Patent Grant
7138452
(a) Field of the Invention
The present invention relates to a nanocomposite blend composition having superior barrier properties, and more particularly to a nanocomposite blend composition having superior mechanical strength and superior barrier properties to oxygen, organic solvent, and moisture, and which is applicable to single/multi-layer blow molding and film processing.
(b) Description of the Related Art
General-purpose resins, such as polyethylene and polypropylene, are used in many fields due to their superior moldability, mechanical properties, and moisture barrier properties. While these resins have good gas barrier properties as well, they are limited in use for packaging or containers for agrochemicals and foods, which require superior oxygen barrier properties. Therefore, packaging or containers (bottles) for such materials are manufactured in multi-layers by co-extrusion, lamination, coating, etc.
Multi-layer plastic products made of an ethylene-vinyl alcohol (EVOH) copolymer and polyamide are transparent and have good gas barrier properties. However, because ethylene-vinyl alcohol and polyamide are more expensive than general-purpose resins, their contents in the products are restricted, and it is required to make the ethylene-vinyl alcohol and polyamide as thin as possible.
To reduce production costs of plastic containers, a method of compounding ethylene-vinyl alcohol and polyamide with inexpensive polyolefin has been proposed. However, because ethylene-vinyl alcohol and polyamide are not very compatible with polyolefin, the blending is not easy. If ethylene-vinyl alcohol and polyamide are blended insufficiently, mechanical properties of produced films or sheets become poor.
In this regard, a method of using a compatibilizer to increase compatibility of ethylene-vinyl alcohol and polyamide to polyolefin has been proposed. Because the compatibilizer increases compatibility of ethylene-vinyl alcohol and polyamide to polyolefin, selection of a good compatibilizer is an important technical issue in improving mechanical strength and chemical barrier properties of products.
U.S. Pat. No. 4,971,864, U.S. Pat. No. 5,356,990, EP No. 15,556, and EP No. 210,725 disclose a method of using a compatibilizer prepared by grafting polyethylene and maleic anhydride. While this compatibilizer increases oxygen barrier properties and mechanical strength, moisture barrier properties are poor due to the hydrophilic properties of ethylene-vinyl alcohol polyamide and ionomers. Therefore, hydrophobic resin processing at the outermost layer is difficult, and there is no suitable processing condition for obtaining effective barrier property morphology.
As disclosed in U.S. Pat. Nos. 4,739,007, 4,618,528, 4,874,728, 4,889,885, 4,810,734, and 5,385,776, a nanocomposite is an exfoliated or intercalated platelet, tactoidal structure, or dispersion mixture thereof of nanometer dimensions, comprising intercalated clay dispersed in a matrix polymer, such as an oligomer, a polymer, or a blend thereof.
In general, nanocomposite manufacturing technology is divided into two methods.
The first method is the manufacturing method of said polyamide nanocomposite. In this method, monomers are inserted within intercalated organic clay, and the clay platelets are dispersed through inter-layer polymerization. This method is restricted in that it is applicable only when cationic polymerization is possible.
The other method is the melt compounding method which inserts melt polymer chains within intercalated clay and exfoliates it through mechanical compounding. Examples of such method are disclosed in Preparation of polystyrene nanocomposite (R. A. Vaia, et. al, Chem. Mater., 5, 1694(1993)), Preparation of polypropylene nanocomposite (M. Kawasumi, et. al, Macromolecules, 30, 6333(1997)), and Preparation of nylon 6 nanocomposite (U.S. Pat. No. 5,385,776), etc.
Therefore, research on nanocomposite blend compositions having superior mechanical strength and chemical barrier properties and that are capable of realizing effective barrier property morphology is needed.
The present invention was made in consideration of the problems of the prior art, and it is an object of the present invention to provide a nanocomposite blend composition having superior mechanical strength and superior barrier properties to oxygen, organic solvent, and moisture, and which is applicable to single/multi-layer blow molding and film processing.
It is another object of the present invention to provide a container and a film that comprise said nanocomposite blend composition.
To achieve said objects, the present invention provides a nanocomposite blend composition having barrier properties, comprising:
The present invention also provides a container and a film that comprise said nanocomposite blend composition.
a is an electron microscopic photograph (×200) of a cross-section of a blow-molded container comprising the nanocomposite blend composition prepared by a preferred embodiment of the present invention.
b is an electron microscopic photograph (×5,000) of a cross-section of a blow-molded container comprising the nanocomposite blend composition prepared by a preferred embodiment of the present invention.
a is an electron microscopic photograph (×2,000) of a cross-section of a blow-molded container comprising a blend composition not comprising the nanocomposite having barrier properties of the present invention.
b is an electron microscopic photograph (×5,000) of a cross-section of a blow-molded container comprising a blend composition not comprising the nanocomposite having barrier properties of the present invention.
