TWI328592B - Gas-barrier nanocomposite composition and article using the same - Google Patents

Description

17430pif.doc IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a composition of a gas-resistant nano-composite and a method for producing the same, and in particular to a method having superior barrier properties and plasticity. The nano composition is a dry blend of a polyolefin resin, including a melt-mixing of a barrier resin and a barrier nano composition, and a compatibilizing agent; and a method of producing the product. [Prior Art] This application is filed on July 21, 2004, and the application of the Korean Patent No. 10-2004-0056996, filed on Jan. 21, 2004, filed on April 8, 2005. The related information disclosed in the No. 10-2005-0047116 application on June 2, 2005 is incorporated herein by reference. Resins for general use such as polyethylene, polypropylene, etc. have excellent plasticity, mechanical properties, and resistance to moisture, and are therefore used in many fields. However, these resins are also restricted to use in industries such as agrochemicals, food packaging or containers that require superior chemical and oxygen barrier properties. One ethylene-vinyl alcohol copolymer [ethylene_vinyl alc〇h〇1 (EV〇H) copolymer] and polyacrylamide resin [p〇iyamideresins] have transparent and good gas barrier properties. However, since these resins are more expensive than general-purpose resins, the content of the products is limited. Therefore, in order to reduce the cost, a mixed resin having a barrier property, such as a vinyl alcohol copolymer [(EVOH)] and a polyamide (polyamide 1328592 17430pi), and an inexpensive olefin are proposed. However, the resistance characteristics expected to be satisfactory were not obtained. In order to improve the barrier properties, a completely exfoliated, or partially exfoliated, inserted, or partially inserted nanocomposite is formed by diffusing a nanometer-sized plug-in clay in a polymer matrix. When an adjusted object is produced, the above nano composition is used. 'The nano composition maintains its shape and has a barrier property even after being shaped, and its plasticity is superior and easy to produce into a sheet or film type'. container. SUMMARY OF THE INVENTION An object of the present invention is to provide a nano composition having excellent mechanical strength and a property of blocking oxygen, organic solvent and moisture, and having good plasticity. A further object of the present invention is to provide an article produced from a barrier composition having a nanostructure. According to one aspect of the present invention, the present invention provides a dry mixed composition comprising: 30 to 95 by weight of an olefin resin; 0.5 to 60 by weight of the molten mixture comprising at least one barrier resin, selected from ethylene-vinyl alcohol copolymerization a group consisting of ethylene-vinyl alcohol (EVOH) copolymer, polyamide resins, ionomers and polyvinyl alcohol (PVA), and at least one resistive nano-composition Free ethylene-vinyl alcohol (EVOH) copolymer/inserted clay nano composition, polyamine/inserted clay nano composition, ionomer/inserted clay nano composition, and a group consisting of a polyvinyl alcohol/insert 17430pif.doc-incorporated clay type nano-composite; and a 1 to 30-weight ratio compatibilizer. In one embodiment of the present invention, the resin having a barrier property and the composition having a barrier property can be melt-mixed in a weight ratio of from 25:75 to 75:25. In other embodiments of the present invention, the resin having a barrier property and the composition having a barrier property are formed using a co-rotation twin screw extruder or a single screw extruder at the melting point of the resin or Melting-mixing can be performed at higher temperatures. According to other embodiments of the present invention, an article made of a composition comprising a nano composition is also proposed. In an embodiment of the present invention, the article may be subjected to blow molding, extrusion molding, pressure molding, or injection molding. manufacturing. In other embodiments of the present invention, the article may be a container, sheet, tube, or film having a resistive property. The above and other objects, features and advantages of the present invention will become more apparent and obvious. The preferred embodiment, in conjunction with the drawings, is described in detail below. [Embodiment] The present invention will be explained in more detail later. The Korean Patent Application No. 2002-76575, which has been previously filed, discloses that the composition of the nano-composite composition comprises: an olefin resin having a weight ratio of from 1 to 97; a composition having a weight-reducing characteristic of from 1 to 95, selected from ethylene-ethylene 1328592 17430pif.doc Alcohol copolymer [ethylene-vinyl alcohol (EVOH) copolymer], with polyethers [polyamide resins], ionomer (ionomer) and a polyvinyl alcohol (PVA) group, and at least one The barrier nano composition is selected from the group consisting of an ethylene-vinyl alcohol (EVOH) copolymer/plug-in clay type nano-polyamide/plug-in clay type nano-ionomer/ionomer/plug-in clay The type of nano-composition, and a group consisting of a polyvinyl alcohol/inserted clay type nano composition; and a 1 to 95-weight ratio of a compatibilizer to complete the present invention. According to an embodiment of the present invention, a composition having a barrier property nano composition is a dry-mixed melt-blending resin having a resistive property and a nano-resistance composition, a polyolefin resin and a compatibilizing agent. . Therefore, the composition of the nano composition is a dry mixed composition comprising: 30 to 95 by weight of a polyolefin resin; 0.5 to 60 by weight of a melt mixture comprising at least one resin having a barrier property selected from ethylene-vinyl alcohol Copolymer [ethylene-vinyl alcohol (EVOH) copolymer], a group consisting of polyamide resins, ionomers and polyglycols (PVA), and at least one resistive nanoparticle The composition is selected from the group consisting of an ethylene-vinyl alcohol (EVOH) copolymer/inserted clay type nanometer, a polyamidamide/inserted clay type nano-composite, an ionomer (ionomer)/inserted clay type nanometer. Composition, and a group consisting of a polyvinyl alcohol/inserted clay type nano composition; and a 1 to 3 weight ratio of a compatibilizer. 