

When the epoxy-modified polystyrene copolymer is used as a compatibilizer, a branch comprising 70 to 99 parts by weight of styrene and 1 to 30 parts by weight of the epoxy compound represented by Formula 1 and 1 to 80 parts by weight of an acrylic monomer of Formula 2 is used. Preferred copolymers include:

[Formula 1]

In Chemical Formula 1,

R and R 'are each independently residues of an aliphatic C1-C20 or C5-C20 aromatic compound having a double bond group at the terminal of the molecular structure.

[Formula 2]

The maleic anhydride-modified (graft) high density polyethylene, maleic anhydride-modified (graft) linear low-density polyethylene, or maleic anhydride-modified (graft) ethylene-vinylacetate copolymer each contains 0.1 maleic anhydride based on 100 parts by weight of the main chain. It is preferable that it is comprised from the branch which consists of 10 weight part. If the content of maleic anhydride is less than 0.1 part by weight, it is difficult to exhibit performance as a compatibilizer, and if it is 10 parts by weight or more, it is not preferable because of a lot of smell when molding the composition.

The barrier nanocomposite composition according to the present invention is molded to prepare a barrier container. The barrier nanocomposite composition is dry-blended and molded while maintaining the morphology of the barrier nanocomposite, and even in the manufactured molded article, the exfoliated nanocomposite maintains a structure in which the exfoliated nanocomposite is dispersed in a polyolefin matrix. Done.

At this time, the molding method may use a conventional molding method such as blow molding, extrusion molding, compression molding, injection molding.

In addition to the barrier container, it is also possible to produce barrier sheets or barrier films.

The barrier container or barrier sheet may be a multilayer barrier container or multilayer barrier sheet further comprising an adhesive layer and a polyolefin layer.

For example, it may be a barrier sheet or barrier container made from a five-layer film composed of HDPE / adhesive layer / blocking nanocomposite composition / adhesive layer / HDPE of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are provided to illustrate the present invention and are not intended to limit the scope of the present invention.

Example

The materials used in the examples below are as follows:

EVOH: product E105B from Kuraray (Japan)

Amorphous nylon: SELAR 2072 from Dupont (USA)

Nylon 6, 12: Dupont (USA), Zytel 158L

Nylon 6: KP Chemicals EN 500

HDPE-g-MAH: compatibilizer. CRAMPTON PRODUCT PB3009

HDPE: LG Chemicals ME6000

Ionomer: Dupont (USA) SURLYN 8527

Clay: SCP Product Closite 30B

Thermal Stabilizer: Product of Songwon Industry IR 1098

Preparation Example 1 (Preparation of EVOH-Layered Clay Compound Nanocomposite)

Ethylene-vinyl alcohol copolymer (EVOH, E-105B (ethylene content 44 mol%), Japan Kuraray Co., Melt Index: 5.5 g / 10min, Density: 1.14 g / cm3) 97 wt% 3 wt% of montmorillonite (Southern Lamellar Clay Compounds Products, USA C2OA) which was introduced into the main hopper of the directional rotary twin screw extruder, Φ40) and layered clay compound, and was heated to the combined weight of EVOH and Lamellar Clay Compound After 0.1 parts by weight of stabilizer IR 1098 was separately introduced into a side feeder, an ethylene-vinyl alcohol copolymer / layered clay compound nanocomposite was prepared in pellet form. At this time, the extrusion temperature was 180-190-200-200-200-200-200 ° C., the screw speed was 300 rpm, and the discharge condition was 15 kg / hr.

Preparation Example 2 (Preparation of Nylon 6-Layered Clay Compound Nanocomposite)

97% by weight of polyamide (nylon 6) was added to the main hopper of a twin screw extruder (SM Platec co-rotating twin screw extruder, Φ40), and 3% by weight of montmorillonite organicated with a layered clay compound and the polyamide and layered 0.1 parts by weight of thermal stabilizer IR 1098 was separately injected into the side feeder based on the combined weight of the clay compound, and then a nylon 6 / layered clay compound nanocomposite was prepared in pellet form. At this time, the extrusion temperature was 220-225-245-245-245-245-245 ° C., the screw speed was 300 rpm, and the discharge condition was 40 kg / hr.