10: Continuous polyolefin phase
11: Discontinuous nanocomposite phase
The present invention will now be explained in more detail.
The present inventors worked to develop a method of improving mechanical strength and chemical barrier properties of a nanocomposite blend. In doing so, they found that a nanocomposite prepared by exfoliating intercalated clay in a resin having barrier properties, such as ethylene-vinyl alcohol (EVOH), a polyamide, an ionomer, and polyvinyl alcohol (PVA), increases barrier properties to moisture and liquid by extending gas and liquid passage inside the resin, and suppresses parison sagging during blow molding by increasing melt strength of the continuous polyolefin phase. Also; they found that a nanocomposite blend comprising the nanocomposite having barrier properties, polyolefin resin, and compatibilizer has superior mechanical strength and superior barrier properties to oxygen, organic solvents, and moisture.
The nanocomposite blend composition of the present invention is characterized by comprising a polyolefin resin (a); a nanocomposite (b) having barrier properties selected from one or more of i) an ethylene-vinyl alcohol (EVOH)/intercalated clay nanocomposite, ii) a polyamide/intercalated clay nanocomposite, iii) an ionomer/intercalated clay nanocomposite, and iv) a polyvinyl alcohol (PVA)/intercalated clay nanocomposite; and a compatibilizer (c).
For the polyolefin resin (a), a high density polyethylene (HDPE), a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), an ethylene-propylene polymer, or an ethylene-propylene copolymer can be used.
The content of the polyolefin resin is preferably 1 to 97 wt %, and more preferably 20 to 97 wt %, of 100 wt % of the nanocomposite blend.
The intercalated clay used in the nanocomposite (b) preferably comprises an organic intercalated clay. The organic content of the intercalated clay is preferably 1 to 45 wt %.
The intercalated clay is one or more materials 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 quaternary ammonium, phosphonium, maleate, succinate, acrylate, benzylic hydrogen, and oxazoline.
The content of ethylene in the ethylene-vinyl alcohol (EVOH)/intercalated clay nanocomposite (b, i) is preferably 10 to 50 mol %. If the ethylene content is below 10 mol %, melt molding becomes difficult due to poor processability. Otherwise, if it exceeds 50 mol %, barrier properties to oxygen and liquid becomes insufficient.
For the polyamide of the polyamide/intercalated clay nanocomposite (b, ii), nylon 4.6, nylon 6, nylon 6.6, nylon 6.10, nylon 6.12, nylon 11, nylon 12, or amorphous nylon can be used.
The ionomer of the ionomer/intercalated clay nanocomposite (b, iii) 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).
The content of the nanocomposite having barrier properties (b) is preferably 1 to 95 wt %, and more preferably 1 to 30 wt %, of 100 wt % of the nanocomposite blend.
The nanocomposite having barrier properties offers favorable conditions for the discontinuous resin to realize the morphology of
Accordingly, the present invention maximizes barrier properties to gas and liquid by compounding the resin having barrier properties and the intercalated clay, dispersing the nanometer-size intercalated clay in the resin, and thereby maximizing the contact area of the polymer chain and the intercalated clay.
The compatibilizer (c) reduces brittleness of the polyolefin resin and improves its compatibility within the nanocomposite to form a composition with a stable structure.
For the compatibilizer, it is preferable to use a hydrocarbon polymer having polar groups. When a hydrocarbon polymer having polar groups is used, the hydrocarbon polymer portion increases affinity of the compatibilizer to the polyolefin resin and to the nanocomposite having barrier properties, and thereby offers a stable structure to the resin composition.
For the compatibilizer, one or more compounds 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 modifications thereof, can be used.
The content of the compatibilizer is preferably 1 to 95 wt %, and more preferably 1 to 30 wt %, of 100 wt % of the nanocomposite blend.
When an epoxy-modified polystyrene copolymer is used for the compatibilizer, a copolymer comprising a main chain which comprises 70 to 99 wt % of styrene and 1 to 30 wt % of an epoxy compound represented by Chemical Formula 1, and branches which comprise 1 to 80 wt % of acrylic monomers, is preferable. Its content is 1 to 80 wt % of 100 wt % of the nanocomposite blend.
