(19)
(11)EP 1 769 028 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
03.09.2014 Bulletin 2014/36

(21)Application number: 05765926.0

(22)Date of filing:  08.07.2005
(51)Int. Cl.: 
C08L 23/04  (2006.01)
C08L 23/26  (2006.01)
B32B 27/32  (2006.01)
C08K 9/00  (2006.01)
C08J 5/18  (2006.01)
(86)International application number:
PCT/KR2005/002195
(87)International publication number:
WO 2006/009360 (26.01.2006 Gazette  2006/04)

(54)

GAS-BARRIER NANOCOMPOSITE COMPOSITION AND ARTICLE USING THE SAME

GASBARRIERE-NANOKOMPOSITZUSAMMENSETZUNG UND GEGENSTAND DAMIT

COMPOSITION NANOCOMPOSITE A BARRIERE GAZEUSE ET ARTICLE COMPORTANT LADITE COMPOSITION


(84)Designated Contracting States:
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

(30)Priority: 21.07.2004 KR 2004056996
08.04.2005 KR 2005029580
02.06.2005 KR 2005047116

(43)Date of publication of application:
04.04.2007 Bulletin 2007/14

(73)Proprietor: LG Chem. Ltd.
Seoul 150-721 (KR)

(72)Inventors:
  • KIM, Myung-Ho, 107-903 Samsung Hanul Apt
    Daejeon-city 305-707 (KR)
  • KIM, Minki, 5-104 LG Company Housing 386-1
    Daejeon-city 305-340 (KR)
  • YANG, Youngchul
    Daejeon-city 302-774 (KR)
  • SHIN, Jaeyong
    Daejeon-city 302-852 (KR)

(74)Representative: Goddar, Heinz J. 
Boehmert & Boehmert Anwaltspartnerschaft mbB Patentanwälte Rechtsanwälte Pettenkoferstrasse 20-22
80336 München
80336 München (DE)


(56)References cited: : 
EP-A1- 1 460 109
WO-A-03/055792
WO-A1-2004/085534
US-A1- 2001 033 924
US-A1- 2004 106 719
WO-A-00/78540
WO-A1-2004/005388
KR-A- 2004 053 621
US-A1- 2004 030 020
US-B1- 6 414 070
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Technical Field



    [0001] The present invention relates to a gas-barrier nanocomposite composition and an article manufactured therefrom, and more particularly, to a nanocomposite composition having superior barrier properties and moldability, which is formed by dry-blending a polyolefin resin with a melt blend of a resin having barrier properties and a nanocomposite having barrier properties and a compatibilizer, and a product manufactured therefrom.

    Background Art



    [0002] General-purpose resins, such as polyethylene and polypropylene, are used in many fields due to their superior moldability, mechanical properties, and moisture barrier properties. However, these resins are limited in their use in packaging or containers for agrochemicals and foods, which require superior chemical and oxygen barrier properties.

    [0003] An ethylene-vinyl alcohol (EVOH) copolymer and polyamide resins have transparency and good gas barrier properties. However, because these resins are more expensive than general-purpose resins, their contents in products are limited.

    [0004] Thus, to reduce costs, a blend of a resin having barrier properties, such as EVOH and polyamide resins, and inexpensive polyolefin was proposed. However, satisfactory barrier properties were not obtained.

    [0005] To improve barrier properties, a fully exfoliated, partially exfoliated, intercalated or partially intercalated nanocomposite formed by dispersing a nano-sized intercalated cl ay in a polymer matrix has been used.

    Disclosure of Invention


    Technical Problem



    [0006] When a molded article is manufactured using the above-described nanocomposite, the nanocomposite should maintain its morphology having barrier property even after being molded and its moldability should be excellent to easily manufacture sheets or films as well as containers.

    Technical Solution



    [0007] The present invention provides a nanocomposite composition having superior mechanical strength and superior oxygen, organic solvent, and moisture barrier properties, and superior moldability.

    [0008] The present invention also provides an article manufactured from the nanocomposite composition having barrier properties.

    [0009] According to an aspect of the present invention, there is providedA nanocomposite composition obtained by dry-blending of:

    30 to 95 parts by weight of polyolefin resin;

    0.5 to 60 parts by weight of a melt blend i.) including at least one resin selected from the group consisting of an ethylene-vinyl alcohol (EVOH) copolymer, a polyamide, an ionomer and a polyvinyl alcohol (PVA); and ii.) at least one nanocomposite selected from the group consisting of an EVOH copolymer/intercalated clay nanocomposite, a polyamide/intercalated clay nanocomposite, an ionomer/intercalated clay nanocomposite and a polyvinylalcohcl/intercalated clay nanocomposite;

    1 to 30 parts by weight of a compatibilizer,
    wherein the resin and the nanocomposite are molten-blended in a weight ratio from 25:75 to 75:25,
    wherein the polyolefin resin is at least one compound selected from the group consisting of a high density polyethylene (HDPE), a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), an ethylene-propylene polymer, and an ethylene-propylene copolymer, and
    wherein the compatibilizer is one or more compounds selected from the group consisting of an ethylene-ethylene anhydride-acrylic acid copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-alkyl acrylate-acrylic acid copolymer, a maleic anhydride modified (graft) high density polyethylene, a maleic anhydride modified (graft) linear low-density polyethylene, an ethylene-alkyl (meth)acrylate-(meth)acrylic acid copolymer, an ethylene-butyl acrylate copolymer, an ethylene-vinyl acetate copolymer, and a maleic anhydride modified (graft) ethylene-vinyl acetate copolymer.



    [0010] The present invention will now be explained in more detail.

    [0011] Korean Patent Application No. 2002-76575, previously filed by the applicant of the present application, discloses a nanocomposite blend composition including: 1 to 97 parts by weight of a polyolefin resin; 1 to 95 parts by weight of a nanocomposite, having barrier properties, selected from the group consisting of an ethylene-vinyl alcohol (EVOH) copolymer/ intercalated clay nanocomposite, a polyamide/intercalated clay nanocomposite, an ionomer / intercalated clay nanocomposite and a polyvinyl alcohol (PVA) / intercalated clay nanocomposite; and 1 to 95 parts by weight of a compatibilizer. This completes the present invention.

    [0012] A nanocomposite composition having barrier properties of an embodiment of the present invention is obtained by dry-blending a melt blend of a resin having barrier properties and a nanocomposite having barrier properties with a polyolefin resin and a compatibilizer.