Preparation Example 3 (Preparation of Nylon 6,12-Layered Clay Compound Nanocomposite)

95% by weight of polyamide (nylon 6,12) was added to the main hopper of a twin screw extruder (SM Platec co-rotating twin screw extruder, Φ 40), and 5% by weight of montmorillonite organicated with a layered clay compound and the polyamide 0.1 parts by weight of thermal stabilizer IR 1098 was separately injected into the side feeder, and nylon 6,12 / layered clay compound nanocomposites were prepared in pellet form. At this time, the extrusion temperature was 225-245-245-245-245-245-240 ℃, the screw speed is 300rpm, the discharge condition was 40kg / hr.

Preparation Example 4 (Amorphous Nylon-Layered Clay Compound Nanocomposite)

95% by weight of polyamide (amorphous nylon) was introduced into a main hopper of a twin screw extruder (SM Platec co-rotating twin screw extruder, Φ40), and 5% by weight of montmorillonite organicated with a layered clay compound and the polyamide 0.1 parts by weight of thermal stabilizer IR 1098 was separately injected into the side feeder based on the combined weight of the layered clay compound, and then amorphous nylon / layered clay compound nanocomposite was prepared in pellet form. At this time, the extrusion temperature was 215-225-235-235-235-235-230 ° C, the screw speed was 300 rpm, and the discharge condition was 40 kg / hr.

Preparation Example 5 (Ionomer-Layered Clay Compound Nanocomposite Preparation)

95% by weight of ionomer was introduced into the main hopper of a twin screw extruder (SM Platec co-rotating twin screw extruder, Φ40), and 5% by weight of montmorillonite organicated with a layered clay compound and the weight of the ionomer and the layered clay compound were added. 0.1 parts by weight of thermal stabilizer IR 1098 was separated and injected into a side feeder, and then an ionomer / layered clay compound nanocomposite was prepared in pellet form. At this time, the extrusion temperature was 220-230-235-235-235-235-230 ° C., the screw speed was 300 rpm, and the discharge condition was 40 kg / hr.

Example 1

40 parts by weight of the EVOH nanocomposite prepared in Preparation Example 1 and 60 parts by weight of EVOH were extruded at 190-200-210-210-210-200 ° C. and melt kneaded to prepare an EVOH nanocomposite / EVOH melt mixture. 70 parts by weight of the high density polyethylene (HDPE) to 20 parts by weight of the melt mixture, compatibilizer (maleic anhydride modified (graft)) high density polyethylene (HDPE-g-MAH, uniroyal chemical, USA, PB3009 (containing 1% MAH), melt index : 5 g / 10min, density: 0.95 g / cm 3) 10 parts by weight of dry mix, and then blow-molded to make a container of 1000ml, processing temperature is 180-195-195-195-195-190 ℃, screw The speed was 22 rpm, and the dry mixture was extruded to form a 30 μm thick film, with a processing temperature of 185-195-195-195-195-190 ° C. and a screw speed of 16 rpm.

Example 2

40 parts by weight of the EVOH nanocomposite prepared in Preparation Example 1 and 60 parts by weight of nylon 6 were extruded at 215-220-210-210-210-200 ° C and melt kneaded to obtain an EVOH nanocomposite / nylon 6 melt mixture. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 190-225-225-220-210. ℃, the screw speed was 23rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-235 ° C. and the screw speed was 16 rpm.

Example 3

40 parts by weight of the EVOH nanocomposite prepared in Preparation Example 1 and 60 parts by weight of nylon 6,12 were extruded at 225-235-245-245-245-240 ° C to melt-kneaded to melt the EVOH nanocomposite / nylon 6,12 melt mixture. Got it. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 200-220-230-225-210. ℃, screw speed was 21rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-235 ° C. and the screw speed was 14 rpm.

Example 4

40 parts by weight of the EVOH nanocomposite prepared in Preparation Example 1 and 60 parts by weight of the amorphous nylon were extruded at 225-235-245-245-245-240 ° C and melt-kneaded to obtain an EVOH nanocomposite / amorphous nylon melted mixture. 70 parts by weight of high density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 185-200-210-200. -190 ° C and screw speed 22 rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-235 ° C. and the screw speed was 16 rpm.

