High-density ethylene-based polymer using hybrid supported catalyst, and preparation method thereof

Abstract

The present invention relates to a high-density ethylene-based polymer exhibiting excellent processability due to the use of a hybrid catalyst composition, and a preparation method thereof, the present invention providing a high-density polyethylene-based polymer having excellent mechanical properties such as excellent optical properties, impact resistance and hardness, as well as excellent stretchability. The high-density ethylene-based polymer according to the present invention can provide a polyethylene-based polymer capable of biaxial stretching or simultaneous stretching.

Description

High-density ethylene polymer using a hybrid supported catalyst and its production method

[0001] The present invention provides a method for producing high-density polyethylene using a hybrid metallocene catalyst and a high-density ethylene polymer exhibiting high processability produced thereby.

[0002] Conventional packaging films require high processability, primarily using low-density polyethylene. While low-density polyethylene has high elongation, its low density reduces physical properties such as hardness, flexural strength, and chemical resistance. Therefore, low-density polyethylene alone cannot produce packaging films that meet these required properties.

[0003] Accordingly, conventional packaging films were manufactured in the form of laminated films by coextruding or bonding polyethylene films such as PET (Polyethylene terephthalate) or PA (Polyamide). However, the laminated films are laminated films of different polymers and do not satisfy more than 90% of a single material resin, so they do not satisfy environmentally friendly regulations, making it difficult to recycle the laminated films and making it difficult to be recognized as environmentally friendly resins.

[0004] Therefore, in order to overcome the above problems of conventional packaging films, it is necessary to develop a new polyethylene that has excellent stretchability while satisfying sufficient properties such as impact strength, chemical resistance, and heat resistance.

[0005] Conventional polyethylene polymerization uses Ziegler-Natta catalysts or chromium-based catalysts, and the resulting polyethylene has a broad molecular weight distribution, which can improve melt flowability. However, Ziegler-Natta catalysts or chromium-based catalysts have non-uniform active sites. Therefore, polyethylene produced using Ziegler-Natta catalysts cannot selectively control the processability and mechanical properties targeted by those skilled in the art, making it difficult to produce packaging materials with excellent processability and optimal properties. Furthermore, ethylene-α-olefin copolymers produced using Ziegler-Natta catalysts have problems such as low molecular weight comonomer distribution due to the unstable active sites of the catalyst, which reduces chemical resistance, mechanical strength, and processability.

[0006] To solve these problems, U.S. Patent No. 6,525,150 proposed a metallocene catalyst that can produce a resin with a narrow molecular weight distribution and, in the case of a copolymer, a uniform distribution of comonomers by utilizing the uniform active sites of metallocene. However, although the mechanical strength was excellent, the molding processability, including extensibility, was still significantly poor.

[0007] In addition, U.S. Patent No. 6,841,631 proposed a method for producing polyolefins having a bimodal molecular weight distribution using catalysts with different reactivity toward comonomers. However, not only was it difficult to obtain a product having uniform physical properties, but the extensibility was also poor and the mechanical strength was also reduced.

[0008] Therefore, there is a need for the development of a new polyethylene-based single resin for packaging that has sufficient optical transparency, impact strength, chemical resistance, heat resistance, and excellent elongation to solve the above problems, and is also recyclable to satisfy environmental regulations.

[0009] The purpose of the present invention is to provide a high-density polyethylene polymer capable of biaxial stretching or simultaneous biaxial stretching at a high magnification and a method for producing a high-density polyethylene polymer capable of producing the same through a single polymerization.

[0010] Another object of the present invention is to provide a high-density polyethylene polymer having excellent optical properties, excellent mechanical properties such as impact resistance and hardness, and excellent processability, and a method for producing a high-density polyethylene polymer capable of producing the same through a single polymerization.

[0011] Another object of the present invention is to provide a high-density polyethylene film that satisfies excellent transparency, excellent mechanical strength, and excellent stretchability even as a single resin, rather than as a laminate or mixed resin of different resins.

[0012] In addition, the present invention aims to provide a high-density polyethylene film that is manufactured from a single resin and is recyclable, thereby serving as an excellent environmentally friendly food packaging material.

[0013] In order to produce the above high-density polyethylene resin, the present invention comprises a method of producing a mixture of ethylene and C4-C in the presence of a hybrid metallocene catalyst including a transition metal compound of the following chemical formulas 1 to 3. 20 A method for producing high-density polyethylene by polymerizing α-olefin is provided, wherein the hybrid metallocene catalyst is included in a molar ratio of Chemical Formula 1: Chemical Formula 2: Chemical Formula 3 = 1: 0.2 to 3: 1 to 7.