    [0013] That is, the nanocomposite composition is a dry-blended composition including: 30 to 95 parts by weight of a polyolefin resin; 0.5 to 60 parts by weight of a melt blend including at least one resin having barrier properties, selected from the group consisting of an ethylene-vinyl alcohol (EVOH) copolymer, a polyamide, an ionomer and a polyvinyl alcohol (PVA) and at least one nanocomposite having barrier properties selected from the group consisting of an EVOH copolymer/intercalated clay nanocomposite, a polyamide/intercalated clay nanocomposite, an ionomer/intercalated clay nanocomposite and a polyvinylalcohol/intercalated clay nanocomposite; and 1 to 30 parts by weight of a compatibilizer.

    [0014] The polyolefin resin may be at least one selected from the group consisting of a high density polyethylene (HDPE), a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), an ethylene-propylene copolymer, metallocene and polypropylene. The polypropylene may be at least one compound selected from the group consisting of a homopolymer of polypropylene, a copolymer of polypropylene, metallocene polypropylene and a composite resin having improved physical properties by adding talc, flame retardant to a homopolymer or copolymer of polypropylene.

    [0015] The content of the polyolefin resin is preferably 30 to 95 parts by weight, and more preferably 70 to 90 parts by weight. If the content of the polyolefin resin is less than 30 parts by weight, molding is difficult. If the content of the polyolefin resin is greater than 90 parts by weight, the barrier properties are poor.

    [0016] The resin/nanocomposite melt blend can be prepared by first forming an exfoliated or partially exfoliated nanocomposite having barrier properties from the resin having barrier properties and the intercalated clay and molten-blending the nanocomposite, with the resin having barrier properties. Specifically, the resin/nanocomposite melt blend can be prepared by melt blending at least one resin having barrier properties, selected from the group consisting of an EVOH copolymer, a polyamide, an ionomer and a polyvinyl alcohol (PVA) and at least one nanocomposite having barrier properties, selected from the group consisting of an EVOH copolymer/intercalated clay nanocomposite, a polyamide/intercalated clay nanocomposite, an ionomer/intercalated clay nanocomposite and a polyvinylalcohol/intercalated clay nanocomposite.

    [0017] The resin having barrier properties is added to the intercalated clay to form a nano-sized exfoliated or partially exfoliated nanocomposite. Due to such a nanocomposite morphology, the passage route of gas and liquid in the resin is extended, and thus moisture and liquid barrier properties of the resin itself are improved, and the melting strength of polyolefin is increased due to the intercalated clay, which prevents drop of parison in blow molding.

    [0018] The weight ratio of the resin having barrier properties to the intercalated clay in the nanocomposite is 58.0:42.0 to 99.9:0.1, and preferably 85:0:15.0 to 99.0:1.0. If the weight ratio of the resin having barrier properties to the intercalated clay is less than 58.0:42.0, the intercalated clay agglomerates and dispersing is difficult. If the weight ratio of the resin having barrier properties to the intercalated clay is greater than 99.9:0.1, the improvement in the barrier properties is negligible.

    [0019] Due to the use of the melt blend of the nanocomposite and the resin having barrier properties, the processing temperature range in molding can be broader. That is, components of the blend can be selected and a blending ratio can be adjusted according to the processing temperature condition required to prepare a molded article.

    [0020] To obtain the resin having barrier property/nanocomposite melt blend, molten-blending is preferably carried out at 175-270 °C .

    [0021] . The intercalated clay is preferably organic intercalated clay. The content of an organic material in the intercalated clay is preferably 1 to 45 wt %. When the content of the organic material is less than 1 wt%, the compatibility of the intercalated clay and the resin having barrier properties is poor. When the content of the organic material is greater than 45 wt%, the intercalation of the resin having barrier properties is difficult.

    [0022] The intercalated clay includes at least one material selected from montmorillonite, bentonite, kaolinite, mica, hectorite, fluorohectorite, saponite, beidelite, nontronite, stevensite, vermiculite, hallosite, volkonskoite, suconite, magadite, and kenyalite; and the organic material preferably has a functional group selected from primary ammonium to quaternary ammonium, phosphonium, maleate, succinate, acrylate, benzylic hydrogen, oxazoline and dimethyldistearylammonium.

    [0023] The resin having barrier properties and the nanocomposite having barrier properties is preferably melt-blended in a weight ratio from 25:75 to 75:25. If the amount of the resin having barrier properties is too large, the barrier properties are not improved. If the amount of the resin having barrier properties is small, the impact strength of a final molded article is reduced.

    [0024] If an ethylene-vinyl alcohol copolymer is included in the nanocomposite, the content of ethylene in the ethylene-vinyl alcohol copolymer is preferably 10 to 50 mol %. If the content of ethylene is less than 10 mol %, melt molding becomes difficult due to poor processability. If the content of ethylene exceeds 50 mol %, oxygen and liquid barrier properties are insufficient.

    [0025] If polyamide is included in the nanocomposite, the polyamide may be nylon 4.6, nylon 6, nylon 6.6, nylon 6.10, nylon 7, nylon 8, nylon 9, nylon 11, nylon 12, nylon 46, MXD6, amorphous polyamide, a copolymerized polyamide containing at least two of these, or a mixture of at least two of these.

    [0026] The amorphous polyamide refers to a polyamide having insufficient crystallinity, that is, not having an endothermic crystalline melting peak when measured by a differential scanning calorimetry (DSC) (ASTM D-3417, 10 °C /min).

    [0027] In general, the polyamide can be prepared using diamine and dicarboxylic acid. Examples of the diamine include hexamethylenediamine, 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)isopropylidene, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, meta-xylenediamine, 1,5-diaminopentane, 1,4-diaminobutane, 1,3-diaminopropane, 2-ethyldiaminobutane, 1,4-diaminomethylcyclohexane, methane-xylenediamine, alkyl-substituted or unsubstituted m-phenylenediamine and p-phenylenediamine. Examples of the dicarboxylic acid include alkyl-substituted or unsubstituted isophthalic acid, terephthalic acid, adipic acid, sebacic acid, butanedicarboxylic acid.

    [0028] Polyamide prepared using aliphatic diamine and aliphatic dicarboxylic acid is general semicrystalline polyamide (also referred to as crystalline nylon) and is not amorphous polyamide. Polyamide prepared using aromatic diamine and aromatic dicarboxylic acid is not easily treated using a general melting process.

    [0029] Thus, amorphous polyamide is preferably prepared, when one of diamine and dicarboxylic acid used is aromatic and the other is aliphatic. Aliphatic groups of the amorphous polyamide are preferably C1-C15 aliphatic or C4-C8 alicyclic alkyls. Aromatic groups of the amorphous polyamide are preferably substituted C1-C6 mono-or bicyclic aromatic groups. However, all the above amorphous polyamide is not preferable in the present invention. For example, metaxylenediamine adipamide is easily crystallized when heated during a thermal molding process or when oriented, therefore, it is not preferable.