Example 5

40 parts by weight of the EVOH nanocomposite prepared in Preparation Example 1 and 60 parts by weight of the ionomer were extruded at 225-235-245-245-245-240 ° C. and melt kneaded to obtain an EVOH nanocomposite / ionomer melt mixture. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 190-210-225-220-210. ℃, screw speed was 23rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-235 ° C. and the screw speed was 14 rpm.

Example 6

40 parts by weight of the nylon 6 nanocomposite prepared in Preparation Example 2 and 60 parts by weight of EVOH were extruded at 220-235-245-245-245-240 ° C. and melt kneaded to obtain a nylon 6 nanocomposite / EVOH melt mixture. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the melt mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 185-195-225-215-200. ℃, screw speed was 14rpm. In addition, the dry mixture was extruded to form a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-235 ° C. and the screw speed was 13 rpm.

Example 7

40 parts by weight of the nylon 6 nanocomposite prepared in Preparation Example 2 and 60 parts by weight of nylon 6 were extruded at 220-235-245-245-245-240 ° C. and melt kneaded to obtain a nylon 6 nanocomposite / nylon 6 melt mixture. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 195-215-220-215-200. ℃, screw speed was 24rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-245-245-245-245-240 ° C. and the screw speed was 13 rpm.

Example 8

40 parts by weight of nylon 6 nanocomposite prepared in Preparation Example 2 and 60 parts by weight of nylon 6,12 were extruded at 230-240-245-245-245-235 ° C. and melt kneaded to melt the nylon 6 nanocomposite / nylon 6,12 A mixture was obtained. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 195-225-225-215-200. ℃, screw speed was 24rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-245-245-245 ° C. and the screw speed was 12 rpm.

Example 9

40 parts by weight of nylon 6 nanocomposite prepared in Preparation Example 2 and 60 parts by weight of amorphous nylon were extruded at 230-240-245-245-245-235 ° C. to melt-kneading to melt the nylon 6 nanocomposite / amorphous nylon melt mixture. Got it. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 185-220-220-215-200. ℃, screw speed was 24rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-235 ° C. and the screw speed was 15 rpm.

Example 10

40 parts by weight of the nylon 6 nanocomposite prepared in Preparation Example 2 and 60 parts by weight of the ionomer were extruded at 210-225-235-235-235-230 ° C. and melt kneaded to obtain a nylon 6 nanocomposite / ionomer melt mixture. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 185-235-235-235-235 -230 ° C, screw speed was 21 rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-240-240 ° C. and the screw speed was 12 rpm.

Example 11

40 parts by weight of the nylon 6,12 nanocomposite prepared in Preparation Example 3 and 60 parts by weight of EVOH were extruded at 220-235-245-245-245-240 ° C. and melt kneaded to melt the nylon 6,12 nanocomposite / EVOH melt mixture. Got it. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 185-225-225-215-200. ℃, screw speed was 21rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 215-225-235-235-235-240 ° C. and the screw speed was 15 rpm.

Example 12

40 parts by weight of nylon 6,12 nanocomposite prepared in Preparation Example 3 and 60 parts by weight of nylon 6 were melt-kneaded by extruding at 220-235-245-245-245-240 ° C. to melt nylon 6,12 nanocomposite / nylon 6 A mixture was obtained. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the melt mixture, followed by blow molding to make a container of 1000 ml, at which time the processing temperature was 185-245-245-245-240. ℃, screw speed was 23rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 205-225-235-240-240-245 ° C. and the screw speed was 12 rpm.

Example 13

40 parts by weight of nylon 6,12 nanocomposite prepared in Preparation Example 3 and 60 parts by weight of nylon 6,12 were extruded at 220-235-245-245-245-240 ° C. to melt-kneaded to nylon 6,12 nanocomposite / nylon 6,12 melt mixtures were obtained. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the melt mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 190-215-230-230-. 225-210 ° C., screw speed 24 rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 210-225-245-245-245-245 ° C. and the screw speed was 13 rpm.

Example 14

40 parts by weight of nylon 6,12 nanocomposite prepared in Preparation Example 3 and 60 parts by weight of amorphous nylon were extruded at 220-235-235-235-235-230 ° C. to melt-kneaded to nylon 6,12 nanocomposite / amorphous A nylon melt mixture was obtained. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 190-220-225-215-200. ℃, screw speed was 24rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-235 ° C. and the screw speed was 12 rpm.

