KR100874031B1 - Nanocomposite compositions with excellent barrier properties and articles made therefrom - Google Patents

Abstract

The present invention relates to a nanocomposite composition having excellent barrier properties and a barrier article prepared therefrom, comprising: a polyolefin resin; Layered clay compounds and mixtures with one or more resins selected from the group consisting of polyester alone or ethylene-vinyl alcohol copolymers (EVOH), polyamides, ionomers and polyvinyl alcohols (PVA) Blocking nanocomposites; And a compatibilizer, which has excellent mechanical strength, excellent oxygen barrier property, organic solvent barrier property, and moisture barrier property, and chemical barrier property, and can be used for single layer, multilayer blow molding, and film processing.

Description

Nanocomposite composition having super barrier property and article using the same}

1 is a schematic diagram showing the dispersion morphology of a blocking nanocomposite with respect to a polyolefin continuous phase in a molded article made from the nanocomposite composition according to the present invention.

Figure 2a is a photograph of the cross-section of the hollow molded container prepared according to Example 1 of the present invention with an electron microscope (x200).

Figure 2b is a photograph of the cross-sectional view of the hollow molded container prepared according to Example 1 of the present invention with an electron microscope (x5,000).

3A is a photograph of a cross section of a hollow molded container according to Comparative Example 3 with an electron microscope (× 2,000).

3B is a photograph of the cross section of the hollow molded container according to Comparative Example 3 with an electron microscope (× 5,000).

Description of the main parts of the drawing

10: polyolefin continuous phase

11: Blocking Nanocomposite Discontinuous Phase

The present invention relates to a nanocomposite composition having excellent barrier properties and a barrier article prepared therefrom. More particularly, the present invention relates to excellent mechanical strength and chemical barrier properties such as oxygen barrier property, organic solvent barrier property and moisture barrier property. In addition to being excellent, the present invention relates to barrier nanocomposite compositions and barrier articles made therefrom that can be used for single layer, multilayer blow molding, and film processing.

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 properties against gas, they have limitations in applications such as food packaging requiring oxygen barrier properties and agrochemical containers requiring chemical barrier properties. Therefore, when manufacturing a food packaging or a container (bottle), etc. are manufactured in multiple layers through co-extrusion, lamination, coating (coating) and the like.

With excellent gas barrier properties and transparency, ethylene-vinyl alcohol copolymers (EVOH, ethylene-vinyl alcohol), polyamide-based and polyester-based resins provide gas and harmful solvent barriers to multilayer plastic products. . However, since the ethylene-vinyl alcohol copolymer, polyamide-based, and polyester-based resins are more expensive than general-purpose resins, the content of the ethylene-vinyl alcohol copolymer is limited, and ethylene-vinyl alcohol is reduced to reduce the cost increase of the multilayer container. , Polyamide-based resins and polyesters had to be as thin as possible.

In order to reduce the cost of the multilayer plastic container as described above, a method of compounding ethylene-vinyl alcohol, polyamide-based and polyester-based resins with low-cost polyolefins has been proposed. There is a problem that is difficult to do. As described above, a film or a sheet prepared in a state in which an ethylene-vinyl alcohol, polyamide-based, and polyester-based resin is incompletely blended has a problem that mechanical properties decrease.

Accordingly, in order to increase the miscibility of ethylene-vinyl alcohol, polyamide-based and polyester-based resins and polyolefins, a method of kneading with a compatibilizer has been proposed, which is an ethylene-vinyl alcohol, polyamide-based and polyester It acts to increase the compatibility between (polyester) resin and polyolefin. Therefore, the choice of compatibilizers is important to increase the mechanical strength, and the chemical barrier resistance of the product.

US Pat. No. 4,971,864, US Pat. No. 5,356,990, EP 15,556, and EP 210,725 disclose a method of using a compatibilizer in which polyethylene is grafted with maleic anhydride. This has the advantage of increasing oxygen permeability and mechanical strength, but due to the hydrophilic properties of ethylene-vinyl alcohol, polyamide-based resin and ionomer, the water barrier property is weak, and the hydrophobic resin has to be multi-layered processed on the outermost layer. There is a problem that there is no suitable processing condition for implementing the barrier morphology.