[0014] [Chemical Formula 1]

[0015]

[0016] [Chemical Formula 2]

[0017]

[0018] [Chemical Formula 3]

[0019]

[0020] (In the above chemical formulas 1 to 3, R1, R2, R3, R4 and R5 are independently C1-C6 alkyl, and R a and R b are each independently C1-C6 alkylene, X is halogen, n and m are integers from 0 to 5, l is integer from 1 to 4, and o1 and o2 are integers from 0 to 4.)

[0021] In one aspect of the present invention, the C4-C 20 The α-olefin may be a C5-C8 α-olefin.

[0022] In one aspect of the present invention, the chemical formula 1 may be the following chemical formula 4, the chemical formula 2 may be the following chemical formula 5, and the chemical formula 3 may be the following chemical formula 6.

[0023] [Chemical Formula 4]

[0024]

[0025] [Chemical Formula 5]

[0026]

[0027] [Chemical Formula 6]

[0028]

[0029] In one aspect of the present invention, the polymerization temperature may be 60 to 90°C.

[0030] In one aspect of the present invention, the hybrid metallocene catalyst may be a supported catalyst in which a transition metal compound and a cocatalyst are supported on a carrier.

[0031] In one aspect of the present invention, the cocatalyst may be at least one selected from the group consisting of compounds represented by chemical formulae 7 to 9.

[0032] [Chemical Formula 7]

[0033]

[0034] [Chemical Formula 8]

[0035]

[0036] [Chemical Formula 9]

[0037] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0038] (In the above chemical formulas 7 to 9, x is an integer greater than or equal to 2, R6 is halogen, C1-C 20 C1-C substituted with alkyl or halogen 20 alkyl, D is aluminum (Al) or boron (B), R6, R7 and R8 are each independently a halogen atom, straight or branched C1-C 20 C1-C substituted with alkyl and halogen 20 Alkyl or C1-C 20 is an alkoxy group, L is a neutral or cationic Lewis base, [LH] + and [L] + is a Bronsted acid, Z is a group 13 element, and A is C6-C 20 Aryl or C1-C 20 It is alkyl.)

[0039] In one aspect of the present invention, the carrier may be at least one selected from the group consisting of silica, aluminum oxide, and magnesium oxide.

[0040] The present invention relates to a process for producing ethylene and C4-C in the presence of a hybrid catalyst. 20A high-density polyethylene resin manufactured by polymerizing α-olefin, wherein the high-density polyethylene resin has a density of 0.94 g / cm3 or more, a PDI of 25 or more, and can be stretched 4 times or more in the MD (Machine Direction) at a speed of 200 % / s at 120 to 130°C and then sequentially biaxially stretched 4 times or more in the TD (Transverse Direction), or can be simultaneously biaxially stretched 4x4 times or more in the MD (Machine Direction) and TD (Transverse Direction).

[0041] In one aspect of the present invention, the hybrid metallocene catalyst may include a transition metal compound represented by the following chemical formulas 1 to 3.

[0042] [Chemical Formula 1]

[0043]

[0044] [Chemical Formula 2]

[0045]

[0046] [Chemical Formula 3]

[0047]

[0048] (In the above chemical formulas 1 to 3, R1, R2, R3, R4 and R5 are independently C1-C6 alkyl, and R a and R b are each independently C1-C6 alkylene, X is halogen, n and m are 0 to 5, l is an integer from 1 to 4, and o1 and o2 are integers from 0 to 4.)

[0049] In one aspect of the present invention, the hybrid metallocene catalyst may be comprised of chemical formula 1: chemical formula 2: chemical formula 3 in a molar ratio of 1: 0.2 to 3: 1 to 7.

[0050] In one aspect of the present invention, the C4-C 20The α-olefin may be a C5-C8 α-olefin.

[0051] In one aspect of the present invention, the high-density polyethylene resin may have an MFR (Melt Flow Rate) of 40 or more.

[0052] In one aspect of the present invention, the high-density polyethylene resin may have a crystallinity (Xc) of 70% or less.

[0053] The present invention can provide a high-density polyethylene film comprising the high-density polyethylene resin.

[0054] In one aspect of the present invention, the high-density polyethylene film may have a haze of 25% or less as measured according to ASTM D1003.

[0055] In one aspect of the present invention, the high-density polyethylene film may have a transparency of 70% or more as measured according to ASTM D1003.

[0056] In one aspect of the present invention, the high-density polyethylene film may have an impact strength of 120 gf or more as measured according to ASTM D1709.

[0057] The present invention can provide a packaging material manufactured from the high-density polyethylene film.