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 straight chain low density polyethylene 17430 pif. doc thin (LLDPE), and a propylene-propylene copolymer. , a metal aromatic (metaU〇cene) and a group of polypropylene. The polypropylene may be at least one compound selected from the group consisting of a polypropylene of a co-phase polymer, a polypropylene of a co-polymer, a metallocene polypropylene, and a composition resin by adding talc (talc). , flame retardant, etc. A polyacrylic in-phase polymer or copolymer is added to improve physical properties. The content of the polyolefin resin is preferably from 30 to 95 by weight, and more preferably from 70 to 90 by weight. If the content of the polyolefin resin is less than 30% by weight, molding may be difficult. If the content of the polyolefin resin is more than 9 Torr, the barrier properties are not good. The melt/mixing of the resin/nano composition may be formed by forming a peeling or partially exfoliating resistive characteristic nano composition from the plugging clay, and then melting-mixing the nano composition and resisting characteristics. Resin. In particular, the melt/mixing of the resin/nano composition may be melted and mixed with at least one resin having a barrier property selected from the group consisting of ethylene-vinyl alcohol (EVOH) copolymer and polyamide resins. a group consisting of an ionomer and a polyacetal (PVA), and at least one nanostructure consisting of a barrier property selected from the group consisting of an ethylene vinyl alcohol (EVOH) copolymer/inserted clay type nanometer Composition, polyamine/inserted clay type nano composition, ionomer/insert clay type nano composition, and a polyvinyl alcohol/inserted clay type nanocomposite. The barrier-resistance resin is added to the plug-in clay to form a nano-sized exfoliated or partially exfoliated nano-composition. Because this nanometer constitutes the type of 13285592 17430pif.doc 'the gas and liquid passage in the resin is expanded, the moisture and liquid resistance properties of the resin itself are improved, and the melting strength of the polyolefin is due to the plug-in clay. Enhanced to prevent the fall of the parison in the bl〇w molding. The weight ratio of the resin having a barrier property to the insert clay is 58.0: 42.0 to 99.9: 0.1, and preferably 85.0: 15.0 to 99.0: 1.0 in the nano composition. If the weight ratio of the resin having the barrier property is less than 58.0: 42.0 with respect to the plug-in clay, the plug-in clay is difficult to aggregate and diffuse. If the weight ratio of the resin having the barrier property is greater than 99.9 : 0.1 with respect to the plug-in clay, the improvement of the barrier property can be ignored. Since the nano composition is melt-mixed with a resin having a barrier property, the range of the process temperature is wide in the molding step. Therefore, the composition of the mixture can be selected and the mixing ratio can be adjusted to prepare the desired shaped article in accordance with the process temperature conditions. In order to obtain the melt mixing of the resin/nano composition having the barrier property, the dissolution-mixing step is preferably carried out at an environment of 175 to 270 °C. The insert clay is preferably an organic insert clay. The content of the organic substance of the insert type clay is preferably from 1 to 45% by weight. When the content of the organic substance is less than 1% by weight, the compatibility of the insert type clay with the resin having a barrier property is not good. When the organic matter content is more than 45% by weight, the peeling of the resin having a barrier property is difficult. The insert clay comprises at least one substance selected from the group consisting of montmorillonite (montmorillonite), bentonite, kaolinite, crystal mica, hectorite, lithium bentonite 10 17430pif.doc (fluorohectorite), saponite, beidelite, nontronite, stevensite, vermiculite, hallosite, buddha Volkonskoite, aconite, magadite and kenyalite; and organic materials preferably including a functional group functional group selected from a primary to a quaternary ammonium salt (phosphonium), maleate, succinate, acrylate, benzylic hydrogen, oxazoline (〇xaz〇line) and bis-di-bis-stearyl A group of dimethyldisteary lammonium. The weight ratio of the resin having the barrier property to the preferred melting-mixing composition of the barrier nano-structure is from 25:75 to 75:25. If the amount of the resin having a barrier property is too large, the barrier property cannot be improved. If the amount of the barrier resin is too small, the impact resistance of the finally molded article is lowered. If the ethylene-vinyl alcohol (EVOH) copolymer comprises the nanostructure, the ethylene content of the ethylene-vinyl alcohol (EVOH) copolymer is preferably from 1% to 50% by mole. If the ethylene content is less than 1% by mole, the melt molding is difficult because of poor processability. If the ethylene content exceeds 50% by mole, the barrier properties of oxygen and liquid are insufficient. If the polyamine comprises the nano composition, the polyamine 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, one non- A crystalline polyamine, a copolymerized polyamine comprising at least two of the foregoing, or a mixture comprising at least two of the foregoing. 1328592 17430pif.doc The amorphous polyamine is equivalent to a polyamylamine with insufficient crystallinity, so 'differential scanning calorimetry (DSC) (model ASTM D-3417, 10 ° C / min) )] When measuring, there is no peak of crystallization of endothermic crystallization. In general, the polyamines can be prepared using diamines and dicarboxylic acids. For example, the diamines include ethylene diamine (hexamethylene diamine), 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethyldiamine. Ethane (2,2,4-trimethylhexamethylene diamine), bis(4-aminocyclohexyl)methane, 2,2-bis(4-amino group) Cyclohexyl)isopropyl diene [2,2-bis(4-aminocyclohexyl)isopropylidene], 1,4-diaminocyclohexane, 1,3-diamino ring 1,3-diaminocyclohexane, meta-xylenediamine, 1,5-diaminopentane, 1,4-diaminobutyline (1 , 4-diaminobutane ), 1,3-diaminopropane, 2-ethyldiaminobutane, 1,4-diaminocarbyl ring 1,4-diaminomethylcyclohexanes, methane-xylenediamine, fen-substituted or unsubstituted bis-m-xylene and p-phenylenediamine. For example, the double residual acid includes an alkyl-substituted or unsubstituted isophthalic acid (isophthalic acid), terephthalic acid, adipic acid, and a 1212328592 17430pif.doc acid ( Sebacic acid), butanedicarboxylic acid, etc. Polyamines prepared from aliphatic diamines and aliphatic dicarboxylic acids are general semi-crystalline polyamines [also known as crystamne nylon rather than amorphous polyamines. Polyamines prepared from diamines and aromatic dicarboxylic acids are not easily handled by a general melting process. Therefore, when one of the diamines and dicarboxylic acids used is aromatic, one of them is a 'It is a preferred preparation method of amorphous polyamine. The aliphatic functional group is preferably an aliphatic or C4-C8 alicyclic alkyl group in the amorphous polyamine. The aromatic of the amorphous polyamine Preferably, the functional group is substituted with a CVC6 mono- or bicyclic aromatic functional group. However, all of the above non-crystalline polydecylamines are not optimal in the present invention, for example, during the thermoplasticization process or when positioning to the process, Xylene diamine, adipamide is easily crystallized, which is not preferred. Examples of preferred amorphous polyamines include hexamethylene bisamine isophthalimide and hexamethylene diamine. Between the polymers of isophthalimide/m-phenylenediamine Phthalic acid/terephthalic acid (isophthalic acid/terephthalic acid) ratio from 99/1 to 60/40, between 2,2,4- and 2,4,4-trimethylhexamethylenediamine a mixture of xylyleneimine's a copolymer of hexamethylenediamine or 2-methylpentamethylenediamine and an isophthalic acid, terephthalic acid or a mixture thereof. When the polyamine It is based on hexamethylene bisamine isophthalimide/m-xylamine, which is highly terephthalic acid. It is useful to be mixed with other diamines by 13 1328592 17430pif.doc, for example 2- Methylpentamethylenediamine is used to produce a non-crystalline polyamine. The aforementioned amorphous polyamine containing only the aforementioned monomers may contain a small amount of lactam, for example, Caprolamine or caprylain (lauryl) is considered to be a co-monomer. It is important that the polyamine is amorphous. Therefore, any uncrystallized The polyamine can be used as a comonomer. About 