On the other hand, the nanocomposite (nanocomposite) is a polymer matrix (such as oligomers, polymers, or blends thereof, as disclosed in US Pat. Nos. 4,739,007, 4,618,528, 4,874,728, 4,889,885, 4,810,734, 5,385,776). nanoscale layered clay compounds in exfoliated, intercalated forms of exfoliated nanocomposites, laminated tactoidal nanocomposites, Or a complex in which a mixture thereof is dispersed.

In general, nanocomposite manufacturing technology can be divided into two.

One is a method for producing a polyamide-based nanocomposite as described above, in which a monomer is inserted between organic clay compound layers by a polymerization method, and the clay compound flakes are dispersed through an interlayer polymerization. However, this method has the disadvantage that it can be used only when cationic polymerization is possible.

The other is a method of inserting a polymer chain in a molten state into an interlayer of a layered clay compound by melt compounding, and peeling it by mechanical mixing. Examples of this method are the preparation of polystyrene nanocomposites (RA Vaia et al., Chem. Mater., 5, 1694 (1993)), the preparation of polypropylene nanocomposites (M. Kawasumi et al., Macromolecules, 30, 6333 (1997)), And the preparation of nylon 6 nanocomposites (US Pat. No. 5,385,776) and the like.

Therefore, there is a need for further studies on nanocomposite compositions that can provide excellent mechanical strength and chemical resistance, and can implement effective barrier morphology.

In particular, in recent years, the development and commercialization of alcohol-containing automobile fuels has been accelerated as an alternative to the high oil prices caused by the exhaustion of petroleum resources and environmental problems. However, the pre-invented ethylene-vinyl alcohol copolymers (EVOH), polyamides, ionomers, and polyvinyl alcohol (PVA) nanocomposites have poor barrier properties to alcohol-containing fuels and have a high content to overcome them. When raised, the disadvantages of inferior low-temperature impact strength were revealed. In particular, polyamide nanocomposites were very prone to deterioration. Ethylene-vinyl alcohol copolymers (EVOH) and polyvinyl alcohol (PVA) nanocomposites are also weak at low temperatures so that their content cannot be increased to overcome alcohol barrier vulnerabilities. In addition, in view of cost competitiveness, ethylene-vinyl alcohol copolymers (EVOH), polyamides, and ionomers have disadvantages in that raw material prices are higher than general-purpose resins.

In order to solve the above problems, the present invention has excellent mechanical strength, excellent chemical barrier properties such as oxygen barrier property, organic solvent barrier property, and moisture barrier property, and particularly excellent alcohol fuel barrier property and low temperature embrittlement. It is an object of the present invention to provide a nanocomposite composition which is excellent in low-temperature impact strength and can be used for single layer, multilayer blow molding and film processing.

Another object of the present invention to provide a container, a film prepared from the nanocomposite composition.

In order to achieve the above technical problem, in the present invention

a) 100 parts by weight of polyolefin resin;

b) (i) polyester alone or at least one resin selected from the group consisting of polyester and ethylene-vinyl alcohol copolymers (EVOH), polyamides, ionomers and polyvinyl alcohols (PVA); 1 to 95 parts by weight of the barrier nanocomposite of the barrier resin and (ii) the layered clay compound; And

c) 1 to 95 parts by weight of a compatibilizer provides a dry blended barrier nanocomposite composition.

The present invention also provides a barrier article prepared from the barrier nanocomposite composition.

According to one embodiment of the composition of the present invention, the weight ratio of the barrier resin and the layered clay compound may be 58.0: 42.0 to 99.9: 0.1.

According to another embodiment of the present invention, the polyolefin resin may be at least one selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene and ethylene-propylene copolymer, metallocene polyethylene, and polypropylene. The polypropylene may be at least one member selected from the group consisting of propylene homopolymers, copolymers, metallocene polypropylenes, and composite resins in which talc, flame retardants, etc. are added to the homopolymers or copolymers to enhance the physical properties of general polypropylenes. Can be.