    [0030] Examples of preferable amorphous polyamides include hexamethylenediamine isophthalamide, hexamethylene diamine isophthalamide/terephthalamide terpolymer having a ratio of isophthalic acid/terephthalic acid of 99/1 to 60/40, a mixture of 2,2,4-and 2,4,4-trimethylhexamethylenediamine terephthalamide, a copolymer of hexamethylenediamine or 2-methylpentamethylenediamine and an isophthalic acid, terephthalic acid or mixtures thereof. While polyamide based on hexamethylenediamine isophthalamide/terephthalamide, which has a high terephthalic acid content, is useful, it should be mixed with another diamine such as 2-methyldiaminopentane in order to produce an amorphous polyamide that can be processed.

    [0031] The above amorphous polyamide comprising only the above monomers may contain a small amount of lactam, such as caprolactam or lauryl lactam, as a comonomer. It is important that the polyamide be amorphous. Therefore, any comonomer that does not crystallize polyamide can be used. About 10 wt% or less of a liquid or solid plasticizer, such as glycerole, sorbitol, or toluenesulfoneamide (Santicizer 8 monsanto) can also be included in the amorphous polyamide. For most applications, a glass transition temperature Tg (measured in a dried state, i.e., with a water content of about 0.12 wt% or less) of amorphous polyamide is 70-170 °C, and preferably 80-160 °C. The amorphous polyamide, which is not blended, has a Tg of approximately 125 °C in a dried state. The lower limit of Tg is not clear, but 70 °C is an approximate lower limit. The upper limit of Tg is not clear, too. However, when polyamide with a Tg of about 170 °C or greater is used, thermal molding is difficult. Therefore, polyamide having both an acid and an amine having aromatic groups cannot be thermally molded due to too high Tg, and thus, is not suitable for the purposes of the present invention.

    [0032] The polyamide may also be a semicrystalline polyamide. The semicrystalline polyamide is generally prepared using lactam, such as nylon 6 or nylon 11, or an amino acid, or is prepared by condensing diamine, such as hexamethylenediamine, with dibasic acid, such as succinic acid, adipic acid, or sebacic acid. The polyamide may be a copolymer or a terpolymer such as a copolymer of hexamethylenediamine/ adipic acid and caprolactam (nylon 6,66). A mixture of two or more crystalline polyamides can also be used. The semicrystalline and amorphous polyamides are prepared by condensation polymerization well-known in the art.

    [0033] If an ionomer is included in the nanocomposite, the ionomer is preferably a copolymer of acrylic acid and ethylene, with a melt index of 0.1 to 10 g/10 min (190 °C, 2,160 g).

    [0034] The content of the melt blend is preferably 0.5 to 60 parts by weight, and more preferably 8 to 30 parts by weight. If the content of the melt blend is less than 0.5 part by weight, an improvement of barrier properties is negligible. If the content of the melt blend is greater than 60 parts by weight, processing is difficult.

    [0035] The compatibilizer improves the compatibility of the polyolefin resin with the resin having barrier properties/the nanocomposite to form a stable composition.

    [0036] The compatibilizer may be a hydrocarbon polymer having polar groups. When a hydrocarbon polymer having polar groups is used, the hydrocarbon polymer portion increases the affinity of the compatibilizer to the polyolefin resin and to the resin having barrier properties/the nanocomposite, thereby obtaining a stable composition.

    [0037] The compatibilizer can include an compound selected from an epoxy-modified polystyrene copolymer, an ethylene-ethylene anhydride-acrylic acid copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-alkyl acrylate-acrylic acid copolymer, a maleic anhydride modified (graft) high-density polyethylene, a maleic anhydride modified (graft) linear low-density polyethylene, an ethylene-alkyl methacrylate-methacrylic acid copolymer, an ethylene-butyl acrylate copolymer, an ethylene-vinyl acetate copolymer, a maleic anhydride modified (graft) ethylene-vinyl acetate copolymer, and a modification thereof.

    [0038] The content of the compatibilizer is preferably 1 to 30 parts by weight, and more preferably 2 to 20 parts by weight. If the content of the compatibilizer is less than 1 part by weight, the mechanical properties of a molded article from the composition are poor. If the content of the compatibilizer is greater than 30 parts by weight, the molding of the composition is difficult.

    [0039] When an epoxy-modified polystyrene copolymer is used as the compatibilizer, a copolymer comprising a main chain which comprises 70 to 99 parts by weight of styrene and 1 to 30 part by weight of an epoxy compound represented by Formula 1, and branches which comprise 1 to 80 parts by weight of acrylic monomers represented by Formula 2, is preferable.



    [0040] where each of R and R' is independently a C1-C20 aliphatic residue or a C5-C20 aromatic residue having double bonds at its termini



    [0041] Each of the maleic anhydride modified (graft) high-density polyethylene, maleic anhydride modified (graft) linear low-density polyethylene, and maleic anhydride modified (graft) ethylene-vinyl acetate copolymer preferably comprises branches having 0.1 to 10 parts by weight of maleic anhydride based on 100 parts by weight of the main chain. When the content of the maleic anhydride is less than 0.1 part by weight, it does not function as the compatibilizer. When the content of the maleic anhydride is greater than 10 parts by weight, it is not preferable due to an unpleasant odor.

    [0042] A container having barrier properties can be manufactured by molding the nanocomposite composition having barrier properties according to the present invention. Due to the dry-blended nanocomposite composition, the nanocomposite morphology having barrier properties can be maintained to obtain a molded article having good barrier properties.

    [0043] The molded article may be obtained by a general molding method including blowing molding, extrusion molding, pressure molding and injection molding.

    [0044] In addition to the container having barrier properties, a sheet or film having barrier properties can be manufactured.

    [0045] The container or sheet having barrier properties can be a multi-layered container or film further including an adhesive layer and a polyolefin layer.

    [0046] For example, the sheet or container having barrier properties can be manufacture from a 5-layered film of HDPE/adhesive/ nanocomposite composition of the present invention/adhesive/HDPE.

    Advantageous Effects



    [0047] The nanocomposite composition according to an embodiment of the present invention has superior barrier properties and moldability, and thus the article manufactured therefrom has an excellent performance as a container, sheet or film having barrier properties.

    [0048] While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.