Example 15

40 parts by weight of nylon 6,12 nanocomposite prepared in Preparation Example 3 and 60 parts by weight of ionomer were extruded and melt kneaded at 215-235-245-245-245-240 ° C. to melt the nylon 6,12 nanocomposite / ionomer melt mixture. Got it. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 195-225-225-225-200. ℃, screw speed was 22rpm. In addition, the dry mixture was extruded to form a film having a thickness of 30 μm, wherein the processing temperature was 225-235-235-235-235-240 ° C. and the screw speed was 13 rpm.

Example 16

40 parts by weight of the amorphous nylon nanocomposite prepared in Preparation Example 4 and 60 parts by weight of EVOH were extruded at 205-215-215-215-215-210 ° C and melt kneaded to obtain an amorphous nylon nanocomposite / EVOH melt mixture. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the melt mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 185-205-215-210-200. ℃, screw speed was 20rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-235 ° C. and the screw speed was 13 rpm.

Example 17

40 parts by weight of the amorphous nylon nanocomposite prepared in Preparation Example 4 and 60 parts by weight of nylon 6 were melt-kneaded by extrusion at 225-235-235-235-235-230 ° C to melt the amorphous nylon nanocomposite / nylon 6 melt mixture. Got it. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 195-215-220-215-200. ℃, screw speed was 23rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-240 ° C. and the screw speed was 13 rpm.

Example 18

40 parts by weight of amorphous nylon nanocomposites prepared in Preparation Example 4 and 60 parts by weight of nylon 6,12 were extruded at 225-240-240-240-240-235 ° C. to melt-kneading amorphous nylon nanocomposites / nylon 6, 12 melt mixtures were obtained. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, at which time the processing temperature was 200-220-225-215-205. ℃, screw speed was 22rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 215-225-235-235-235-240 ° C. and the screw speed was 12 rpm.

Example 19

40 parts by weight of amorphous nylon nanocomposite prepared in Preparation Example 4 and 60 parts by weight of amorphous nylon were extruded and melt kneaded at 225-240-240-240-240-235 ° C. to melt amorphous nylon nanocomposite / amorphous nylon. A mixture was obtained. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 190-205-215-205-195. ℃, screw speed was 24rpm. In addition, the dry mixture was extruded to form a film having a thickness of 30 μm, wherein the processing temperature was 200-215-215-215-215-220 ° C. and the screw speed was 13 rpm.

Example 20

40 parts by weight of the amorphous nylon nanocomposite prepared in Preparation Example 4 and 60 parts by weight of the ionomer were extruded at 225-240-240-240-240-235 ° C. and melt kneaded to obtain an amorphous nylon nanocomposite / ionomer melt mixture. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 195-215-220-215-205. ℃, screw speed is 22rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-240 ° C. and the screw speed was 12 rpm.

Example 21

40 parts by weight of the ionomer nanocomposite prepared in Preparation Example 5 and 60 parts by weight of EVOH were extruded at 225-235-235-240-240-235 ° C. and melt kneaded to obtain an ionomer nanocomposite / EVOH melt mixture. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 190-215-220-215-200. ℃, screw speed was 2. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 210-225-235-235-235-240 ° C. and the screw speed was 14 rpm.

Example 22

40 parts by weight of the ionomer nanocomposite prepared in Preparation Example 5 and 60 parts by weight of nylon 6 were extruded at 225-240-245-245-245-240 ° C. and melt kneaded to obtain an ionomer nanocomposite / nylon 6 melt mixture. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 195-215-225-220-210. ℃, screw speed was 23rpm. In addition, the dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-240 ° C. and the screw speed was 13 rpm.

Example 23

40 parts by weight of the ionomer nanocomposite prepared in Preparation Example 5 and 60 parts by weight of nylon 6,12 were extruded at 225-245-245-245-245-240 ° C. and melt kneaded to melt the ionomer nanocomposite / nylon 6,12 melt mixture. Got it. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 225-245-245-245-245. The dry mixture was extruded to form a 30 μm thick film, with a processing temperature of 220-235-235-235-235-240 ° C. and a screw speed of 14 rpm. .