According to another embodiment of the present invention, the layered clay compound is montmorillonite, bentonite, kaolinite, mica, hectorite, fluoride hectorite, saponite, bedelite, nontronite, stevensite, vermiculite, halosite It may be at least one selected from the group consisting of volconscote, sukconite, margotite and kenyarite.

According to another embodiment of the present invention, the polyamide 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) to Mixtures of two or more of the polyamides of 12) can be selected and used.

According to another embodiment of the present invention, the polyester may be at least one of polybutylene terephthalate and polyethylene terephthalate.

According to another embodiment of the present invention, the compatibilizer is an ethylene-ethylene-acrylic acid-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-alkyl acrylate-acrylic acid copolymer, maleic anhydride modified (graft) high density polyethylene, Maleic anhydride modified (graft) linear low density polyethylene, ethylene-alkyl methacrylate-methacrylic acid copolymer, ethylene-butylacrylate copolymer, ethylene-vinylacetate copolymer and maleic anhydride modified (graft) ethylene-vinyl acetate It may be at least one selected from the group consisting of copolymers.

According to another embodiment of the present invention, the barrier article may include a pipe, a container, a sheet, a film, and the like, and each of the single layer and the multilayer ( multi layer).

 Hereinafter, the present invention will be described in detail.

While the present inventors have been researching a method for improving the mechanical strength and chemical resistance of nanocomposite composition, the layered clay compound is ethylene-vinyl alcohol copolymer (EVOH), polyamide, and ionomer. As a result of preparing nanocomposites by peeling nanoparticles into the polyvinyl alcohol (PVA) and the polyester-based barrier resin, the barrier resin itself was formed by lengthening the gas and liquid permeation path inside the barrier resin. In addition to increasing the water barrier properties and liquid barrier properties of the polyolefin in the continuous phase to increase the melt strength to suppress the sagging of the parison during blow molding, as well as the blocking resin nanocomposite, Nanocomposite compositions comprising polyolefin resins and compatibilizers are only excellent in mechanical strength, oxygen barrier properties, organic solvent barrier properties, and moisture barrier properties. As well as confirming the excellent alcohol fuel barrier properties and low-temperature impact strength, the present invention was completed.

Nanocomposite composition of the present invention comprises a) 100 parts by weight of a polyolefin resin;

b) (i) polyester alone or at least one resin selected from the group consisting of polyester and ethylene-vinyl alcohol copolymers (EVOH), polyamides, ionomers and polyvinyl alcohols (PVA); 1 to 95 parts by weight of a barrier nanocomposite of a barrier resin and a layered clay compound; And

c) 1 to 95 parts by weight of the compatibilizer is dry mixed.

The polyolefin resin of a) used in the present invention is a high density polyethylene (HDPE), low density polyethylene (LDPE, low density polyethylene), linear low density polyethylene (LLDPE, liner low density polyethylene), ethylene-propylene copolymer, It may be at least one selected from the group consisting of metallocene polyethylene, and polypropylene. The polypropylene resin is selected from the group consisting of propylene homopolymers, copolymers, metallocene polypropylenes and propylene homopolymers or copolymers, by adding talc, a flame retardant, or the like to strengthen the properties of general polypropylene. It may be one or more selected.

The weight ratio in the nanocomposite of the barrier resin of b) and the layered clay compound used in the present invention is 58.0: 42.0 to 99.9: 0.1, preferably 85.0: 15.0 to 99.0: 1.0. When the weight ratio of the barrier resin is less than 58, agglomeration of the layered clay compound occurs and dispersion is not appropriate, and when it exceeds 99.9, the barrier property synergistic effect is insignificant, which is not preferable.

When the barrier resin is a mixture of polyester and one or more resins selected from the group consisting of polyvinyl alcohol, ethylene vinyl alcohol copolymers, ionomers and polyamides, the weight ratio of polyester to the other resins is 10:90. To 90:10, preferably. Too little polyester outside the above range may reduce alcohol fuel barrier properties, and too much may hinder the specialized organic solvent barrier properties of the other resins.