10 wt% or less of a liquid or solid plasticizer, such as glycerol , sorbitol, or toluenesulfoneamide (Santicizer 8 monsanto) can also be included in the amorphous polyamine. For most applications, the glass transition temperature Tg of an amorphous polyamine ( Measured in a dry state, such as a moisture content of about 0.12% by weight or less, at about 7 (M 70 ° C, and preferably at about 80-160 ° C. The unmixed amorphous polyamine, It has a glass transition temperature Tg of about 125 ° C in a dry state. The lower limit of the glass transition temperature (Tg) is not clear, but 70 ° C is about a lower limit. The higher limit of the glass transition temperature (Tg) is also unclear. In any case, when a polyamine having a glass transition temperature (Tg) of about 170 ° C or higher is used, the thermoplastic type is difficult. However, polyamines having an acid and an aromatic functional amine are not suitable for the purpose of the present invention because the glass transition temperature (Tg) is too high to be thermoplastic. The polyamine can also be a half crystalline polyamine. The semi-crystalline polyamines are generally prepared using indoleamine, such as nylon 6 or nylon 11, or an amino acid, or prepared by concentrating a diamine, such as hexamethylene hexamethylene diamine, with two 1328592 17430pif.doc Dibasic acid, such as succinic acid 'adipic acid', sebacic acid. The polyamine can be a co-polymer or a terpolymer such as a copolymer of hexamethylenediamine/adipic acid and caprolactam (nylon 6,66). A mixture of two or more crystallized polyamines can also be used. The preparation of the semicrystalline and amorphous polyamines is a conventional technique by concentration polymerization. • If the ion body is contained in the nanocomposite, a preferred copolymer of acrylic acid and ethylene having a melting point of 0.1 to 10 g/10 min (190 ° C) , 2,160 g). The content of the melt mixing is preferably from 0.5 to 60 by weight, and more preferably from 8 to 30 by weight. If the melt mixture content ratio is less than 〇.5, the effect of improving the barrier properties is neglected. If the melt mixing content is more than 60% by weight, the process may be difficult. The compatibilizer improves the compatibility of the polyolefin resin with the resin/residual composition of the barrier properties to form a stable composition. The compatibilizer may be a hydrocarbon polymer having a polar functional group. When a polar functional group hydrocarbon polymer is used, the hydrocarbon polymer portion increases the affinity of the compatibilizing agent to the polyolefin resin and the resistive property/the nanocomposite resin to obtain a stable Composition. The compatibilizer comprises a compound selected from the group consisting of an epoxide-adjusted poly-ethylene copolymer, a polyethylene-ethylene anhydride-acrylic acid copolymer, and an ethylene. ·ethylene-ethyl acrylate copolymer, ethylene-alkyl propionate · 15 1328592 17430pif.doc ethylene-alkyl-acrylate-acrylic acid copolymer, one horse Anhydride-adjusted (branched) high-density polyethylene, monomaleic anhydride-adjusted (branched) linear low-density polyethylene, monovinyl-alkylmethylpropionate-methylpropionic acid Polymer, monoethylene-butyl propionate copolymer, monoethylene-ethylene acetate copolymer, monomaleic anhydride-adjusted (branched) ethylene·ethylene acetate copolymer, and adjusted analog. The content of the compatibilizer is preferably from 1 to 30 by weight, and more preferably from 2 to 20 by weight. If the weight ratio of the compatibilizer is 1, the plastic article of the composition is inferior in mechanical properties. If the content ratio of the compatibilizer is more than 30, the composition is plastically difficult. When an epoxide-adjusted polystyrene copolymer is used as the compatibilizer, the co-polymer comprises a stearyl group having a main chain weight ratio of 70 to 99, and an epoxy compound having a weight ratio of 1 to 30. a monomer represented by the formula 1, and the branch includes acrylic acid having a weight ratio of 1 to 80, preferably: -R-CH-CH-R'

* I wherein each R and R' are independent of an aliphatic functional group or - the C5-C2() aromatic function has a double bond and a double bond at the end. -CH2—CH-

c=o I CH, (2) 1328592 17430pif.d〇c Each maleic anhydride-adjusted (branched) high-density polyethylene, maleic anhydride-adjusted (branched) linear low-density polyethylene, and Preferred branches of the maleic anhydride-adjusted (branched) ethylene-ethylene acetate copolymer include maleic anhydride in a weight ratio of from 0.1 to ίο, with a weight ratio of the main chain of 1 。. When the maleic anhydride weight ratio is less than less than ο·1 by weight, it is not used as a compatibilizer. 'When the maleic anhydride content is more than 1 〇 by weight' is not preferred because the taste is not pleasing. According to the present invention, a container having a barrier property can be produced by casting a composition comprising the barrier property nano. Because of the dry mixed composition of the nano composition, the nano-composition type of the barrier property can be maintained in a cast molded article having good barrier properties. The cast-formed article can be produced by a method such as blow molding, extrusion molding, pressure molding, or injection molding. Further, the container having the barrier property can be produced by a sheet or film having a barrier property. The container or the sheet having the barrier property may be a multi-layered container, or the film further includes an adhesive layer and a polyolefin layer. For example, the container having the barrier property can be made of a 5-layer film. The 5-layer film comprises a high density polyethylene (HDPE)/adhesive agent/the composition of the nano composition of the invention/adhesive agent/ High density polyethylene (HDPE). In the following, the present invention will describe more details by way of example. The following examples are merely illustrative of the invention but are not intended to limit the invention. 17 1328592 17430pif.doc Example: The examples used are as follows: Ethylene-vinyl alcohol (EVOH): E105B (Kuraray, Japan) Non-crystalline nylon: SELAR 2072 (Dupont, USA) Nylon 6,12: Zytel 158L ( Dupont, USA) Nylon 6 : ΕΝ 500 (KP Chemicals) High Density Polyethylene (HDPE)-g-MAH : Compatibilizer, PB3009 (CRAMPTON) High Density Polyethylene (HDPE) : ME6000 (LG CHEM) Ion: SURLYN 8527 (Dupont, USA) Clay: Closite 30B (SCP) Thermal stabilizer: IR 1098 (Songwon Inc.) Preparation Example 1 (Preparation of ethylene-vinyl alcohol (EVOH)/insert clay composition) 97% by weight Ethylene-vinyl alcohol (EVOH) copolymer; E-105B (ethyl content: 44 mol%; Kuraray, Japan); melting parameters: 5.5 g/10 min; density: 1.14 g/cm3) One of the main feed hoppers is a twin-screw extruder (SM Platek co-rotating twin-screw extruder; φ40). Thereafter, 3% by weight of organic montmorillonite (Southern insert clay product, USA; C2〇A) was treated as a plug-in clay with 0.1 weight ratio of IR 1098 as a heat stabilizer, made at 100 It is the basis of the total weight ratio of ethylene-vinyl alcohol (EVOH) copolymer, and the organic montmorillonite is separately placed into one side feeder of the double screw 17430pif.doc rod extruder to separate and prepare. Nine-shaped ethylene-vinyl alcohol (EVOH)/inserted clay composed of nanometers. The extrusion temperature conditions include 180-190-200-200-200-200-200 ° C, the screw rotation speed is 300 i*pm, and the release condition is 15 kg/hr. Preparation Example 2 (Preparation of nylon 6/inserted clay nano composition) One hundredth of a weight percent of polyamine (nylon 6) was placed in one of the main feed hoppers of a twin screw extruder (SM Platek - Rotating twin-screw extruder; φ4〇). Thereafter, 3% by weight of organic montmorillonite (Southern insert clay product, USA; C20A) was treated as a plug-in clay with 0.1 weight ratio of IR 1098 as a heat stabilizer. For the total weight ratio of polyamide, the organic montmorolonite is placed in one side feeder of the twin-screw extruder to separate and form a nylon 6/nano composition. Plug-in clay. The extrusion temperature conditions include 220-225-245-245-245-245-2456C, the screw rotation speed is 300 rpm, and the release condition is 40 kg/hr. Preparation Example 3 (Preparation of nylon 6,12/inserted clay composed of nanometer)