    Description of Drawings



    [0049] The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which:

    FIG. 1 is an electron microscopic photograph (× 200) of the cross section of an article blow-molded from a nanocomposite composition according to an embodiment of the present invention; and

    FIG. 2 is an electron microscopic photograph (× 5000) of the cross section of an article blow-molded from a nanocomposite composition according to an embodiment of the present invention.


    Best Mode


    Examples



    [0050] The materials used in the following examples are as follows:

    EVOH: E105B (Kuraray, Japan)

    Amorphous nylon: SELAR 2072 (Dupont, USA)

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

    Nylon 6: EN 500 (KP Chemicals)

    HDPE-g-MAH: Compatibilizer, PB3009 (CRAMPTON)

    HDPE: ME6000 (LG CHEM)

    Ionomer: SURLYN 8527 (Dupont, USA)

    Clay: Closite 30B (SCP)

    Thermal stabilizer: IR 1098 (Songwon Inc.)


    Preparation Example 1


    (Preparation of EVOH/Intercalated Clay Nanocomposite)



    [0051] 97 wt % of an ethylene-vinyl alcohol copolymer (EVOH; E-105B (ethylene content: 44 mol %); Kuraray, Japan; melt index: 5.5 g/10 min; density: 1.14 g/cm3) was put in the main hopper of a twin screw extruder (SM Platek co-rotation twin screw extruder; ϕ 40). Then, 3 wt% of organic montmorillonite (Southern Intercalated Clay Products, USA; C2OA) as an intercalated clay and 0.1 part by weight of IR 1098 as a thermal stabilizer based on total 100 parts by weight of the EVOH copolymer and the organic montmorillonite was separately put in the side feeder of the twin screw extruder to prepare an EVOH/intercalated clay nanocomposite in a pellet form. The extrusion temperature condition was 180-190-200-200-200-200-200 °C , the screws were rotated at 300 rpm, and the discharge condition was 15 kg/hr.

    Preparation Example 2


    (Preparation of Nylon 6/Intercalated Clay Nanocomposite)



    [0052] 97 wt % of a polyamide (nylon 6) was put in the main hopper of a twin screw extruder (SM Platek co-rotation twin screw extruder; ϕ 40). Then, 3 wt% of organic montmorillonite as an intercalated clay and 0.1 part by weight of IR 1098 as a thermal stabilizer based on total 100 parts by weight of the polyamide and the organic montmorillonite was separately put in the side feeder of the twin screw extruder to prepare a nylon 6/intercalated clay nanocomposite in a pellet form. The extrusion temperature condition was 220-225-245-245-245-245-245 °C , the screws were rotated at 300 rpm, and the discharge condition was 40 kg/hr.

    Preparation Example 3


    (Preparation of Nylon 6,12/Intercalated Clay Nanocomposite)



    [0053] 95 wt % of a polyamide (nylon 6,12) was put in the main hopper of a twin screw extruder (SM Platek co-rotation twin screw extruder; ϕ 40). Then, 5 wt% of organic montmorillonite as an intercalated clay and 0.1 part by weight of IR 1098 as a thermal stabilizer based on total 100 parts by weight of the polyamide and the organic montmorillonite was separately put in the side feeder of the twin screw extruder to prepare a nylon 6,12/intercalated clay nanocomposite in a pellet form. The extrusion temperature condition was 225-245-245-245-245-245-240 °C , the screws were rotated at 300 rpm, and the discharge condition was 40 kg/hr.

    Preparation Example 4


    (Preparation of Amorphous Nylon/Intercalated Clay Nanocomposite)



    [0054] 95 wt % of a polyamide (amorphous nylon) was put in the main hopper of a twin screw extruder (SM Platek co-rotation twin screw extruder; ϕ 40). Then, 5 wt% of organic montmorillonite as an intercalated clay and 0.1 part by weight of IR 1098 as a thermal stabilizer based on total 100 parts by weight of the polyamide and the organic montmorillonite was separately put in the side feeder of the twin screw extruder to prepare an amorphous nylon/intercalated clay nanocomposite in a pellet form. The extrusion temperature condition was 215-225-235-235-235-235-230 °C, the screws were rotated at 300 rpm, and the discharge condition was 40 kg/hr.

    Preparation Example 5


    (Preparation of Ionomer/Intercalated Clay Nanocomposite)



    [0055] 95 wt % of an ionomer was put in the main hopper of a twin screw extruder (SM Platek co-rotation twin screw extruder; ϕ 40). Then, 5 wt% of organic montmorillonite as an intercalated clay and 0.1 part by weight of IR 1098 as a thermal stabilizer based on total 100 parts by weight of the ionomer and the organic montmorillonite was separately put in the side feeder of the twin screw extruder to prepare an ionomer/ intercalated clay nanocomposite in a pellet form. The extrusion temperature condition was 220-230-235-235-235-235-230 °C, the screws were rotated at 300 rpm, and the discharge condition was 40 kg/hr.

    Example 1



    [0056] 40 parts by weight of the EVOH nanocomposite obtained in the Preparation Example 1 and 60 parts by weight of EVOH were molten-blended at a temperature condition of 190-200-210-210-210-200 °C to prepare a EVOH nanocomposite/EVOH melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer (maleic anhydride modified (graft) high density polyethylene (HDPE-g-MAH, uniroyal chemical, USA, PB3009 (1% MAH content), melt index: 5 g/10 min, density: 0.95 g/cm3). Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 180-195-195-195-195-190 °C and the screws were rotated at 22 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 185-195-195-195-195-190 °C and the screws were rotated at 16 rpm.

    Example 2



    [0057] 40 parts by weight of the EVOH nanocomposite obtained in the Preparation Example 1 and 60 parts by weight of nylon 6 were molten-blended at a temperature condition of 215-220-210-210-210-200 °C to prepare a EVOH nanocomposite/nylon 6 melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 190-225-225-220-210 °C and the screws were rotated at 23 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-235 °C and the screws were rotated at 16 rpm.

    Example 3



    [0058] 40 parts by weight of the EVOH nanocomposite obtained in the Preparation Example 1 and 60 parts by weight of nylon 6,12 were molten-blended at a temperature condition of 225-235-245-245-245-240 °C to prepare a EVOH nanocomposite/nylon 6,12 melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 200-220-230-225-210 °C and the screws were rotated at 21 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-235 °C and the screws were rotated at 14 rpm.

    Example 4



    [0059] 40 parts by weight of the EVOH nanocomposite obtained in the Preparation Example 1 and 60 parts by weight of amorphous nylon were molten-blended at a temperature condition of 225-235-245-245-245-240 °C to prepare a EVOH nanocomposite/amorphous nylon melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 185-200-210-200-190 °C and the screws were rotated at 22 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-235 °C and the screws were rotated at 16 rpm.