The layered clay compound of b) is preferably an organic layered clay compound in which the organic agent is interposed between the layers of the layered clay compound. The organic agent content in the layered clay compound is preferably 1 to 45% by weight.

The layered clay compound may be montmorllonite, bentonite, bentonite, kaolinite, mica, hectorite, hectorite, fluorohectorite, saponite, and vadel Beidelite, nontronite, stevensite, vermiculite, halosite, volkonskoite, suconite, sugite, magadite, kenya At least one selected from the group consisting of kenyalite and hydrotalcite is preferable, and the organic agent may be primary ammonium, quaternary ammonium, phosphonium, or maleate ( maleate, succinate, acrylate, benzylic hydrogens, oxazoline and dimethyldisteaylammonium That the emitter organic material containing any of the functional groups selected preferred.

The ethylene content of the ethylene-vinyl alcohol copolymer of b) used in the present invention is preferably 10 to 50 mol%. If the content of the ethylene is less than 10 mol%, workability is lowered, making it difficult to melt molding, and if it exceeds 50 mol%, oxygen barrier property and liquid barrier property are not sufficient.

The polyamide of b) used in the present invention 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) to 12 Mixtures of two or more of the polyamides of) can 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-phenylenediamine. 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.

Therefore, 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 polycondensation well known to those skilled in the art.

The ionomer of b) used in the present invention is preferably a copolymer of acrylic acid and ethylene, and the melt index is preferably in the range of 0.1 to 10 g / 10 min (190 ° C., 2,160 g).

Examples of the polyester of b) include polybutylene terephthalate (PBT) and polyethylene terephthalate (PET), and polybutylene terephthalate (PBT) is prepared by polycondensation of butyl alcohol and terephthalic acid. Polyethylene terephthalate (PET) may be prepared through condensation polymerization of ethyl alcohol and terephthalic acid.

The blocking nanocomposite of b) is preferably 1 to 95 parts by weight, more preferably 1 to 30 parts by weight based on 100 parts by weight of polyolefin. If the barrier nanocomposite is less than 1 part by weight, the effect of improving barrier properties is small. If the barrier nanocomposite is more than 95 parts by weight, processing is not easy, which is not preferable.

The barrier nanocomposite imparts favorable conditions for implementing the morphology shown in FIG. 1 by the barrier nanocomposite discontinuous depending on the layered clay compound content. At this time, the finely peeled layered clay compound inside the barrier resin, which is a discontinuous phase, exhibits an excellent barrier effect. This is because the finely peeled layered clay compound inside the barrier resin forms a barrier film, which serves to improve the barrier property and mechanical properties of the barrier resin itself, and ultimately, the barrier property of the molded article manufactured from the composition, and mechanical The effect of improving the physical properties will be obtained.

Accordingly, in the present invention, the barrier resin and the layered clay compound are kneaded to disperse the layered clay compound in nano size in the barrier resin to maximize the contact area between the polymer chain and the layered clay compound, thereby preventing gas permeability and liquid. Maximize penetration inhibition.

The compatibilizer of c) used in the present invention serves to improve the compatibility of the polyolefin resin and the 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. When using a hydrocarbon-based polymer containing a polar group, the affinity of the compatibilizer with the polyolefin resin and the compatibilizer with the blocking nanocomposite becomes good due to the hydrocarbon polymer portion composed of the polymer base, resulting in the nanocomposite composition. To form a stable structure.

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) polypropylene, maleic anhydride modified (grafted) linear low density polyethylene, ethylene-alkyl (meth) acrylate- (meth) acrylic acid copolymer, ethylene-butylacrylate copolymer, ethylene-vinylacetate copolymer, and A maleic anhydride modified (grafted) ethylene-vinylacetate copolymer may be used one or more compounds selected from the group consisting of, or mixtures thereof.

The compatibilizer is preferably included in an amount of 1 to 95 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the polyolefin resin. 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. If the compatibilizer is more than 30 parts by weight, the molding process of the composition is not easy, which is not preferable.