[0058] The present invention can provide a high-density polyethylene polymer capable of biaxial stretching or simultaneous stretching at a high magnification using the hybrid metallocene catalyst and a method for producing the same.

[0059] In addition, the present invention can provide a high-density polyethylene polymer having excellent optical properties, impact resistance, hardness, and other excellent mechanical properties, as well as excellent processability, and a method for producing the same.

[0060] In addition, the present invention can provide a high-density polyethylene polymer and a method for producing the same using a metallocene catalyst capable of biaxial stretching or simultaneous stretching at a high magnification, for example, simultaneous and sequential stretching at least 4 times in the MD and TD directions.

[0061] Hereinafter, the present invention will be described in detail. However, this is merely exemplary and the present disclosure is not limited to the specific embodiments described as examples.

[0062] Unless otherwise defined herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. The terminology used in this disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the present invention.

[0063] Additionally, the singular forms used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly dictates otherwise.

[0064] Additionally, when a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0065] In addition, the terms "about", "substantially", etc. used in this specification are used in a meaning close to or at the numerical value when manufacturing and material tolerances inherent to the meanings mentioned are presented, and are used to prevent unscrupulous infringers from unfairly using the disclosure contents in which exact or absolute values ​​are mentioned to aid understanding of the present invention.

[0066] Additionally, the polyethylene used in the present specification may be an ethylene homopolymer or a polyethylene copolymer containing at least 80 mol% or more of ethylene repeating units.

[0067] The present invention provides a high-density polyethylene capable of producing a packaging material even as a single material, and for this purpose, provides a method for producing high-density polyethylene using a hybrid metallocene catalyst including three types of transition metal compounds.

[0068] The present invention relates to a process for producing ethylene and C4-C in the presence of a hybrid metallocene catalyst. 20 A high-density polyethylene resin manufactured by polymerizing α-olefin, wherein the high-density polyethylene resin has a density of 0.94 g / cm3 or more, a PDI of 25 or more, and can be stretched 4 times or more in the MD (Machine Direction) at a speed of 200 % / s at 120 to 130°C and then sequentially biaxially stretched 4 times or more in the TD (Transverse Direction) or can be simultaneously biaxially stretched 4x4 times or more in the MD (Machine Direction) and TD (Transverse Direction).

[0069] As one aspect of the present invention, the hybrid metallocene catalyst may include a transition metal compound of the following chemical formulas 1 to 3, and may include the compound in a molar ratio of chemical formula 1: chemical formula 2: chemical formula 3 = 1: 0.2 to 3: 1 to 7.

[0070] [Chemical Formula 1]

[0071]

[0072] [Chemical Formula 2]

[0073]

[0074] [Chemical Formula 3]

[0075]

[0076] (In the above chemical formulas 1 to 3, R1, R2, R3, R4 and R5 are independently C1-C6 alkyl, and R a and R bare each independently C1-C6 alkylene, X is halogen, n and m are integers from 0 to 5, l is integer from 1 to 4, and o1 and o2 are integers from 0 to 4.)

[0077] The above high-density polyethylene resin may be a high-density polyethylene that can be used to manufacture a packaging material by using a hybrid metallocene catalyst comprising a transition metal compound of compound 1, a transition metal compound of chemical formula 2, and a transition metal compound of chemical formula 3 in a molar ratio defined above, and that satisfies the properties described above with only one polymerization process.

[0078] The above high-density polyethylene manufacturing method is described in more detail below.

[0079] As one aspect of the present invention, the C4-C 20 α-olefins are specifically C4-C 12 It may be an α-olefin, more specifically, 1-hexene. Another example is C4-C 20 The α-olefin may be at least one selected from the group consisting of 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, and 3,4-dimethyl-1-hexene.

[0080] In one embodiment of the present invention, the high-density polyethylene may have a PDI of 25 or more, 26 or more, 28 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or less, 60 or less, 50 or less, 55 or less, 50 or less, or 40 or less, for example, 25 to 70, 25 to 60, or any of the above values ​​and any value therebetween.

[0081] High-density polyethylene having a PDI in the above range can have a balanced combination of the excellent mechanical strength of high-molecular-weight polyethylene and the excellent processability and flexural elasticity of low-molecular-weight polyethylene, and thus can be manufactured into a high-density polyethylene film having excellent transparency and excellent mechanical strength.

[0082] For example, the high-density polyethylene may have a weight average molecular weight of 50,000 to 20,000 g / mol, 70,000 to g / mol, or 90,000 to 15,000 g / mol, and a number average molecular weight of 2,000 to 10,000 g / mol, 3,000 to 7,000 g / mol, or 3,000 to 5,000 g / mol.