    Example 5



    [0060] 40 parts by weight of the EVOH nanocomposite obtained in the Preparation Example 1 and 60 parts by weight of ionomer were molten-blended at a temperature condition of 225-235-245-245-245-240 °C to prepare a EVOH nanocomposite/ionomer melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 190-210-225-220-210 °C and the screws were rotated at 23 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-235 °C and the screws were rotated at 14 rpm.

    Example 6



    [0061] 40 parts by weight of the nylon 6 nanocomposite obtained in the Preparation Example 2 and 60 parts by weight of EVOH were molten-blended at a temperature condition of 220-235-245-245-245-240 °C to prepare a nylon 6 nanocomposite/EVOH melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 185-195-225-215-200 °C and the screws were rotated at 14 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-235 °C and the screws were rotated at 13 rpm.

    Example 7



    [0062] 40 parts by weight of the nylon 6 nanocomposite obtained in the Preparation Example 2 and 60 parts by weight of nylon 6 were molten-blended at a temperature condition of 220-235-245-245-245-240 °C to prepare a nylon 6 nanocomposite/nylon 6 melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 195-215-220-215-200 °C and the screws were rotated at 24 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-245-245-245-245-240 °C and the screws were rotated at 13 rpm.

    Example 8



    [0063] 40 parts by weight of the nylon 6 nanocomposite obtained in the Preparation Example 2 and 60 parts by weight of nylon 6,12 were molten-blended at a temperature condition of 230-240-245-245-245-235 °C to prepare a nylon 6 nanocomposite/nylon 6,12 melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 195-225-225-215-200 °C and the screws were rotated at 24 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-245-245-245 °C and the screws were rotated at 12 rpm.

    Example 9



    [0064] 40 parts by weight of the nylon 6 nanocomposite obtained in the Preparation Example 2 and 60 parts by weight of amorphous nylon were molten-blended at a temperature condition of 230-240-245-245-245-235 °C to prepare a nylon 6 nanocomposite/amorphous nylon melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 185-220-220-215-200 °C and the screws were rotated at 24 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-235 °C and the screws were rotated at 15 rpm.

    Example 10



    [0065] 40 parts by weight of the nylon 6 nanocomposite obtained in the Preparation Example 2 and 60 parts by weight of ionomer were molten-blended at a temperature condition of 210-225-235-235-235-230 °C to prepare a nylon 6 nanocomposite/ ionomer melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 185-235-235-235-235-230 °C and the screws were rotated at 21 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-240-240 °C and the screws were rotated at 12 rpm.

    Example 11



    [0066] 40 parts by weight of the nylon 6,12 nanocomposite obtained in the Preparation Example 3 and 60 parts by weight of EVOH were molten-blended at a temperature condition of 220-235-245-245-245-240 °C to prepare a nylon 6,12 nanocomposite/ EVOH melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 185-225-225-215-200 °C and the screws were rotated at 21 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 215-225-235-235-235-240 °C and the screws were rotated at 15 rpm.

    Example 12



    [0067] 40 parts by weight of the nylon 6,12 nanocomposite obtained in the Preparation Example 3 and 60 parts by weight of nylon 6 were molten-blended at a temperature condition of 220-235-245-245-245-240 °C to prepare a nylon 6,12 nanocomposite/ nylon 6 melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 185-245-245-245-240 °C and the screws were rotated at 23 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 205-225-235-240-240-245 °C and the screws were rotated at 12 rpm.

    Example 13



    [0068] 40 parts by weight of the nylon 6,12 nanocomposite obtained in the Preparation Example 3 and 60 parts by weight of nylon 6,12 were molten-blended at a temperature condition of 220-235-245-245-245-240 °C to prepare a nylon 6,12 nanocomposite/ nylon 6,12 melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 190-215-230-230-225-210 °C and the screws were rotated at 24 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 210-225-245-245-245-245 °C and the screws were rotated at 13 rpm.

    Example 14



    [0069] 40 parts by weight of the nylon 6,12 nanocomposite obtained in the Preparation Example 3 and 60 parts by weight of amorphous nylon were molten-blended at a temperature condition of 220-235-235-235-235-230 °C to prepare a nylon 6,12 nanocomposite/amorphous nylon melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 190-220-225-215-200 °C and the screws were rotated at 24 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-235 °C and the screws were rotated at 12 rpm.

    Example 15



    [0070] 40 parts by weight of the nylon 6,12 nanocomposite obtained in the Preparation Example 3 and 60 parts by weight of ionomer were molten-blended at a temperature condition of 215-235-245-245-245-240 °C to prepare a nylon 6,12 nanocomposite/ ionomer melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 195-225-225-225-200 °C and the screws were rotated at 22 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 225-235-235-235-235-240 °C and the screws were rotated at 13 rpm.

    Example 16



    [0071] 40 parts by weight of the amorphous nylon nanocomposite obtained in the Preparation Example 4 and 60 parts by weight of EVOH were molten-blended at a temperature condition of 205-215-215-215-215-210 °C to prepare an amorphous nylon nanocomposite/EVOH melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 185-205-215-210-200 °C and the screws were rotated at 20 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-235 °C and the screws were rotated at 13 rpm.

    Example 17



    [0072] 40 parts by weight of the amorphous nylon nanocomposite obtained in the Preparation Example 4 and 60 parts by weight of nylon 6 were molten-blended at a temperature condition of 225-235-235-235-235-230 °C to prepare an amorphous nylon nanocomposite/nylon 6 melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 195-215-220-215-200 °C and the screws were rotated at 23 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-240 °C and the screws were rotated at 13 rpm.

    Example 18



    [0073] 40 parts by weight of the amorphous nylon nanocomposite obtained in the Preparation Example 4 and 60 parts by weight of nylon 6,12 were molten-blended at a temperature condition of 225-240-240-240-240-235 °C to prepare an amorphous nylon nanocomposite/nylon 6,12 melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 200-220-225-215-205 °C and the screws were rotated at 22 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 215-225-235-235-235-240 °C and the screws were rotated at 12 rpm.

    Example 19



    [0074] 40 parts by weight of the amorphous nylon nanocomposite obtained in the Preparation Example 4 and 60 parts by weight of amorphous nylon were molten-blended at a temperature condition of 225-240-240-240-240-235 °C to prepare an amorphous nylon nanocomposite/amorphous nylon melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 190-205-215-205-195 °C and the screws were rotated at 24 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 200-215-215-215-215-220 °C and the screws were rotated at 13 rpm.