In Chemical Formula 1, R and R′ are C1-20 aliphatic residues or C5-20 aromatic residues having double bonds at termini.
The maleic anhydride modified (graft) high-density polyethylene, maleic anhydride modified (graft) linear low-density polyethylene, or maleic anhydride modified (graft) ethylene-vinyl acetate copolymer preferably comprises branches having 0.1 to 10 wt % of maleic anhydride for 100 wt % of the main chain.
The nanocomposite blend composition of the present invention can be applied to manufacture of blow-molded products, single-layered products, and multi-layered products. Also, it can be manufactured as containers (bottles) and films by blow molding, extrusion molding, injection molding, or thermoforming.
The manufacturing methods are as follows.
Manufacturing by Single Process
In blow molding and injection molding for producing final products, the nanocomposite having barrier properties (b) is dispersed in the matrix resin (a: polyolefin resin) at the same time using a single screw extruder, a co-rotation twin screw extruder, a counter-rotation twin screw extruder, a continuous compounder, a planetary gear extruder, etc.
Manufacturing by Multi Processes
The nanocomposite having barrier properties (b) is prepared by using a polymer compounder such as a single screw extruder, a co-rotation twin screw extruder, a counter-rotation twin screw extruder, a continuous compounder, a planetary gear compounder, a batch compounder, etc. Then, the nanocomposite is mixed with the matrix resin (a: polyolefin resin) to obtain the final products.
For the manufacturing method, blow molding, extrusion molding, injection molding, and thermoforming can be used. However, the present invention is not limited to said methods, and includes all processing methods for manufacturing containers having barrier properties.
Hereinafter, the present invention is described in more detail through examples. However, the following examples are only for the understanding of the present invention, and the present invention is not limited to the following examples.
(Preparation of Nanocomposite having Barrier Properties)
15 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) and 13.3 wt % of maleic anhydride modified (graft) high-density polyethylene (HDPE-g-MAH; Uniroyal Chemical, USA; PB3009 (MAH content: 1%); melt index: 5 g/10 min; density: 0.95 g/cm3), as a compatibilizer, were put in the main hopper of a twin screw extruder (ZSK 25; W&P, USA). Then, 3.3 wt % of montmorillonite (Southern intercalated clay Products, USA; C2OA) organified with intercalated clay was put in separately to the side feeder to prepare an ethylene-vinyl alcohol/intercalated clay nanocomposite. The extrusion temperature condition was 180-190-200-200-200-200-200° C., the screw rate was 300 rpm, and the discharge condition was 10 kg/hr.
(Preparation of Nanocomposite Blend)
The prepared ethylene-vinyl alcohol/intercalated clay nanocomposite was dry-blended with 68.4 wt % of high-density polyethylene (BDO390; LG Chem; melt index: 0.3 g/10 min; density: 0.949 g/cm3) and put in a twin screw extruder. The mixture was extruded to obtain a nanocomposite blend. The extrusion temperature condition was 180-190-190-190-190-190-190° C., the screw rate was 300 rpm, and the discharge condition was 10 kg/hr.
(Manufacture of Container)
The prepared nanocomposite blend was blow-molded to manufacture a 1000 mL container. The processing temperature condition was 160-190-190-190-185° C., and the screw rate was 33 rpm.
(Preparation of Nanocomposite having Barrier Properties)
15 wt % of ethylene-vinyl alcohol copolymer and 13.3 wt % of maleic anhydride modified (graft) high-density polyethylene were put in the main hopper of a twin screw extruder. Then, 3.3 wt % of montmorillonite organified with intercalated clay was put in separately to the side feeder to prepare an ethylene-vinyl alcohol/intercalated clay nanocomposite. The extrusion temperature condition was 180-190-200-200-200-200-200° C., the screw rate was 300 rpm, and the discharge condition was 10 kg/hr.
(Preparation of Nanocomposite Blend and Container)
The prepared ethylene-vinyl alcohol/intercalated clay nanocomposite was dry-blended with 68.4 wt % of high-density polyethylene and blow-molded to manufacture a 1000 mL container. The processing temperature condition was 160-190-190-190-185° C., and the screw rate was 33 rpm.
(Preparation of Nanocomposite having Barrier Properties)
97 wt % of polyamide (nylon 6) was put in the main hopper of a twin screw extruder. Then, 3 wt % of montmorillonite organified with intercalated clay was put in separately to the side feeder to prepare a polyamide/intercalated clay nanocomposite. The extrusion temperature condition was 220-230-245-245-245-245-245° C., the screw rate was 300 rpm, and the discharge condition was 10 kg/hr.