[0083] As another example, the high-density polyethylene may have a Z-weight average molecular weight of 200,000 to 500,000 g / mol, 250,000 to 500,000 g / mol, or 300,000 to 500,000 g / mol.

[0084] The above high-density polyethylene has a wide PDI as described above and a Z-weight average molecular weight within the above range, so that it can have excellent film processability, and the high-density polyethylene film produced can have high mechanical strength and strength characteristics that enable biaxial stretching.

[0085] In one embodiment of the present invention, the high-density polyethylene may be stretched 4 times or more in the MD (Machine Direction) at a speed of 200 % / s at 120 to 130°C and then stretched 4 times or more in the TD (Transverse Direction) at a stretch rate of 5 times or more, 6 times or more, 7 times or more, 9 times or more, or 20 times or less, for example, 4 to 20 times, 5 to 20 times, 6 to 15 times, 7 to 15 times, or each of the above values ​​and values ​​therebetween.

[0086] The above high-density polyethylene can be stretched four times in MD and then stretched in TD within the above range, so that the film processability can be excellent even through a sequential biaxial stretching process, and the manufactured high-density polyethylene film can have excellent appearance, excellent mechanical strength, and excellent transparency.

[0087] In another aspect of the present invention, the high-density polyethylene resin can be simultaneously stretched in the MD (Machine Direction) and the TD (Transverse Direction) at a rate of 200 % / s at 120 to 130°C by 4 times or more, 5 times or more, 6 times or more, 7 times or more, 9 times or more, or 20 times or less, for example, 4 to 20 times, 5 to 20 times, 6 to 15 times, 7 to 15 times, or any of the above values ​​and any value therebetween.

[0088] Since the above high-density polyethylene can be simultaneously stretched in MD and TD within the range described above, it can have excellent film processability even through a simultaneous biaxial stretching process, and the high-density polyethylene film produced can have excellent appearance, excellent mechanical strength, and excellent transparency.

[0089] That is, the high-density polyethylene has the advantage of excellent film formability regardless of whether the film is processed using a sequential biaxial stretching process or a simultaneous biaxial stretching process.

[0090] In one embodiment of the present invention, the high-density polyethylene may have a density of 0.94 g / cm3 or more, 0.96 g / cm3 or more, 0.99 g / cm3 or less, 0.98 g / cm3 or less, 0.97 g / cm3 or less, or 0.96 g / cm3 or less, for example, 0.94 to 0.99 g / cm3, 0.96 to 0.99 g / cm3, or any of the above values ​​and any value therebetween.

[0091] The above high-density polyethylene not only has excellent stretchability as described above, but also satisfies the density within the above range, so that a high-density polyethylene film having even better mechanical strength can be manufactured.

[0092] In one embodiment of the present invention, the high-density polyethylene may have a Melt Flow Ratio (MFR) of 40 or more, 45 or more, 50 or more and 100 or less, 80 or less, or 70 or less, for example, 40 to 100, 40 to 80, 40 to 70, or each of the above values ​​and values ​​therebetween.

[0093] The above high-density polyethylene resin has a high density, but satisfies the MFR of the above range, so it does not break when stretched and can be formed into a film with an excellent appearance.

[0094] The above MFR may be the ratio of melting indices MI(21.6 kg) and MI(2.16 kg) at 190°C under a load of 21.6 kg and a load of 2.16 kg, respectively (MI(21.6 kg) / MI(2.16 kg)) according to ASTM D 1238.

[0095] In one embodiment of the present invention, the high-density polyethylene resin may have a crystallinity (Xc) measured using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument) of 70% or less, 30% or more, 40% or more, 50% or more, for example, 30 to 70%, or 40 to 70%, or any of the above values ​​and any value therebetween.

[0096] The high-density polyethylene resin has the above crystallinity, so it has a high amorphous region, has excellent processability, especially excellent stretchability, and can be preferred because a film manufactured including it can realize better transparency.

[0097] In addition, the high-density polyethylene resin has a lamellar structure in addition to amorphous properties, and some high molecular weight polyethylenes also have a crystallinity region, so high mechanical strength can be achieved.

[0098] That is, the high-density polyethylene resin according to the present invention is capable of sequential biaxial stretching and simultaneous biaxial stretching at the above-described magnification, and has processability exhibiting superior stretchability compared to conventional high-density polyethylene, so that it can be applied to polyethylene packaging materials and have the effect of being used as a single polyethylene packaging material. This can solve the problem that conventional polyethylene packaging materials could not achieve high mechanical properties and stretchability, making it impossible to manufacture packaging materials made of a single polyethylene component.