    Example 20



    [0075] 40 parts by weight of the amorphous nylon nanocomposite obtained in the Preparation Example 4 and 60 parts by weight of ionomer were molten-blended at a temperature condition of 225-240-240-240-240-235 °C to prepare an amorphous nylon nanocomposite/ionomer melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 195-215-220-215-205 °C and the screws were rotated at 22 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-240 °C and the screws were rotated at 12 rpm.

    Example 21



    [0076] 40 parts by weight of the ionomer nanocomposite obtained in the Preparation Example 5 and 60 parts by weight of EVOH were molten-blended at a temperature condition of 225-235-235-240-240-235 °C to prepare an ionomer nanocomposite/ EVOH melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 190-215-220-215-200 °C and the screws were rotated at 24 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 210-225-235-235-235-240 °C and the screws were rotated at 14 rpm.

    Example 22



    [0077] 40 parts by weight of the ionomer nanocomposite obtained in the Preparation Example 5 and 60 parts by weight of nylon 6 were molten-blended at a temperature condition of 225-240-245-245-245-240 °C to prepare an ionomer nanocomposite/nylon 6 melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 195-215-225-220-210 °C and the screws were rotated at 23 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-240 °C and the screws were rotated at 13 rpm.

    Example 23



    [0078] 40 parts by weight of the ionomer nanocomposite obtained in the Preparation Example 5 and 60 parts by weight of nylon 6,12 were molten-blended at a temperature condition of 225-245-245-245-245-240 °C to prepare an ionomer nanocomposite/nylon 6,12 melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 225-245-245-245-245-240 °C and the screws were rotated at 23 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-240 °C and the screws were rotated at 14 rpm.

    Example 24



    [0079] 40 parts by weight of the ionomer nanocomposite obtained in the Preparation Example 5 and 60 parts by weight of amorphous nylon were molten-blended at a temperature condition of 215-230-235-235-235-230 °C to prepare an ionomer nanocomposite/amorphous nylon melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the blow-molding process was performed to manufacture a 1000 mL container. At this time, the temperature condition was 185-215-220-215-200 °C and the screws were rotated at 24 rpm. Also, the dry blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 215-235-235-235-235-240 °C and the screws were rotated at 15 rpm.

    Example 25



    [0080] 40 parts by weight of the ionomer nanocomposite obtained in the Preparation Example 5 and 60 parts by weight of ionomer were molten-blended at a temperature condition of 215-235-235-235-235-240 °C to prepare an ionomer nanocomposite/ ionomer melt blend. 20 parts by weight of the melt blend was dry-blended with 70 parts by weight of HDPE and 10 parts by weight of a compatibilizer. Then, the nanocomposite composition was blow-molded into a 5-layered structure (HDPE/adhesive/nanocomposite composition/adhesive/HDPE) to manufacture a 1000 mL container. At this time, the temperature condition was 195-225-225-225-215 °C and the screws were rotated at 23 rpm. Also, the dry blend was extruded into a 5-layered structure (HDPE/adhesive/nanocomposite composition/adhesive/HDPE) to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-240 °C and the screws were rotated at 12 rpm.

    Example 26



    [0081] 40 parts by weight of the nylon 6 nanocomposite obtained in the Preparation Example 2 and 60 parts by weight of amorphous nylon were molten-blended at a temperature condition of 230-240-245-245-245-235 °C to prepare a nylon 6 nanocomposite/amorphous nylon melt blend. 4 parts by weight of the melt blend was dry-blended with 94 parts by weight of HDPE and 2 parts by weight of a compatibilizer to obtain a nanocomposite composition. Then, the nanocomposite composition was blow-molded into a 5-layered structure (HDPE/adhesive/nanocomposite composition/adhesive/HDPE) to manufacture a 1000 mL container. At this time, the temperature condition was 195-225-225-225-215 °C and the screws were rotated at 23 rpm. Also, the nanocomposite composition was extruded into a 5-layered structure (HDPE/adhesive/nanocomposite composition/ adhesive/HDPE) to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-240 °C and the screws were rotated at 12 rpm.

    Example 27



    [0082] 40 parts by weight of the nylon 6 nanocomposite obtained in the Preparation Example 2 and 60 parts by weight of amorphous nylon were molten-blended at a temperature condition of 230-240-245-245-245-235 °C to prepare a nylon 6 nanocomposite/amorphous nylon melt blend. 60 parts by weight of the melt blend was dry-blended with 35 parts by weight of HDPE and 5 parts by weight of a compatibilizer to obtain a nanocomposite composition. Then, the nanocomposite composition was blow-molded into a 5-layered structure (HDPE/adhesive/nanocomposite composition/adhesive/HDPE) to manufacture a 1000 mL container. At this time, the temperature condition was 195-225-225-225-215 °C and the screws were rotated at 23 rpm. Also, the nanocomposite composition was extruded into a 5-layered structure (HDPE/adhesive/nanocomposite composition/ adhesive/HDPE) to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-240 °C and the screws were rotated at 12 rpm.

    Comparative Example 1



    [0083] 70 parts by weight of HDPE, 10 parts by weight of a compatibilizer and 20 parts by weight of EVOH copolymer were blended and blow-molded to manufacture a 1000 mL container. At this time, the temperature condition was 180-190-190-185-180 °C and the screws were rotated at 22 rpm. Also, the blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-240 °C and the screws were rotated at 14 rpm.

    Comparative Example 2



    [0084] 70 parts by weight of HDPE, 10 parts by weight of a compatibilizer and 20 parts by weight of nylon 6 were blended and blow-molded to manufacture a 1000 mL container. At this time, the temperature condition was 210-220-225-215-200 °C and the screws were rotated at 21 rpm. Also, the blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-240 °C and the screws were rotated at 13 rpm.

    Comparative Example 3



    [0085] 70 parts by weight of HDPE, 10 parts by weight of a compatibilizer and 20 parts by weight of nylon 6,12 were blended and blow-molded to manufacture a 1000 mL container. At this time, the temperature condition was 215-225-230-215-205 °C and the screws were rotated at 22 rpm. Also, the blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-240-240-240-245 °C and the screws were rotated at 12 rpm.

    Comparative Example 4



    [0086] 70 parts by weight of HDPE, 10 parts by weight of a compatibilizer and 20 parts by weight of ionomer were blended and blow-molded to manufacture a 1000 mL container. At this time, the temperature condition was 205-215-225-220-215 °C and the screws were rotated at 14 rpm. Also, the blend was extruded to manufacture a 30 □ thick film. At this time, the temperature condition was 220-235-235-235-235-240 °C and the screws were rotated at 14 rpm.