Example 24

40 parts by weight of the ionomer nanocomposite prepared in Preparation Example 5 and 60 parts by weight of the amorphous nylon were extruded at 215-230-235-235-235-230 ° C and melt kneaded to obtain an ionomer nanocomposite / amorphous nylon melt mixture. 70 parts by weight of high-density polyethylene (HDPE) and 10 parts by weight of a compatibilizer were mixed with 20 parts by weight of the molten mixture, followed by blow molding to make a container of 1000 ml, wherein the processing temperature was 185-215-220-215-200. ℃, screw speed was 24rpm. The dry mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 215-235-235-235-235-240 ° C. and the screw speed was 15 rpm.

Example 25

40 parts by weight of nylon 6 nanocomposite prepared in Preparation Example 2 and 60 parts by weight of amorphous nylon were extruded at 230-240-245-245-245-235 ° C. to melt-kneading to melt the nylon 6 nanocomposite / amorphous nylon melt mixture. Obtained 70 weight part of high density polyethylene (HDPE) and 10 weight part of compatibilizers were dry-mixed to 20 weight part of said melt mixtures, and the nanocomposite composition was obtained. Using the nanocomposite composition prepared by blow molding into a structure of five layers (HDPE / adhesive / nanocomposite composition / adhesive / HDPE) to make a container of 1000ml, the processing temperature is 195-225-225-225- 215 ″ ° C., screw speed was 23 rpm. Also, the nanocomposite composition was extruded into a structure of 5 layers (HDPE / adhesive / nanocomposite composition / adhesive / HDPE) to make a film having a thickness of 30 μm. When the processing temperature was 220-235-235-235-235-240 ℃, the screw speed was 12rpm.

Example 26

40 parts by weight of nylon 6 nanocomposite prepared in Preparation Example 2 and 60 parts by weight of amorphous nylon were extruded at 230-240-245-245-245-235 ° C. to melt-kneading to melt the nylon 6 nanocomposite / amorphous nylon melt mixture. Obtained 94 parts by weight of high density polyethylene (HDPE) and 2 parts by weight of a compatibilizer were dry mixed to 4 parts by weight of the molten mixture to obtain a nanocomposite composition. Using the nanocomposite composition prepared by blow molding into a structure of five layers (HDPE / adhesive / nanocomposite composition / adhesive / HDPE) to make a container of 1000ml, the processing temperature is 195-225-225-225- 215 ° C., screw speed was 23 rpm. Also, the nanocomposite composition was extruded into a structure of 5 layers (HDPE / adhesive / nanocomposite composition / adhesive / HDPE) to make a film having a thickness of 30 μm. The processing temperature was 220-235-235-235-235-240 ° C and the screw speed was 12 rpm.

Example 27

40 parts by weight of nylon 6 nanocomposite prepared in Preparation Example 2 and 60 parts by weight of amorphous nylon were extruded at 230-240-245-245-245-235 ° C. to melt-kneading to melt the nylon 6 nanocomposite / amorphous nylon melt mixture. Obtained The nanocomposite composition was obtained by dry mixing 35 parts by weight of high density polyethylene (HDPE) and 5 parts by weight of a compatibilizer to 60 parts by weight of the melt mixture. Using the nanocomposite composition prepared by blow molding into a structure of five layers (HDPE / adhesive / nanocomposite composition / adhesive / HDPE) to make a container of 1000ml, the processing temperature is 195-225-225-225- 215 ° C., screw speed was 23 rpm. Also, the nanocomposite composition was extruded into a structure of 5 layers (HDPE / adhesive / nanocomposite composition / adhesive / HDPE) to make a film having a thickness of 30 μm. The processing temperature was 220-235-235-235-235-240 ° C and the screw speed was 12 rpm.

Comparative Example 1

70 parts by weight of the high density polyethylene, 10 parts by weight of the compatibilizer and 20 parts by weight of the ethylene-vinyl alcohol copolymer were mixed and then blow molded to form a 1000 ml container. At this time, the processing temperature was 180-190-190-185-180 ° C, and the screw speed was 22 rpm. In addition, the mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-240 ° C. and the screw speed was 14 rpm.

Comparative Example 2

70 parts by weight of high density polyethylene, 10 parts by weight of compatibilizer and 20 parts by weight of nylon 6 were mixed and then blow molded to make a 1000 ml container. At this time, the processing temperature was 210-220-225-215-200 ° C., and the screw speed was 21 rpm. In addition, the mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-240 ° C. and the screw speed was 13 rpm.