When the epoxy-modified polystyrene copolymer is used as a compatibilizer, a main chain including 70 to 99 parts by weight of styrene and 1 to 30 parts by weight of an epoxy compound represented by the following Formula 1, and 1 to 80 parts by weight of an acrylic monomer of Formula 2 below Copolymers containing are preferred.

[Formula 1]

In Chemical Formula 1,

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

[Formula 2]

In addition, the maleic anhydride-modified (graft) high density polyethylene, maleic anhydride-modified (graft) linear low density polyethylene, or maleic anhydride-modified (graft) ethylene-vinylacetate copolymer are each 0.1 parts maleic anhydride per 100 parts by weight of the main chain. It is preferable that it is comprised from the branch which consists of 10 weight part.

The nanocomposite composition of the present invention can be usefully used for the manufacture of blow molding, single layer products and multilayer products, which are blow molding, extrusion molding, injection molding, Or by press-molding to produce bottles and films. At this time, the barrier nanocomposite composition is dry-blended to be molded while maintaining the morphology of the barrier nanocomposite, and even in the manufactured molded article, the peeled nanocomposite is maintained in a dispersed structure in the polyolefin matrix. Will be excellent.

The manufacturing method is based on the following two methods.

Manufacturing method by a single process

In the case of using blow molding, injection molding, etc. which is a general polymer processing process to produce the final product, single screw extruder, co-rotating twin screw extruder, two-way rotary twin screw extruder, continuous kneader, planetary gear It is a method of manufacturing by dispersing the components constituting the barrier nanocomposite of b) simultaneously in the matrix resin (polyolefin resin) of a) using a continuous kneader such as an extruder.

Manufacturing method by multistage process

After producing the barrier nanocomposite of b) using a polymer kneader such as a single screw extruder, a coaxially rotating twin screw extruder, a two-way rotating twin screw extruder, a continuous kneader, a planetary gear extruder, a batch kneader, the a) Is mixed with a matrix resin (polyolefin resin) at a predetermined ratio and introduced into a molding machine to form a final product.

As the molding method used therein, blow molding, extrusion molding, injection molding, thermoforming, and the like may be used, but the application of the present invention is not limited thereto. It includes all processing processes for making barrier containers.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

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

Polybutylene Terephthalate: (LG Chemicals SV-1120M)

Clay: SCP Product Closite 30B

Thermal Stabilizer: Product of Songwon Industry IR 1098

Example 1

 (Manufacture of Blocking Resin / Layered Clay Compound Nanocomposite)

97% by weight of polybutylene terephthalate (PBT) was added to the main hopper of a twin screw extruder, and 3% by weight of montmorillonite organicated with a layered clay compound was separately introduced into a side feeder, and then polybutylene terephthalate (PBT) was used. ) / Layered clay compound nanocomposites were prepared. At this time, the extrusion temperature was 220-230-245-245-245-245-245 ° C., the screw speed was 300 rpm, and the discharge condition was 10 kg / hr.

(Manufacture of Nanocomposite Compositions and Containers)

Dry-mix the polybutylene terephthalate (PBT) / Layered clay compound nanocomposite 19.23 parts by weight with polyolefin resin and 8.97 parts by weight of maleic anhydride modified (grafted) high density polyethylene with a compatibilizer. Blow molding to prepare a 1000 mL vessel, where the processing temperature is 180-190-200-220-230 ℃, screw speed was 30 rpm. As a result of observing the cross-section of the prepared blown container with an electron microscope (× 200, × 5,000), it showed a structure of a multiple-lamella form, which is shown in Figures 2a and 2b.

Example 2

(Blockable Nanocomposite)

50% by weight of polyamide (nylon 6) and 47% by weight of polybutylene terephthalate (PBT) were added to the main hopper of a twin screw extruder, and 3% by weight of montmorillonite organicated with a layered clay compound was separated into a side feeder. After that, a polyamide / layered clay compound nanocomposite was prepared. At this time, the extrusion temperature was 220-230-245-245-245-245-245 ° C., the screw speed was 300 rpm, and the discharge condition was 10 kg / hr.