    [0087] For the blow-molded containers and films manufactured in Examples 1-27 and Comparative Examples 1-4, barrier properties were tested and the results were shown in Tables 1 and 2.

    Experimental Example



    [0088] Toluene and M15 (a mixture of 85% toluene/isooctane (50/50) and 15% methanol) were put in the containers manufactured in Examples 1-27 and Comparative Examples 1-4. Then, the weight change was determined after 15 days in a dry oven at 50 °C

    [0089] The film manufactured in Examples 1-27 and Comparative Examples 1-4 were left alone under a temperature of 23 °C and a relative humidity of 50% for 1 day. Then, the gas penetration rate was determined (Mocon OX-TRAN 2/20, U.S.A).
    Table 1
    Barrier properties of containers
     Toluene (weight loss, %)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
    Table 2
    Barrier properties of films
     Oxygen penetration rate (ml/m2 × 24hrs 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


    [0090] As shown in Tables 1 and 2, containers and films of Examples 1 to 27 using the dry-blended composition including a polyolefin resin, a compatibilizer and a resin having barrier properties/nanocomposite melt blend have superior barrier properties to liquid and gas compared to those of Comparative Examples 1 to 4 using the composition including a polyolefin resin, a compatibilizer and a resin having barrier properties.

    [0091] Electron microscopic photographs of the cross section of the blow-molded container manufactured in Example 7 are shown in FIGS. 1 (× 200) and 2 (× 5000). As can be seen from FIGS. 1 and 2, the container manufactured from the nanocomposite composition having barrier properties includes the nanocomposite dispersed in the continuous polyolefin resin to have good barrier properties.


    Claims

    1. A nanocomposite composition obtained by dry-blending of:

    30 to 95 parts by weight of polyolefin resin;

    0.5 to 60 parts by weight of a melt blend i.) including at least one resin selected from the group consisting of an ethylene-vinyl alcohol (EVOH) copolymer, a polyamide, an ionomer and a polyvinyl alcohol (PVA); and ii.) at least one nanocomposite selected from the group consisting of an EVOH copolymer/intercalated clay nanocomposite, a polyamide/intercalated clay nanocomposite, an ionomer/intercalated clay nanocomposite and a polyvinylalcohol/intercalated clay nanocomposite;

    1 to 30 parts by weight of a compatibilizer,

    wherein the resin and the nanocomposite are molten-blended in a weight ratio from 25:75 to 75:25,

    wherein the polyolefin resin is at least one compound selected from the group consisting of a high density polyethylene (HDPE), a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), an ethylene-propylene polymer, and an ethylene-propylene copolymer, and

    wherein the compatibilizer is one or more compounds selected from the group consisting of an ethylene-ethylene anhydride-acrylic acid copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-alkyl acrylate-acrylic acid copolymer, a maleic anhydride modified (graft) high density polyethylene, a maleic anhydride modified (graft) linear low-density polyethylene, an ethylene-alkyl (meth)acrylate-(meth)acrylic acid copolymer, an ethylene-butyl acrylate copolymer, an ethylene-vinyl acetate copolymer, and a maleic anhydride modified (graft) ethylene-vinyl acetate copolymer.


     
    2. The composition of claim 1, wherein the intercalated clay is at least one compound selected from the group consisting of montmorillonite, bentonite, kaolinite, mica, hectorite, fluorohectorite, saponite, beidelite, nontronite, stevensite, vermiculite, hallosite, volkonskoite, suconite, magadite, and kenyalite.
     
    3. The composition of claim 1, wherein the intercalated clay comprises 1 to 45 wt.-% of an organic material.
     
    4. The composition of claim 3, wherein the organic material has at least one functional group selected from the group consisting of from primary ammonium to quaternary ammonium, phosphonium, maleate, succinate, acrylate, benzylic hydrogen, oxazoline and dimethylstearylammonium.
     
    5. The composition of claim 1, wherein the ethylene-vinyl alcohol copolymer contains 10 to 50 mol % of ethylene.
     
    6. The composition of claim 1, wherein the polyamide is nylon 4.6, nylon 6, nylon 6.6, nylon 6.10, nylon 7, nylon 8, nylon 9, nylon 11, nylon 12, nylon 46, MXD6, amorphous polyamide, a copolymerized polyamide containing at least two of these, or a mixture of at least two of these.
     
    7. The composition of claim 1, wherein the ionomer has a melt index of 0.1 to 10 g/10 min (190°C, 2,160 g).
     
    8. The composition of claim 1, wherein the weight ratio of the resin to the intercalated clay in the nanocomposite is 58.0:42.0 to 99.9:0.1.
     
    9. An article including the nanocomposite composition of any one of claims 1-8.
     


    Ansprüche

    1. Nanokomposit-Zusammensetzung, erhältlich durch Trocken-Mischen von:

    30-95 Gewichtsteilen eines Polyolefinharzes;

    0,5 bis 60 Gewichtsteile einer Schmelzmischung i.) umfassend zumindest ein Harz ausgewählt aus der Gruppe, bestehend aus einem Ethylen-Vinylalkohol (EVOH)-Copolymer, einem Polyamid, einem Ionomer und einem Polyvinylalkohol (PVA); und ii.) zumindest einem Nanokomposit, ausgewählt aus der Gruppe, bestehend aus einem EVOH-Copolymer/eingelagerter-Ton-Nanokomposit, einem Polyamid/eingelagerter-Ton-Nanokomposit, einem Ionomer/eingelagerter-Ton-Nanokomposit und einem Polyvinylalkohol/eingelagerter-Ton-Nanokomposit;

    1 bis 30 Gewichtsteile eines Verträglichkeitsvermittlers,

    wobei das Harz und das Nanokomposit in einem Gewichtsverhältnis von 25:75 bis 75:25 geschmolzen gemischt sind,

    wobei das Polyolefinharz zumindest eine Verbindung, ausgewählt aus der Gruppe, bestehend aus einem Polyethylen hoher Dichte (HDPE), einem Polyethylen niedriger Dichte (LDPE), einem linearen Polyethylen niedriger Dichte (LLDPE), einem Ethylen-Propylenpolymer und einem Ethylen-Propylencopolymer, ist, und

    wobei der Verträglichkeitsvermittler eine oder mehrere Verbindungen ist, die ausgewählt sind aus der Gruppe, bestehend aus einem Ethylen-Ethylenanhydrid-Acrylsäure-Copolymer, einem Ethylen-Ethylacrylat-Copolymer, einem Ethylen-Alkylacrylat-Acrylsäure-Copolymer, einem Maleinsäureanhydrid modifizierten (Pfropf) Polyethylen hoher Dichte, einem Maleinsäureanhydrid modifizierten (Pfropf) linearen Polyethylene niedriger Dichte, einem Ethylen-Alkyl(meth)acrylat-(Meth)acrylsäure-Copolymer, einem Ethylen-Butylacrylatcopolymer, einem EthylenVinylacetat-Copolymer und einem Maleinsäureanhydrid modifizierten (Pfropf) Ethylen-Vinylacetatcopolymer.