One hundred percent by weight of polyamine (nylon 6,12) was placed in one of the main feed hopper twin screw extruders (SM Platek co-rotating twin screw extruder; φ40). Thereafter, 5% by weight of organic montmorillonite is used as a plug-in clay and 〇.1 by weight of IR 1328592 17430pif.doc 1098 as a thermal stabilizer, with 100 as the total weight ratio of polyamine Benchmark, at the same time, the organic montmorillonite was placed in the twin-screw extruder to prepare a nylon-shaped 6,12/nano-type plug-in clay. The extrusion temperature conditions include 225-245-245-245-245-245-240 ° C, the screw rotation speed is 300 rpm, and the release condition is 40 kg/hr. Preparation Example 4 (Preparation of non-crystalline nylon/inserted clay composed of nanometer) 95% by weight of polyamine (non-crystalline nylon) was placed in one of the main feed hoppers Machine (SM I>latek co-rotating twin screw extruder; φ40). Thereafter, 5% by weight of organic montmorillonite is used as a plug-in clay and 0.1 weight ratio of IR 1098 as a thermal stabilizer, with 100 as the weight ratio of polyamine, and the organic The montmorillonite was separately placed in the twin-screw extruder to prepare a non-crystalline nylon/inserted plug-type clay which was formed into a nine-shape. The extrusion temperature conditions include 215-225-235-235-235-235-230 ° C, the screw rotation speed is 300 rpm, and the release condition is 40 kg / hr. Preparation Example 5 (Preparation of ionomer/inserted clay composed of nanometer) 95% by weight One ion body was placed in one of the main feed hoppers of a twin screw extruder (SM Platek co-rotating twin screw) Extrusion machine; 20 1328592 17430pif.doc φ40). Thereafter, 5% by weight of organic montmorillonite is used as a plug-in clay and 10·1 liter ratio of IR 1098 as a thermal stabilizer, using 1 〇〇 as the total weight ratio of the ion, while The organic montmorillonite was separately placed in the twin-screw extruder to prepare a plug-form clay which was formed into a nine-shaped ion/nano. The extrusion molding temperature conditions included 220-230-235-235-235-235-230 °C', the screw rotation speed was 300 rpm, and the release condition was 40 kg/hr. Example 1 An ethylene-vinyl alcohol (EVOH) nano composition having a weight ratio of 40 was prepared by the method of Preparation Example 1, while 60 parts by weight of ethylene-vinyl alcohol (EVOH) was melted-mixed at a temperature of 190-200-210- An ethylene-vinyl alcohol (EVOH) nano composition/ethylene vinyl alcohol (EVOH) was prepared by performing melt mixing at 210-210-200 °C. The melt blending at a weight ratio of 20 is a dry blended weight ratio of 70 high density polyethylene (HDPE) to a weight ratio of 10 compatibilizer (maleic anhydride adjusted (branched) high density polyethylene (HDPE) -g-MAH, uniroyal chemical, USA, PB3009 (1% ΜΑΗ content), melting parameter: 5 g/10 min, density: 0.95 g/cm3). Thereafter, a blow molding process is performed to make a l〇〇 At the same time, the temperature condition is 180-195_195-195-195-190 ° C, and the screw rotation speed is 22 rpm. At the same time, the dry mixing is extruded to produce a film having a thickness of 30 Å. The temperature conditions include 185-195-195-195-195-190 ° C, and the screw rotation speed is 16 rpm. 21 1328592 17430 pif.doc Example 2 Ethylene-vinyl alcohol (EVOH) nano composition with a weight ratio of 40 to prepare The method of the first example, while 60 weight ratio of nylon 6 is melted and mixed to perform a melt mixing at a temperature of 215-220-210_210-210-200 ° C to prepare an ethylene vinyl alcohol (EVOH) nano composition / nylon 6 The melt ratio of the weight ratio of 20 to dry mix weight ratio of 70 high density polyethylene (HDPE) and weight A compatibilizer having a ratio of 10. After that, the blow molding process is carried out to form a 1000 mL container. At the same time, the temperature condition is 190-225-225-220-210 ° C, and the screw rotation speed is 23 At the same time, the dry mixing is extruded to produce a film having a thickness of 30 angstroms. At the same time, the temperature conditions include 220-235-235-235-235-235t: and the screw rotation speed is 16 rpm. A composition of 40 ethylene-vinyl alcohol (EVOH) nanometer was prepared to prepare the method of Example 1, while 60 weight ratio of nylon 6,12 was melted-mixed at a temperature of 225-235-245-245-245-240 ° C. To perform melt-mixing to prepare an ethylene-vinyl alcohol (EVOH) nano composition/nylon 6,12. The melt-mixed weight ratio of 20 is a dry mix weight ratio of 70 high density polyethylene (HDPE) to a weight ratio of 1〇. After a blowing agent molding process, a 1000 mL container is prepared, and the temperature condition is 200-220-230-225_210 ° C, and the screw rotation speed is 21 rpm. Mix and produce a film with a thickness of 30 (10) by extrusion. The same temperature as 22 1328592 17430pif.doc Conditions include 220-235-235-235-235-235 ° C, and the screw rotation speed is 16 rpm. Example 4 An ethylene-vinyl alcohol (EVOH) nano composition having a weight ratio of 40 was prepared by the method of Preparation Example 1, while 60 parts by weight of the amorphous nylon was melt-mixed at a temperature of 225-235-:245-245- 245-240. (: To perform melt-mixing to prepare an ethylene-vinyl alcohol (EVOH) nano composition/non-crystalline nylon. The weight ratio of the melt-mixed high-density polyethylene (HDPE) to weight ratio of 70 in a dry mix ratio A compatibilizer of 1 Torr. Thereafter, the blow molding process is carried out to form a 1000 mL container. At the same time, the temperature condition is 185-200-210-200-190 ° C, and the rotation speed of the screw is At the same time, the dry mixing was extruded to produce a film having a thickness of 30 / μ. Meanwhile, the temperature conditions included 220-235-235-235-235-235 ° C, and the screw rotation speed was 16 rpm. Example 5 Ethylene-vinyl alcohol (EVOH) nanocomb composition with a weight ratio of 40 to prepare the method of Example 1, while a 60 weight ratio of an ion body was melt-mixed at a temperature of 225-235-245-245-245- An ethylene-vinyl alcohol (EVOH) nanocomposite/ionic body was prepared by melt-mixing at 240 ° C. The melt-mixed weight ratio of 20 was a dry mix weight ratio of 7 〇 high density polyethylene (HDPE) to weight ratio. Is a compatibilizer of 1 。. After that, the blow molding process is performed to make a 1 〇〇〇 mL At the same time, the temperature conditions include 23 1328592 17430 pif.doc 190-210-225-220-210 ° C, and the screw rotation speed is 23 rPm. At the same time, the dry mixing is extruded to produce a film having a thickness of 30 (four). At the same time, the temperature conditions include 220-235-235-235-235-235 ° C ' and the