(Manufacture of Nanocomposite Compositions and Containers)

Dry-mix 19.23 parts of the polyamide / polybutylene terephthalate / layered clay compound nanocomposite prepared above with 100 parts by weight of high density polyethylene with polyolefin resin and 8.97 parts by weight of maleic anhydride-modified (grafted) high density polyethylene with a compatibilizer. And, by blow molding it to prepare a container of 1000 mL, the processing temperature was 180-190-200-220-230 ℃, screw speed was 33 rpm.

Comparative Example 1

A 100 mL container was prepared by blow molding 100% by weight of high density polyethylene.

Comparative Example 2

The same process as in Example 1 was performed except that the organic clayed montmorillonite, which is a layered clay compound, was not used. The cross section of the manufactured blow molded container was observed with an electron microscope (x2,000, x5,000), and the results are shown in FIGS. 3a and 3b.

Comparative Example 3

(Manufacture of Blocking Resin / Layered Clay Compound Nanocomposite)

97 parts by weight of high-density polyethylene was added to the main hopper of the twin screw extruder, and 3 parts by weight of montmorillonite organicized with the layered clay compound was separately introduced into a side feeder, and then a high-density polyethylene / layered clay compound nanocomposite was prepared. At this time, the extrusion temperature was 175-190-190-190-190-190-190 ° C, the screw speed was 300 rpm, and the discharge condition was 10 kg / hr.

(Vessel manufacturing)

The prepared high-density polyethylene / layered clay compound nanocomposite was blown to prepare a container of 1000 mL, wherein the processing temperature is 160-190-190-190-185 ℃, screw speed was 33 rpm.

Comparative Example 4

(Manufacture of Blocking Resin / Layered Clay Compound Nanocomposite)

97% by weight of amorphous polyamide (Nylon 6) was added to the main hopper of the twin screw extruder, and 3% by weight of montmorillonite organicated with the layered clay compound was separately introduced into the side feeder, followed by polyamide / layered clay compound nanocomposite. Was prepared. At this time, the extrusion temperature was 220-230-245-245-245-245-245 ° C., the screw speed was 300 rpm, and the discharge condition was 10 kg / hr.

(Manufacture of Nanocomposite Compositions and Containers)

15% by weight of the prepared polyamide / layered clay compound nanocomposite was 7% by weight of maleic anhydride-modified (grafted) high density polyethylene with a compatibilizer, and dry-mixed with 78% by weight of high density polyethylene with a polyolefin-based resin, followed by blow molding. 1000 mL of vessel was prepared, wherein the processing temperature was 190-215-215-215-195 ° C. and the screw speed was 33 rpm.

Experimental Example

In Examples 1 to 2 and Comparative Examples 1 to 4, the liquid barrier property and the gas barrier property were measured by the following method using the hollow molded containers, and the results are shown in Table 1 below.

A) Liquid barrier property-alcohol fuel E10 (Fuel C 90% + ethyl alcohol 10%), herbicide decis (deltametrine 1% + emulsifiers, stabilizers, solvents, light agricultural co., Ltd.), pesticide BATSA (BPMC 50% + emulsifiers, solvents) 50%), and ethyl alcohol were filled into 1000 mL containers blow molded in Examples 1 and 2 and Comparative Examples 1 to 4, and then the weight change rate of the contents was measured for 30 days in a forced exhaust environment at 50 ° C.

B) gas barrier properties (㏄ / m 2 .work.barometric pressure) —1000 mL vessels blown in Examples 1 to 2 and Comparative Examples 1 to 4 were subjected to a temperature of 23 ° C. for 1 day, and a relative humidity of 50%. After standing under the conditions, it was measured using a gas permeability meter (Mocon OX-TRAN 2/20, USA).