     
    2. Zusammensetzung nach Anspruch 1, wobei der eingelagerte Ton zumindest eine Verbindung ist, die ausgewählt ist aus der Gruppe, bestehend aus Montmorillonit, Bentonit, Kaolinit, Glimmer, Hektorit, Fluorhektorit, Saponit, Beidellit, Nontronit, Stevensit, Vermiculit, Halloysit, Volkonskoit, Suconit, Magadiit und Kenyalit.
     
    3. Zusammensetzung nach Anspruch 1, wobei der eingelagerte Ton 1 bis 45 Gewichtsprozent eines organischen Materials umfasst.
     
    4. Zusammensetzung nach Anspruch 3, wobei das organische Material zumindest eine funktionelle Gruppe hat, die ausgewählt ist aus der Gruppe, bestehend aus primärem Ammonium bis quaternärem Ammonium, Phosphonium, Maleat, Succinat, Acrylat, benzylischem Wasserstoff, Oxazolin und Dimethylstearylammonium.
     
    5. Zusammensetzung nach Anspruch 1, wobei das Ethylen-Vinylalkohol-Copolymer 10 bis 50 Mol.-% Ethylen umfasst.
     
    6. Zusammensetzung nach Anspruch 1, wobei das Polyamid Nylon 4.6, Nylon 6, Nylon 6.6, Nylon 6.10, Nylon 7, Nylon 8, Nylon 9, Nylon 11, Nylon 12, Nylon 46, MXD6, amorphes Polyamid, ein copolymerisiertes Polyamid, das zumindest zwei der Vorangehenden umfasst, oder ein Gemisch von zumindest zwei der Vorangehenden ist.
     
    7. Zusammensetzung nach Anspruch 1, wobei das Ionomer einen Schmelzindex von 0,1 bis 10 g/10 min. (190°C; 2,160 g) hat.
     
    8. Zusammensetung nach Anspruch 1, wobei das Gewichtsverhältnis des Harzes zu dem eingelagerten Ton in dem Nanokomposit von 58,0:42,0 bis 99,9:0,1 ist.
     
    9. Artikel, der die Nanokomposit-Zusammensetzung nach einem der vorangehenden Ansprüche 1 bis 8 umfasst.
     


    Revendications

    1. Une composition nanocomposite comprenant :

    30 à 95 parties en poids d'une résine polyoléfine ;

    0,5 à 60 parties en poids d'un mélange fondu i.) incluant au moins une résine sélectionnée dans le groupe constitué d'un copolymère d'éthylène-alcool vinylique (EVOH), un polyamide, un ionomère et un alcool polyvinylique (PVA) ; et ii) au moins un nanocomposite sélectionné dans le groupe constitué d'un nanocomposite de copolymère EVOH/argile intercalée, un nanocomposite de polyamide/argile intercalée, un nanocomposite d'ionomère/argile intercalée et un nanocomposite d'alcool polyvinylique/argile intercalée ;

    1 à 30 parties en poids d'un agent de compatibilité,

    où la résine et le nanocomposite sont mélangés-fondus dans un rapport en poids de 25/75 à 75/25,

    où la résine polyoléfine est au moins un composé sélectionné parmi le groupe constitué d'un polyéthylène haute densité (HDPE), un polyéthylène basse densité (LDPE), un polyéthylène basse densité linéaire (LLDPE), un polymère d'éthylène-propylène et un copolymère d'éthylène-propylène, et

    où l'agent de compatibilité est un ou plusieurs composés sélectionnées parmi le groupe constitué d'un copolymère d'éthylène-anhydride d'éthylène-acide acrylique, un copolymère d'éthylène-acrylate d'éthyle, un copolymère d'éthylène-acrylate d'alkyle-acide acrylique, un polyéthylène haute densité modifié par un anhydride maléique (greffe), un polypropylène modifié par un anhydride maléique (greffe), un polyéthylène basse densité linéaire modifié par un anhydride maléique (greffe), un copolymère d'éthylène-(méth)acrylate d'alkyle-acide (méth)acrylique, un copolymère d'éthylène-acrylate de butyle, un copolymère d'éthylène-acétate de vinyle et un copolymère d'éthylène-acétate de vinyle modifié par un anhydride maléique (greffe).


     
    2. La composition selon la revendication 1, où l'argile intercalée est au moins un composé sélectionné parmi le groupe constitué de montmorillonite, bentonite, kaolinite, mica, hectorite, fluorohectorite, saponite, beidelite, nontronite, stevensite, vermiculite, hallosite, volkonskoite, suconite, magadite et kenyalite.
     
    3. La composition selon la revendication 1, où l'argile intercalée comprend 1 à 45% en poids d'une matière organique.
     
    4. La composition selon la revendication 3, où la matière organique a au moins un groupe fonctionnel sélectionné parmi le groupe constitué d'ammonium primaire à amonium quaternaire, phosphonium, maléate, succinate, acrylate, hydrogène benzylique, oxazoline et diméthyl stéaryl ammonium.
     
    5. La composition selon la revendication 1, où le copolymère d'éthylène-alcool vinylique contient 10 à 50 mol% d'éthylène.
     
    6. La composition selon la revendication 1, où le polyamide est un nylon 4.6, nylon 6, nylon 6.6, nylon 6.10, nylon 7, nylon 8, nylon 9, nylon 11, nylon 12, nylon 46, MXD6, polyamide amorphe, un polyamide copolymérisé contenant au moins deux de ceux-ci ou un mélange d'au moins deux de ceux-ci.
     
    7. La composition selon la revendication 1, où l'ionomère a un indice de fusion de 0,1 à 10 g/10 min (190°C, 2160 g).
     
    8. La composition selon la revendication 1, où le rapport en poids de la résine et de l'argile intercalée dans le nanocomposite est compris entre 58,0/42,0 et 99,9/0,1
     
    9. Un article incluant la composition nanocomposite selon l'une quelconque des revendications 1 à 8.
     




    Drawing