Comparative Example 3

70 parts by weight of high density polyethylene, 10 parts by weight of compatibilizer and 20 parts by weight of nylon 6,12 were mixed and then blow molded to make a 1000 ml container. At this time, the processing temperature was 215-225-230-215-205 ° C, and the screw speed was 22 rpm. In addition, the mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-240-240-240-245 ° C. and the screw speed was 12 rpm.

Comparative Example 4

70 parts by weight of the high density polyethylene, 10 parts by weight of the compatibilizer and 20 parts by weight of the ionomer were mixed and then blow molded to form a 1000 ml container. At this time, the processing temperature was 205-215-225-220-215 ℃, screw speed was 14rpm. In addition, the mixture was extruded to make a film having a thickness of 30 μm, wherein the processing temperature was 220-235-235-235-235-240 ° C. and the screw speed was 14 rpm.

The barrier test was performed on the hollow molded containers and films prepared in Examples and Comparative Examples, and the results are shown in Tables 1 and 2 below.

Barrier test

Toluene and M15 (a mixture of 85% toluene / isooctane (50/50) and 15% methanol) were respectively filled in the containers prepared in Examples and Comparative Examples, weighed, and weighed for 15 days in a drying oven at 50 ° C. The weight after standing and weighed was checked.

In addition, the films prepared in Examples and Comparative Examples were measured using a gas permeability meter (Mocon OX-TRAN 2/20, U.S.A.) after being left at a temperature of 23 ° C. and a relative humidity of 50% for 1 day.

Blocking test of molding container division Toluene (weight loss rate,%) M15 (% weight loss) Example 1 0.114 0.150 Example 2 0.085 0.098 Example 3 0.083 0.091 Example 4 0.135 0.177 Example 5 0.196 0.203 Example 6 0.092 0.099 Example 7 0.051 0.067 Example 8 0.059 0.063 Example 9 0.076 0.092 Example 10 0.122 0.138 Example 11 0.120 0.135 Example 12 0.044 0.048 Example 13 0.038 0.040 Example 14 0.059 0.067 Example 15 0.093 0.098 Example 16 0.120 0.158 Example 17 0.085 0.095 Example 18 0.064 0.073 Example 19 0.095 0.106 Example 20 0.145 0.153 Example 21 0.352 0.382 Example 22 0.288 0.295 Example 23 0.264 0.283 Example 24 0.293 0.309 Example 25 0.463 0.569 Example 26 0.692 0.853 Example 27 0.341 0.483 Comparative Example 1 1.679 3.324 Comparative Example 2 1.452 3.028 Comparative Example 3 1.311 2.540 Comparative Example 4 3.806 4.237

Barrier Test of Film division Oxygen transmittance (ml / m ² x24hrs 1atm) Example 1 126.27 Example 2 93.26 Example 3 84.26 Example 4 143.25 Example 5 183.49 Example 6 92.67 Example 7 53.69 Example 8 63.99 Example 9 83.28 Example 10 134.52 Example 11 131.48 Example 12 52.24 Example 13 41.38 Example 14 62.06 Example 15 119.42 Example 16 133.19 Example 17 110.42 Example 18 77.04 Example 19 101.06 Example 20 235.63 Example 21 489.18 Example 22 432.83 Example 23 415.90 Example 24 441.84 Example 25 415.49 Example 26 538.17 Example 27 885.92 Comparative Example 1 2238.19 Comparative Example 2 1324.51 Comparative Example 3 1255.66 Comparative Example 4 3342.01

As can be seen in Table 1 and Table 2, the container and the film according to the embodiment using a composition obtained by dry mixing a molten mixture of the barrier resin / blocking nanocomposite with the polyolefin resin and the compatibilizer, mixed only the barrier resin. All showed excellent barrier properties compared to the container and film according to the comparative example using one composition.

In addition, the cross-sectional view of the blow molding vessel manufactured in Example 7 is shown in FIG. 1 (x200) and FIG. 2 (x5000). 1 and 2, it can be seen that the container prepared from the barrier nanocomposite composition according to the present invention exhibits excellent barrier properties by forming a barrier nanocomposite dispersed phase in the polyolefin continuous phase.