C) Elongation at low temperature and impact strength-Tensile elongation and tensile strength by temperature to evaluate the impact resistance at low temperatures by cutting the container molded in Examples 1 to 2 and Comparative Example 4 to produce a tensile specimen and a specimen for IZOD Evaluation was conducted. The results are shown in Table 2.

division Liquid barrier property (%) Gas barrier property (㏄ / ㎡. Japanese air pressure) Weight change rate at high temperature (50 ℃) Oxygen permeability CO ₂ permeability E10 Desisis Batha Ethyl alcohol Example 1 0.98 0.63 0.08 0.0018 580 520 Example 2 1.89 0.54 0.05 0.0020 530 511 Comparative Example 1 50.2 26.61 5.60 0.20 12,312 23,097 Comparative Example 2 25.3 14.34 3.10 0.12 1,320 1,824 Comparative Example 3 48.7 25.9 4.90 0.193 12,110 22,991 Comparative Example 4 5.80 0.52 0.04 0.051 522 504

Tensile Elongation (room temperature) (%) Tensile Elongation (-40 degrees) (%) Room Temperature Shock (KJ / m ² ) (IZOD, Notched) Low Temperature Shock (KJ / m ² ) (IZOD, Unnotched) Example 1 359 130 21 100 Example 2 320 110 18 80 Comparative Example 4 310 92 13 34

Through the above Table 1, the molded article prepared from the nanocomposite composition of Examples 1 to 2 of the present invention is superior to the molded article of Comparative Examples 1 to 4 liquid blocking effect, including the alcohol fuel (E10), and gas barrier effect Could confirm.

In addition, it can be seen from Table 2 that the physical specimens prepared from the nanocomposite compositions of Examples 1 to 2 of the present invention have superior low temperature impact properties compared to the physical specimens of Comparative Example 4.

As described above, the nanocomposite composition of the present invention has excellent mechanical strength, excellent oxygen barrier property, organic solvent barrier property, and moisture barrier property, and chemical barrier property as well as single layer, multilayer blow molding, and There is an advantage that can be used for film processing.

Claims (21)