screw rotation speed is 14 rpm. Example 6 The weight ratio of 40 nylon 6 nanometer composition to prepare the example 2 method, while 60 weight ratio The ethylene vinyl alcohol (EVOH) was melt-mixed to perform a melt mixing at a temperature of 220-235-245-245-245-240 ° C to prepare a nylon 6 nano composition/ethylene vinyl alcohol (EVOH). The melt mixture of weight ratio of 20 is dry mixed with a high density polyethylene (HDPE) having a weight ratio of 70 and a compatibilizer having a weight ratio of 10. Then, a blow molding machine is formed to form a 1000 mL container. The temperature condition is 185-195-225-215-200 ° C, and the screw rotation speed is 14 rpm. At the same time, the dry mixing is extruded to produce a film having a thickness of 30 glazing. Meanwhile, the temperature conditions include 220-235-235. -235-235-235 ° C, and the screw rotation speed is 13 rpm. Example 7 Weight A nylon 6 nanometer composition of 40 was prepared by the method of Preparation Example 2, while 60 weight ratio of nylon 6 was melt-mixed, melt-mixed, and subjected to melt mixing preparation at a temperature of 220-235-245-245-245-240 °C. A nylon 6 nm composition / nylon 6. The melt blending at a weight ratio of 20 is a dry blending weight ratio of 70 high density polyethylene (HDPE) to a weight ratio of 24 1328592 17430 pif.doc a compatibilizer. The blow molding process is then carried out to make a 1000 mL container. At the same time, the temperature conditions are 195-215-220-215-200. (3, and the screw rotation speed is 24 rpm. At the same time, the dry mixing is extruded to produce a film having a thickness of 30 qing. Meanwhile, the temperature condition includes 220-245-245-245-245-240 ° C ' and The screw rotation speed was 13 rpm. Example 8 Φ A weight ratio of 40 nylon 6 nanometer composition to prepare the method of Example 2, while 60 weight ratio of nylon 6,12 was melted-mixed and melted and mixed at a temperature of 230- 240-245-245-245-235 ° C to perform melt mixing to prepare a nylon 6 nanometer composition / nylon 6,12. The weight ratio of 20 of the melt mixing to - dry mix weight ratio of 7 〇 high density polyethylene (HDPE) and a compatibilizer with a weight ratio of 10. A blow molding machine molding process is then carried out to make a 1000 mL container. At the same time, the temperature condition is 195-225-225-215-200 ° C, and the screw rotates. The rotation speed was 24 rpm. At the same time, the dry mixing was extruded to produce a film having a thickness of 30. Meanwhile, the temperature conditions included 220-235-235-245-245-245 ° C, and the screw rotation speed was 13 rpm. 9 weight ratio of 40 nylon 6 nanometer composition to prepare the method of Example 2, while 60 weight ratio of non-crystal Nylon mining melt-mixing is melted-mixed to perform a melt mixing at a temperature of 230-240-245-245-245-235 ° C to prepare a nylon 6 nanometer composition/non-crystalline nylon. The weight ratio is 20 Melt and mix to dry mix a high density polyethylene (HDPE) of 70 by weight with a compatibilizer of weight ratio of 25 1328592 17430 pif.doc of 10. A blow molding machine is then formed to form a 1000 mL container. The temperature condition is 185-220-220-215-200 ° C, and the screw rotation speed is 24 rpm. At the same time, the dry mixing is extruded to produce a film having a thickness of 30 / an. Meanwhile, the temperature conditions include 220-235. -235-235-235-235 ° C, and the screw rotation speed is 15 rpm. Example 10 A weight ratio of 40 nylon 6 nanometer composition to prepare the sample 2 method 'at the same time 60 weight ratio of ionic melt-mixing Melt-mixing is carried out by melt-mixing at a temperature of 210-225-235-235-235-230 ° C to prepare a nylon 6 nanometer composition/ionic body. The weight ratio of the melt mixing is 20 in dry mixing ratio. 7 〇 high density polyethylene (HDPE) with a weight ratio of 10 compatibilizer. Stretch blow molding machine process to prepare a 1000 mL container. At the same time, the temperature condition was 185-235-235-235-235-230 ° C 'and the screw rotation speed is 21 rpm. At the same time, the dry mixing is produced by extrusion to produce a film having a thickness of 30 inches. At the same time, the temperature conditions include 220-235-235-235-240-240 ° C, and the screw rotation speed is 12 pm ° Example 11 weight ratio of 40 nylon, 12 nm composition to prepare the sample 3 method, while 60 weight The ratio of ethylene-vinyl alcohol (EVOH) to melt-mixing is melted-mixed to a temperature of 220-235-245-245-245-240 ° C to perform fusion mixing to prepare a nylon 6,12 nm composition / ethylene - Vinyl alcohol (EVOH). The melt mixing in a weight ratio of 20 is a dry blending weight ratio of 26 1328592 17430 pif.doc 70 of high density polyethylene (HDPE) to a compatibilizer of weight ratio of 10. Further, a blow molding process was carried out to prepare a 1 〇〇〇 mL container. At the same time, the temperature condition was 185-225-225-215-20 CTC, and the screw rotation speed was 21 rpm. At the same time, the dry mixing produces a film having a thickness of 30 by extrusion molding. At the same time, the temperature conditions include 215-225-235-235-235-240 ° C, and the screw rotation speed is 15 π π ^ Example 12 weight ratio of 40 nylon, 12 nm group composition to prepare the example 3 method, while 60 The weight ratio of nylon 6 was melted-mixed, melted-mixed, and subjected to melt mixing at a temperature of 220-235-245-245-245-240 ° C to prepare a nylon 6,12 nm composition/nylon 6. The melt mixture in a weight ratio of 20 was a dry blending weight ratio of 70 high density polyethylene (HDPE) to a compatibilizer having a weight ratio of 10. The blow molding process is then carried out to make a 1000 mL container. At the same time, the temperature condition was 185-245-245-245-240 ° C and the screw rotation speed was 23 rpm. At the same time, the dry mixing produces a film having a thickness of 30 (four) by extrusion molding. At the same time, the temperature conditions include 205-225-235-240-240-245 ° C, and the screw rotation speed is 12 rpm. Example 13 A nylon 6,12 nm composition having a weight ratio of 40 was prepared to prepare the method of Example 3, while 60 parts by weight of nylon 6,12 was melt-mixed and melted-mixed at a temperature of 220-235-245-245- A nylon 6,12 nm composition/nylon 6,12 was prepared by performing melt mixing at 245-240 °C. The weight ratio is 2 〇 the melted 27 1328592 17430 pif.doc mixed with a dry mix weight ratio of 70 high density polyethylene (HDPE) to a compatibilizer with a weight ratio of 10. Then, a blow molding machine molding process was carried out to prepare a lOOOOmL container. At the same time, the temperature conditions were 190-215-230-230-225-210 °C and the screw rotation speed was 24 rpm. At the same time, the dry mixing produces a film having a thickness of 30 Å by extrusion molding. Meanwhile, the temperature conditions include 210-225-245-245-245-245 ° C, and the screw rotation speed is 13 rpm. Example 14 A nylon 6,12 nm composition having a weight ratio of 40 was prepared to prepare the method of Example 3, while 60 parts by weight of the amorphous nylon was melted-mixed and melted-mixed at a temperature of 220-235-235-235- A nylon 6,12 nm composition/amorphous nylon was prepared by performing melt mixing at 235-230 °C. The melt blending at a weight ratio of 20 is a dry blend of a high density polyethylene (HDPE) having a weight ratio of 70 and a compatibilizer having a weight ratio of 10. Then, a blow molding process is carried out to make a l〇〇〇mL