Since the nanocomposite composition of the present invention has excellent barrier properties and moldability, the articles prepared therefrom have excellent performance as barrier containers, barrier sheets and barrier films.

Claims (19)

(a) 30 to 95 parts by weight of a polyolefin resin; (b) at least one barrier resin selected from (i) ethylene-vinyl alcohol copolymers, polyamides, ionomers and polyvinyl alcohols, and (ii) ethylene-vinyl alcohol copolymers / layered clay compound nanocomposites, polyamides. 0.5 to 60 parts by weight of a melt mixture of at least one barrier nanocomposite selected from a layered clay compound nanocomposite, an ionomer / layered clay compound nanocomposite and a polyvinyl alcohol / layered clay compound nanocomposite; And (c) 1 to 30 parts by weight of the compatibilizer is dry-blending nanocomposite composition. The composition according to claim 1, wherein (i) the barrier resin and (ii) the barrier nanocomposite are melt mixed in a weight ratio of 25:75 to 75:25. The composition according to claim 1, wherein the polyolefin resin of (a) is at least one selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-propylene polymer and ethylene-propylene copolymer. The method of claim 1, wherein the layered clay compound in the blocking nanocomposite of (ii) is montmorillonite, bentonite, kaolinite, mica, hectorite, hexafluoride, saponite, baydelite, nontronite, A composition characterized in that it is at least one selected from the group consisting of stevensite, vermiculite, halosite, volconscote, stoneconite, margotite and kenyalite. The composition according to claim 1, wherein the layered clay compound in the blocking nanocomposite of (ii) comprises 1 to 45% by weight of organic matter in the layered clay compound. 6. The functional group of claim 5, wherein the organic material is selected from the group consisting of primary to quaternary ammonium, phosphonium, maleate, succinate, acrylate, benzylic hydrogen dimethyl distearylammonium and oxazoline. Composition comprising the organic material. The composition according to claim 1, wherein the ethylene content of the ethylene-vinyl alcohol copolymer of (i) is 10 to 50 mol%. The method of claim 1, wherein the polyamide of (i) is 1) nylon 4.6, 2) nylon 6, 3) nylon 6.6, 4) nylon 6.10, 5) nylon 7, 6) nylon 8, 7) nylon 9, 8 Nylon 11, 9) Nylon 12, 10) Nylon 46, 11) MXD6, 12) Amorphous polyamide, 13) Copolymerized polyamide having two or more components in 1) to 12) polyamide, or 14) 1) At least one member selected from the group consisting of a mixture of two or more of the polyamides of ˜12). The composition of claim 1, wherein the ionomer of (i) is in the range of 0.1 to 10 g / 10 min (190 ° C, 2,160 g) of melt index. The method of claim 1, wherein the compatibilizer is an ethylene-ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-alkyl acrylate-acrylic acid copolymer, maleic anhydride modified (grafted) high density polyethylene, maleic anhydride modified (Graft) Consists of linear low density polyethylene, ethylene-alkyl methacrylate-methacrylic acid copolymer, ethylene-butyl acrylate copolymer, ethylene-vinylacetate copolymer and maleic anhydride modified (graft) ethylene-vinyl acetate copolymer At least one member selected from the group. The composition of claim 1, wherein the (i) barrier resin and the (ii) barrier nanocomposite are melt mixed at a temperature above the melting point of the resin using a coaxial twin screw extruder or a single screw extruder. An article made by molding the nanocomposite composition according to claim 1. The article of claim 12, wherein the article is manufactured by blow molding, extrusion molding, press molding, or injection molding. 13. The article of claim 12, wherein the article is a barrier container. 13. The article of claim 12, wherein the article is a barrier pipe. 13. The article of claim 12, wherein the article is a barrier sheet. 15. The article of claim 14, wherein the barrier container is a multilayer barrier container further comprising an adhesive layer and a polyolefin resin layer. 17. The article of claim 16, wherein the barrier sheet is a multilayer barrier sheet further comprising an adhesive layer and a polyolefin resin layer. The article of claim 1, wherein the weight ratio of the blocking resin to the layered clay compound in the blocking nanocomposite is 58.0: 42.0 to 99.9: 0.1.

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