a) 100 parts by weight of polyolefin resin; b) (i) polyester alone or at least one resin selected from the group consisting of polyesters and ethylene-vinyl alcohol copolymers (EVOH), polyamides, ionomers, and polyvinyl alcohols (PVA) 1 to 95 parts by weight of a barrier nanocomposite of a barrier resin and a layered clay compound; And c) 1 to 95 parts by weight of compatibilizer The dry-blending barrier nanocomposite composition.     The method of claim 1       Blocking nanocomposite composition, characterized in that the barrier resin and the layered clay compound is contained in a weight ratio of 58.0: 42.0 to 99.9: 0.1.  The blocking nanocomposite composition of claim 1, wherein the polyester is at least one selected from polybutylene terephthalate (PBT) and polyethylene terephthalate (PET). The method of claim 1, The polyolefin resin of a) is high density polyethylene (HDPE), low density polyethylene (LDPE, low density polyethylene), linear low density polyethylene (LLDPE, liner low density polyethylene), ethylene-propylene copolymer, metallocene polyethylene, And at least one member selected from the group consisting of polypropylene. The polypropylene resin according to claim 4, wherein the polypropylene resin is at least one member selected from the group consisting of propylene homopolymers, copolymers, metallocene polypropylenes, and composite resins in which talc or flame retardant is added to the homopolymers or copolymers. A blocking nanocomposite composition. The method of claim 1, The layered clay compound included in the blocking nanocomposite of b) is montmorllonite, bentonite, kaolinite, mica, hectorite, fluorohectorite ), Saponite, beidelite, nontronite, stevensite, vermiculite, hallosite, volkonskoite, suconite ), Magadite, kenyalite and hydrotalcite Blocking nanocomposite composition, characterized in that at least one member selected from the group consisting of. The method of claim 1, Blocking nanocomposite composition characterized in that the layered clay compound contained in the blocking nanocomposite of b) comprises 1 to 45% by weight of an organic agent in the layered clay compound. The method of claim 7, wherein The organizing agent may be primary to quaternary ammonium, phosphonium, maleate, succinate, acrylate, benzylic hydrogens Blocking nanocomposite composition, characterized in that it is selected from an organic agent comprising any functional group selected from the group consisting of, oxazoline (oxazoline), and dimethyl distealylammonium (dimethyldisteaylammonium). The method of claim 1, Blocking nanocomposite composition, characterized in that the ethylene content of the ethylene-vinyl alcohol copolymer of b) is 10 to 50 mol%. The method of claim 1, The polyamide of b) 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) Copolyamide having two or more components in 1) -12) polyamide, or 14) 1) -12) Polyamide Blocking nanocomposite composition, characterized in that the mixture of two or more. The barrier nanocomposite composition of claim 10, wherein the amorphous polyamide has a glass transition temperature of 70 ^° C to 170 ^° C. The hexamethylenediamine isophthalamide / terephthalamide terpolymer according to claim 10, wherein the amorphous polyamide has a hexamethylenediamine isophthalamide ratio of isophthalic acid / terephthalic acid of 99/1 to 60/40. A mixture of 4- and 2,4,4-trimethylhexamethylenediamine terephthalamide, and isophthalic acid or terephthalic acid, or a mixture thereof and a copolymer of hexamethylenediamine or 2-methylpentamethylenediamine Blocking nanocomposite composition. The blocking nanocomposite composition according to claim 12, wherein the amorphous polyamide is a hexamethylenediamine isophthalamide / terephthalamide terpolymer having an isophthalic acid / terephthalic acid ratio of 70/30. The method of claim 1, Blocking nanocomposite composition, characterized in that the melt index of the ionomer of b) is in the range of 0.1 to 10 g / 10 min (190 ℃, 2,160 g). The method of claim 1, The compatibilizer of c) is an epoxy-modified polystyrene copolymer, an ethylene-ethylene-acrylate-acrylic acid copolymer, an ethylene-ethylacrylate copolymer, an ethylene-alkylacrylate-acrylic acid copolymer, maleic anhydride-modified (graft) high density polyethylene, anhydrous Maleic acid modified (graft) polypropylene, maleic anhydride modified (graft) linear low density polyethylene, ethylene-alkyl methacrylate-methacrylic acid copolymer, ethylene-butylacrylate copolymer, ethylene-vinylacetate copolymer, and maleic anhydride A barrier nanocomposite composition, characterized in that it is a mixture of at least one compound selected from the group consisting of acid-modified (graft) ethylene-vinylacetate copolymers, or a modified product thereof. The method of claim 15, Blocking nanocomposite composition, characterized in that the epoxy-modified polystyrene copolymer is a copolymer containing styrene and an epoxy compound as a main chain, containing an acrylic monomer. The method of claim 16, The epoxy modified polystyrene copolymer a) iii) 70 to 99 parts by weight of styrene; And   Ii) 1 to 30 parts by weight of the epoxy compound represented by Formula 1   A main chain comprising a; And b) 1 to 80 parts by weight of the acrylic monomer represented by Formula 2    Branches containing Blocking nanocomposite composition, characterized in that the copolymer comprising: [Formula 1]

In Chemical Formula 1, R and R 'are each independently residues of a C1-C20 aliphatic or C5-C20 aromatic compound having a double bond group at the terminal of the molecular structure; [Formula 2]

The method of claim 15, The maleic anhydride modified (grafted) high density polyethylene, maleic anhydride modified (grafted) linear low density polyethylene, maleic anhydride modified (grafted) polypropylene, and maleic anhydride modified (grafted) ethylene-vinylacetate copolymer, respectively. Blocking nanocomposite composition, characterized in that consisting of branches consisting of 0.1 to 10 parts by weight of maleic anhydride with respect to 100 parts by weight. The mixture of the polyester and at least one resin selected from the group consisting of ethylene vinyl alcohol copolymers, ionomers, polyamides and polyvinyl alcohols is mixed in a weight ratio of 10:90 to 90:10. Blocking nanocomposite composition, characterized in that. A container made from the blocking nanocomposite composition according to claim 1. A film made from the blocking nanocomposite composition according to claim 1.

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