container. Meanwhile, the temperature condition was 190-220-225-215-200 ° C and the screw rotation speed was 24 rpm ,, and the dry mixing was extrusion-molded to produce a film having a thickness of 30 qing. At the same time, the temperature conditions include 220-235-235-235-235-235 °C, and the screw rotation speed is 12 rpm. Example 15 A nylon 6,12 nm composition having a weight ratio of 40 was prepared to prepare the method of Example 3, while a 60 weight ratio of the ion body was melt-mixed at a temperature of 215-235-245-245-245-240 ° C. Perform a melt mixing to prepare a nylon 28 1328592 17430 pif.doc 6, 12 nm composition / ion body. The melt blending at a weight ratio of 20 was a dry blending weight ratio of 7 Å high density polyethylene (HDPE) to a compatibilizer having a weight ratio of 10. The blow molding process is then carried out to make a 1 〇〇〇 mL container. At the same time, the temperature conditions were 195-225-225_225-200 ° C and the screw rotation speed was 22 rpm. At the same time, the dry mixing is extruded to produce a film having a thickness of 30 Å. At the same time, the temperature conditions include 225-235-235-235-235_240 ° C, and the screw rotation speed is 13 rpm. Example 16 A non-crystalline nylon nanostructure having a weight ratio of 40 was prepared to prepare the method of Example 4, while 60 parts by weight of ethylene-vinyl alcohol (EVOH) was melt-mixed at a temperature of 205-215-215-215-215. A non-crystalline nylon nano composition/ethylene-vinyl alcohol (EVOH) was prepared by performing melt mixing at -210 °C. The melt mixture having a weight ratio of 20 was dry mixed with a high density polyethylene (HDPE) having a weight ratio of 70 and a compatibilizer having a weight ratio of 10. Then, a blow molding machine was used to form a 1000 mL container. At the same time, the temperature condition was l85-205-215-210-200 ° C and the screw rotation speed was 22 rpm. At the same time, the dry mixing was extruded to produce a film having a thickness of 30 Å. At the same time, the temperature conditions include 220-235-235-235-235-235 °C, and the screw rotation speed is 13 rpm. Example 17 A non-crystalline nylon nanostructure having a weight ratio of 40 was prepared by the method of Preparation Example 4 while a 60 weight ratio of nylon 6 was melted-mixed at a temperature of 29 1328592 17430 pif.doc 225-235-235-235-235 A non-crystalline nylon nano composition/nylon 6 was prepared by performing melt mixing at -230 °C. The melt blending at a weight ratio of 20 was dry blended with a high density polyethylene (HDPE) in a weight ratio of 70 and a compatibilizer in a weight ratio of 10. The blow molding process is then carried out to make a 1000 mL container. At the same time, the temperature condition is 195-215-220-215-20 (TC and the screw rotation speed is 22 rpm. At the same time, the dry mixing is extruded to produce a film having a thickness of 30 / M. Meanwhile, the temperature condition includes 220- 235-235-235-235-240 ° C, and the screw rotation speed is 13 rpm. Example 18 A weight ratio of 40 amorphous nylon nano composition to prepare the method of Example 4, while 60 weight ratio of nylon 6,12 Melt-mixing is carried out at a temperature of 225-240-240-240-240-235 ° C to perform melt mixing to prepare a non-crystalline nylon nano composition / nylon 6,12. The melt mixture is dry at a weight ratio of 20. A high-density polyethylene (HDPE) with a weight ratio of 70 and a compatibilizer with a weight ratio of 10. A blow molding machine is used to form a 1000 mL container. At the same time, the temperature condition is 200-220-225- 215-205 ° C and the screw rotation speed is 22 rpm. At the same time, the dry mixing is extruded to produce a film having a thickness of 30 / μ. At the same time, the temperature conditions include 215-225-235-235-235-240 ° C And the screw rotation speed is 12 rpm. Example 19 The weight ratio of 40 is made of amorphous nylon nano Method of Example 4, while the non-crystalline nylon 60 by weight ratio of mining melt - mixed to a temperature of 30 1328592 17430pif.doc

Condition (3)···2.24^2.235. ^ To perform heteromixing to prepare non-junction & nylon nylon composition/non-crystalline nylon. The melt was mixed at a mass ratio of 2 Torr to a dry blending weight ratio of 70 high density polyethylene (HDpE) to a compatibilizer having a weight ratio of 10. A blow molding machine molding process is then performed to make a 1000 mL hopper. At the same time, the temperature condition is 190 205_215_205_195 <>C and the screw rotation speed is 24 rpn^, and the dry mixing produces a film of thickness 30 mils by extrusion molding. At the same time, the temperature conditions include φ 200-215_215_215-215-22 〇 ° C, and the screw rotation speed is 13 rpm. Example 20 A composition of a non-crystalline nylon nanoparticle having a weight ratio of 40 to prepare the method of Example 4, while a 60-weight ratio of ionic body melt-mixing was performed at a temperature condition of 225-240-240-240-240-235 °C. Melt mixing to prepare a non-crystalline 'nylon nano composition/ion body. The melt blending at a weight ratio of 20 was a dry blending weight ratio of 70 high density polyethylene (HDPE) to a compatibilizer having a weight ratio of 10. A blow molding machine molding process is then performed to make a 1000 mL susceptor. At the same time, the temperature conditions were 195-215-220-215-205 ° C and the screw rotation speed was 22 rpm. At the same time, the dry mixing is extruded to produce a film having a thickness of 30 Å. At the same time, the temperature conditions include 220-235-235-235-235-240 ° C, and the screw rotation speed is 12 rpm. Example 21 A ionic nanocomposite having a weight ratio of 40 to prepare the method of Example 5, while 60 weight ratio of ethylene-vinyl alcohol (EVOH) was melted-mixed to a temperature of 31 1328592 17430 pif.doc condition 225_235-235-240-240 -235t: To perform melt mixing to prepare an ion nano composition/ethylene-vinyl alcohol (EVOH). The melt ratio of a weight ratio of 20 was a dry blending weight ratio of 70 high density polyethylene (HDPE) to a compatibilizer having a weight ratio of 10. The blow molding process is then carried out to make a 1000 mL container. At the same time, the temperature conditions were 190-215-220-215-200 ° C and the screw rotation speed was 24 rpm. At the same time, the dry mixing produces a film of thickness 30 mils by extrusion molding. At the same time, the temperature conditions include 210-225-235-235-235-240t: and the screw rotation speed is 14 rpm. Example 22 A ionic body composition having a weight ratio of 40 to prepare the method of Example 5, while 60 parts by weight of nylon 6 was melt-mixed to perform melt mixing at a temperature condition of 225-240-245-245-245-240 °C. An ion nano composition/nylon 6 was prepared. The melt mixture having a weight ratio of 20 was mixed with a high density polyethylene (HDPE) having a dry weight ratio of 70 and a compatibilizer having a weight ratio of 10. The blow molding process is then carried out to make a 1000 mL container. At the same time, the temperature conditions were 195-215-225-220-210 ° C and the screw rotation speed was 23 rpm. At the same time, the dry mixing was extruded to produce a film having a thickness of 30 thick. At the same time, the temperature conditions include 220-235-235-235-235-240 ° C, and the screw rotation speed is 13 rpm. Example 23 A ionic nano-composition with a weight ratio of 40 to prepare the method of Example 5, while 60 weight ratios of nylon 6,12 were melt-mixed to a temperature