(Preparation of Nanocomposite Blend and Container)
15 wt % of the prepared polyamide/intercalated clay nanocomposite was dry-blended with 7 wt % of maleic anhydride modified (graft) high-density polyethylene, a compatibilizer, and 68 wt % of high-density polyethylene, and blow-molded to manufacture a 1000 mL container. The processing temperature condition was 160-190-190-190-185° C., and the screw rate was 33 rpm. A disc-patterned structure was identified when the cross-section of the blow-molded container was observed with an electron microscope (×200; ×5,000). The results are shown in
(Preparation of Nanocomposite having Barrier Properties)
97 wt % of polyamide (nylon 6) was put in the main hopper of a twin screw extruder. Then, 3 wt % of montmorillonite organified with intercalated clay was put in separately to the side feeder to prepare a polyamide/intercalated clay nanocomposite. The extrusion temperature condition was 220-230-245-245-245-245-245° C., the screw rate was 300 rpm, and the discharge condition was 10 kg/hr.
(Preparation of Nanocomposite Blend and Container)
The prepared polyamide/intercalated clay nanocomposite was dry-blended with 7 wt % of epoxy-modified polystyrene copolymer (311×121×41; Johnson Polymer, USA), a compatibilizer, and 68 wt % of high-density polyethylene, and blow-molded to manufacture a 1000 mL container. The processing temperature condition was 160-190-190-190-185° C., and the screw rate was 33 rpm.
100 wt % of high-density polyethylene was blow-molded to manufacture a 1000 mL container.
The same procedure of Example 1 was carried out, except that montmorillonite organified with intercalated clay was not used.
The same procedure of Example 2 was carried out, except that montmorillonite organified with intercalated clay was not used.
The same procedure of Example 3 was carried out, except that montmorillonite organified with intercalated clay was not used.
The same procedure of Example 4 was carried out, except that montmorillonite organified with intercalated clay was not used. The cross-section of the blow-molded container was observed with an electron microscope (×2,000; ×5,000). The results are shown in
(Preparation of Nanocomposite having Barrier Properties)
97 wt % of high-density polyethylene was put in the main hopper of a twin screw extruder. Then, 3 wt % of montmorillonite organified with intercalated clay was put in separately to the side feeder to prepare a high-density polyethylene/intercalated clay nanocomposite. The extrusion temperature condition was 175-190-190-190-190-190-190° C., the screw rate was 300 rpm, and the discharge condition was 10 kg/hr.
(Preparation of Nanocomposite Blend and Container)
The prepared high-density polyethylene/intercalated clay nanocomposite was blow-molded to manufacture a 1000 mL container. The processing temperature condition was 160-190-190-190-185° C., and the screw rate was 33 rpm.
For the blow-molded containers manufactured in Examples 1 and 2 and Comparative Examples 1 to 3, barrier properties to liquid and gas were determined by the following method. The results are shown in Table 1.
a) Liquid barrier properties—Toluene, Desys herbicide (1% of deltametrine+emulsifier, stabilizer, and solvent; Kyung Nong), Batsa insecticide (50% of BPMC+50% of emulsifier and solvent), and water were put in the containers manufactured in Examples 1 and 2 and Comparative Examples 1 to 3. Then, the weight change was determined after 30 days under a condition of forced exhaust at 50° C.
b) Gas barrier properties (cC/m2·day·atm)—The containers blow-molded in Examples 1 and 2 and Comparative Examples 1 to 3 were left alone under the condition of 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).
As shown in Table 1, nanocomposite blend compositions of Examples 1 to 4 according to the present invention, which comprise a polyolefin resin; one or more nanocomposites having barrier properties, selected from an ethylene-vinyl alcohol (EVOH)/intercalated clay nanocomposite, a polyamide/intercalated clay nanocomposite, an ionomer/intercalated clay nanocomposite, and a polyvinyl alcohol (PVA)/intercalated clay nanocomposite; and a compatibilizer, have better barrier properties to liquid and gas than those of Comparative Examples 1 to 6.
As described above, the nanocomposite blend composition of the present invention has superior mechanical strength and superior barrier properties to oxygen, organic solvent, and moisture. Also, it has good chemical barrier properties, and is applicable to single/multi-layer blow molding and film processing.
| Number | Date | Country | Kind |
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