condition of 32 1328592 17430 pif.doc 225-245-245-245-245- An ion nanostructure/nylon 6,12 was prepared by performing melt mixing at 240 °C. The melt mixture having a weight ratio of 20 was dry mixed with a high density polyethylene (HDPE) having a weight ratio of 70 and a compatibilizer having a weight ratio of 10. Then, a blow molding machine molding process was carried out to prepare a 1 〇〇〇 mL container. At the same time, the temperature conditions were 225-245-245-245-245-240 ° C and the screw rotation speed was 23 rpm. At the same time, the dry mixing was extruded to produce a film of 30 cm thick. At the same time, the temperature conditions include 220-235-235-235-235-240 ° C, and the screw rotation speed is 14 rpm. Example 24 A ionic nano-composition having a weight ratio of 40 to prepare the method of Example 5, while 60 parts by weight of amorphous nylon was melted and mixed at a temperature condition of 215-230-235-235-235-230 ° C. Ionic nanostructure/non-crystalline nylon was prepared by melt mixing. The melt blending at a weight ratio of 20 was dry blended with a high density polyethylene (HDPE) of 7 Torr and a compatibilizer having a weight ratio of 10. The blow molding process is then carried out to make a 1000 mL container. At the same time, the temperature conditions were 185-215-220-215-200 ° C and the screw rotation speed was 24 rpm. At the same time, the dry mixing was extruded to produce a film of 30 cm thick. At the same time, the temperature conditions include 215-235-235-235-235-240 ° C, and the screw rotation speed is 15 rpm. Example 25 Ionic Nanoparticle Composition with a Weight Ratio of 40 to Prepare the Method of Example 5' Simultaneous 60 Weight Ratio of Ion Body Melting-Mixing to a Temperature Condition 33 1328592 17430pif.doc 215-235-235-235-235-240° C is used to perform melt mixing to prepare an ion nano composition/ion body. The melt blending at a weight ratio of 20 was dry blended with a high density polyethylene (HDPE) of 70 by weight and a compatibilizer having a weight ratio of 10. Thereafter, the nano composition is formed into a 5-layer structure by a blow molding process [High Density Polyethylene (HDPE) / Adhesive / Nano Composition / Adhesive / High Density Polyethylene (HDPE) 】 One 1000 mL container. At the same time, the temperature conditions were 195-225-225-225-215 °C and the screw rotation speed was 23 rpm. At the same time, the dry mixing is produced by extrusion to produce a 5-layer structure [High Density Polyethylene (HDPE) / Adhesive / Nano Composition / Adhesive / High Density Polyethylene (HDPE)] . At the same time, the temperature conditions include 220-235-235-235-235-240T: and the screw rotation speed is 15 rpm. Example 26 A nylon 6 nanometer composition having a weight ratio of 40 was prepared to prepare the method of Example 2, while 60 weight ratio of amorphous nylon was melt-mixed and executed at a temperature condition of 230-240-245-245-245-235 °C. A nylon 6 nanocomposition/non-crystalline nylon was prepared by melt mixing. The melt blending at a weight ratio of 4 has a composition of one nanometer in a dry mix of high density polyethylene (HDPE) having a weight ratio of 94 and a compatibilizer having a weight ratio of 2. Thereafter, the nano composition is formed into a 5-layer structure by a blow molding process [High Density Polyethylene (HDPE) / Adhesive / Nano Composition / Adhesive / High Density Polyethylene (HDPE) 】 One 1000 mL container. At the same time, the temperature conditions were 195-225-225-225-215 ° C and the screw rotation speed was 23 rpm. Same as 34 1328592 17430pif.doc, the dry mixing is extruded to produce a 5-layer structure [high density polyethylene (HDPE) / adhesive / nano composition / adhesive / high density polyethylene (HDPE)] Film of thickness 30 Qiu. At the same time, the temperature conditions include 220-235-235-235-235-240 ° C, and the screw rotation speed is 12 rpm. Example 27 A nylon 6 nanometer composition having a weight ratio of 40 to prepare the method of Example 2, while 60 weight ratio of amorphous nylon was melt-mixed to perform melt mixing at a temperature condition of 230-240-245-245-245-235 °C. A nylon 6 nanocomposition/non-crystallinity was prepared. The melt mixture having a weight ratio of 60 was dry-mixed with a high-density polyethylene (HDPE) of 35 by weight and a compatibilizer of a weight ratio of 5 to obtain a composition of one nanometer. Thereafter, the nano composition is formed into a 5-layer structure by a blow molding process [High Density Polyethylene (HDPE) / Adhesive / Nano Composition / Adhesive / High Density Polyethylene (HDPE) 】 One 1000 mL container. At the same time, the temperature conditions were 195-225-225-225-215 ° C and the screw rotation speed was 23 rpm. At the same time, the dry mixing was extruded to produce a 5-layer structure [HDPE/adhesive/nano composition/adhesive/high density polyethylene (HDPE)] film having a thickness of 30 μη. At the same time, the temperature conditions include 220-235-235-235-235-240 ° C, and the screw rotation speed is 12 rpm. Comparative Example 1 High density polyethylene (HDPE) in a weight ratio of 70, a compatibilizer in a weight ratio of 10, and an ethylene-vinyl alcohol (EVOH) copolymer in a weight ratio of 20, 1 352,592, 17430 pif.doc were mixed and carried out. A blow molding machine molding process was used to make a 1000 mL container. At the same time, the temperature condition is 180-190-19 (M85-180 ° C and the screw rotation speed is 22 rpm. At the same time, the mixing is extruded to produce a film having a thickness of 30 / M. Meanwhile, the temperature conditions include 220-235 -235-235-235-240 ° C, and the rotation speed of the screw is 14 rpm. Comparative Example 2 High density polyethylene (HDPE) with a weight ratio of 70, a compatibilizer with a weight ratio of 10, and a weight ratio of 20 The nylon 6 is mixed and subjected to a blow molding process to form a l〇〇〇mL container. At the same time, the temperature condition is 210-220-225-215-200 ° C and the screw rotation speed is 21 rpm. The mixing is performed by extrusion to produce a film having a thickness of 30 sec. At the same time, the temperature conditions include 220-235-235-235-235-240 ° C, and the screw rotation speed is 13 rpm. Comparative Example 3 The weight ratio is 70 High-density polyethylene (HDPE), a compatibilizer with a weight ratio of 10, and nylon 6,12 with a weight ratio of 20 are mixed and subjected to a blow molding process to form a l〇〇〇mL container. The condition is 215-225-230-215-205 ° C and the screw rotation speed is 22 rpm. At the same time, the mixing is produced by extrusion molding. Film with a thickness of 30. At the same time, the temperature conditions include 220-235-240-240-240-245 ° C ' and the screw rotation speed is 12 rpm. Comparative Example 4 36 1328592 17430pi £doc High-density polyethylene with a weight ratio of 70 (HDPE), a compatibilizer having a weight ratio of 10 以及 and an ionomer having a weight ratio of 20 are mixed and subjected to a blow molding process to prepare a 1 〇〇〇 mL container. Meanwhile, the temperature condition is 205-215. -225-220-215 ° C and the screw rotation speed is 22 rpm» at the same time, the mixing is extruded to produce a film of thickness 30. Meanwhile, the temperature conditions include 220-235-235-235-235-240°. C, and the screw rotation speed is 14 rpm. The container and film produced by the draw molding process are tested in Examples 1-27 and Comparative Examples 1-4, and the resistance characteristics are tested and the results are shown in Tables 1 and 2. Experimental Example Toluene and M15 (a mixture of - 85% toluene/isooctane (50/50) and 15% methanol) were placed in a container to produce in the manner of Examples 1-27 and Comparative Examples 1-4. This was carried out after being placed in an oven at 50 ° C for 15 days. The film production was prepared by way of Example 27 and Comparative Examples 1-4. At a temperature of 23 ° C and a relative humidity of 50% environment released one day. The gas then transmittance was also measured (Mocon OX-TRAN 2/20, U.S.A). 37 1328592 17430pif.doc Table 1 container blocking characteristics

Toluene (loss of weight %) M15 (loss of weight %) 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 38 1328592 17430pif.doc Table 2 Oxygen permeability (ml/m2x24hrs latm) 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 13 1.48 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 Comparison Example 1 2238.19 Comparative Example 2 1324.51 Comparative Example 3 1255.66 Comparative Example 4 3342.01 39 1328592 17430pif.doc As shown in Tables 1 and 2, the dry mixed composition used in the containers and films of Examples 1 to 27 includes a polyolefin resin. a compatibilizer and a resin having a resistive property/nano composition are melt-mixed to produce superior barrier properties to liquids and gases, while comparing the compositions used in Comparative Examples 1 to 4 including polyolefin resins, a compatible The agent and a resin have a blocking property. An electron microscope sectional view of the container formed by the blow molding machine by the method of Example 7 is shown in Fig. 1 (χ200) and Fig. 2 (χ5000). As with Figures 1 and 2, the container produced from the nanocomposite composition having barrier properties includes spreading the nano composition in the continuous phase of the polyolefin resin to produce superior barrier properties. The nanocomposition composition has excellent resistance properties and plasticity according to the embodiment of the present invention, and the produced article has superior resistance properties to the container sheet or film. Although the present invention has been described above in terms of the preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view of an electron microscope (Fig. 200) of an article formed by a blow molding machine in accordance with an embodiment of the present invention. FIG. 2 is a view of the present invention. The embodiment is a cross-sectional view of an electron microscope (χ5000) diagram of an article made of a composition of one nanometer in accordance with a blow molding process. 40 1328592 17430pif.doc [Key component symbol description]

Claims (1)

1328592 17430pif.doc X. Apply for a patent garden: ^ 1. A dry mixed nano composition comprising 'a polyolefin resin having a weight ratio of 30 to 95; a melt blend of one of 0.5 to 60 by weight, the melt blend comprising at least one resin having at least one resistive property and at least one Resisting characteristic nano composition 'The resistive resin is selected from the group consisting of a vinyl-vinyl alcohol (EVOH) copolymer, a polyamine, an ion, and a polyvinyl alcohol (PVA) The nano-component of the barrier property is selected from the group consisting of an ethylene-vinyl alcohol (EV0H) copolymer/inserted clay nano, a polyamine/inserted clay nano, an ion/insert clay nano composition, and a a group consisting of a polyvinyl alcohol/inserted clay nano-composite; and a compatibilizer having a weight ratio of 1 to 30, wherein the resin having a barrier property is composed of the resin having a barrier property, both of which are melt-mixed The weight ratio is mixed from 25:75 to 75:25. 2. The dry-mixed nano-composition composition according to claim 1, wherein the polyolefin resin is at least one compound selected from the group consisting of a high density polyethylene (HDPE) and a low density polyethylene (LDPE). A group consisting of a chain of low density polyethylene (LLDPE), an ethylene-propylene polymer, and an ethylene-propylene copolymer. 3. The dry-mixed nano-composition composition according to claim 1, wherein the insert clay is at least one compound selected from the group consisting of montmorillonite, bentonite, kaolinite' crystal mica. Mica, hectorite, fluorohectorite, saponite, beidelite, 42 1328592 17430pif.doc nontronite, magnesium talc (stevensite), vermiculite, hallosite, volkonskoite, suconite, magadite and kenyalite. 4. The dry-mixed nano-composite composition of claim 1, wherein the insert clay comprises from 1 to 45% by weight of an organic substance. 5. The composition of the dry mixed nanometer of claim 4, wherein the organic substance comprises at least a functional group selected from the group consisting of primary ammonium to quaternary ammonium, phosphonium, maleic acid ( Maleate ), succinate, acryiate, benzylic hydrogen, oxazoline (〇xaz〇iine) and dimethyldisteary lammonium. 6. The composition of dry mixed nano-combination as described in claim 1, wherein the ethylene-vinyl alcohol copolymer comprises from 10 to 50% by mole of ethylene. 7. The dry-mixed nano composition according to claim 1, wherein the polyamine is selected from the group consisting of nylon 4.6, nylon 6, nylon 6.6, nylon 6.10, nylon 7, nylon 8, nylon 9, Nylon 11, nylon 12, nylon 46, reinforced polyamine (MXD6), amorphous polyamine, a copolymerized polyamine containing at least two of the foregoing, or a mixture comprising at least two of the foregoing. </ RTI> <RTIgt; 160 g). 9. The dry-mixed nano-composition composition of claim 1, wherein the compatibilizer is one or more compounds selected from the group consisting of an ethylene-vinyl anhydride-acrylic acid copolymer, an ethylene-acrylic acid. Ethyl ester copolymer, monoethylene-alkyl acrylate-acrylic acid copolymer, monomaleic anhydride-adjusted (branched) high-density polyethylene, monomaleic anhydride-adjusted (branched) linear low-density poly Ethylene, ethylene-alkyl (meth)acrylate, (meth)acrylic acid copolymer, monoethylene-butyl propionate copolymer, ethylene-ethylene acetate copolymer, monomaleic anhydride adjustment a group of (branched) ethylene-ethylene acetate copolymers. 10. The dry-mixed nano-composite composition according to claim 1, wherein the resistive characteristic resin and the resistive nano-composition are both melt-mixed and mixed by a twin-screw pressure. The exit or single screw extruder is performed at the melting point of the resin or higher. 11. The composition of the dry mixed nano-composite according to claim 1, wherein the weight ratio of the resin having a barrier property is from 58.0: 42.0 to 99.9: 0.1 with respect to the plug-in clay composed of nanometers. . 12. An article produced by the composition of dry-mixed nano-aliens according to any one of claims 1 to 3, wherein the article of claim 12 is as claimed in claim 12 The production method can be produced by a method such as blow molding, extrusion molding 13285592 17430 pif. doc (extrusion molding), pressure molding, or injection molding. 14. The article of claim 12, wherein the article is a container having a barrier property. 15. The article of claim 12, wherein the article is a tubular article having a barrier property. 16. The article of claim 12, wherein the article is a sheet having a barrier property. 17. The article of claim 14, wherein the article is a multi-layer container, further comprising an adhesive layer and a polyolefin resin layer. 18. The article of claim 16, wherein the article is a multi-layer sheet, further comprising an adhesive layer and a polyolefin resin layer. 〆 45