[0099] Accordingly, the high-density polyethylene resin according to the present invention enables easy manufacturing of packaging materials using a single material called high-density polyethylene with excellent mechanical properties, thereby replacing packaging materials with a laminated structure using low-density polyethylene that was not recyclable, including conventional resins.

[0100] Therefore, the high-density polyethylene resin according to the present invention has a remarkable effect in terms of economic and environmental protection in that it can be applied to polyethylene packaging materials to provide packaging materials that can be recycled.

[0101] In addition, the high-density polyethylene resin according to the present invention satisfies the values ​​of density, PDI, MFR and crystallinity (Xc) described above, exhibits high optical properties and elongation properties, and thus has the effect of exhibiting properties that enable it to be used as a packaging material and a single resin product, despite being a high-density polyethylene.

[0102] Although this does not limit the interpretation, it can be interpreted that the high-density polyethylene has high hardness, chemical resistance, transparency, and biaxial stretching characteristics by having a high PDI value, low crystallinity, and high MFR while satisfying the above-described density range.

[0103] The present invention provides a high-density polyethylene film comprising the above-described high-density polyethylene resin.

[0104] The high-density polyethylene film of the present invention can be used in products requiring high mechanical properties and stretching properties, including high density, high PDI, low crystallinity, high MFR, and biaxial stretching properties, as it contains the high-density polyethylene resin described above, and in particular, can be applied to the polyethylene packaging material described above to produce a polyethylene single packaging material.

[0105] The high-density polyethylene film of the present invention can be manufactured by extruding and stretching the high-density polyethylene resin described above or by blow molding, but is not limited to any method that can form the high-density polyethylene resin into a film.

[0106] In one embodiment of the present invention, the high-density polyethylene film may have a haze measured according to ASTM D1003 of 25% or less, 20% or less, 18% or less, 16% or less, 1% or more, 5% or more, or 10% or more, for example, 1 to 25%, 5 to 20%, or any of the above values ​​and any value therebetween.

[0107] In one aspect of the present invention, the high-density polyethylene film may have a transparency measured according to ASTM D1003 of 50% or more, 60% or more, 70% or more, 99% or less, 98% or less, 95% or less, or 90% or less, for example, 50 to 99%, specifically 60 to 99%, more specifically 80 to 99%, or a value between the above values ​​or a value between the above values.

[0108] In addition, the high-density polyethylene film can have excellent transparency in the range described above even when manufactured by sequential biaxial stretching of a high-density polyethylene resin, and when manufactured by simultaneous biaxial stretching of a high-density polyethylene resin, it can have excellent transparency with a haze of 1 / 1.5 to 1 / 3 compared to the high-density polyethylene film manufactured by sequential biaxial stretching, and thus can be preferred.

[0109] In one embodiment of the present invention, the high-density polyethylene film may have an impact strength measured according to ASTM D1709 of 120 gf or more, 150 gf or more, 200 gf or more, 210 gf or more, 250 gf or more, 300 gf or more, 350 gf or more, 360 gf or more, 370 gf or more, 380 gf or more, 500 gf or less, 450 gf or less, or 400 gf or less, for example, 100 to 500 gf, 120 to 450 gf, or a value between the above values ​​or a value between the above values.

[0110] Since the high-density polyethylene film described above includes the high-density polyethylene resin, it can provide a high-quality high-density polyethylene film with a uniform surface and high strength by utilizing high elongation characteristics. In addition, the manufactured high-density polyethylene film exhibits low haze, high transparency, and impact strength, making it easy to apply to polyethylene products. Therefore, it not only has high commercialization value, but can also be very advantageously applied to the manufacture of polyethylene single packaging materials in particular.

[0111] Hereinafter, a manufacturing method for manufacturing high-density polyethylene that can be applied as a packaging film as described above will be described in detail.

[0112] The present invention relates to a method for producing ethylene and C4-C under a hybrid metallocene catalyst comprising a transition metal compound of the following chemical formulas 1 to 3. 20 A method for producing high-density polyethylene by polymerizing α-olefin, wherein the hybrid metallocene catalyst is included in a molar ratio of Chemical Formula 1: Chemical Formula 2: Chemical Formula 3 = 1: 0.2 to 3: 1 to 7.

[0113] [Chemical Formula 1]

[0114]

[0115] [Chemical Formula 2]

[0116]

[0117] [Chemical Formula 3]

[0118]

[0119] (In the above chemical formulas 1 to 3, R1, R2, R3, R4 and R5 are independently C1-C6 alkyl, and R a and R b are each independently C1-C6 alkylene, X is halogen, n and m are integers from 0 to 5, l is integer from 1 to 4, and o1 and o2 are integers from 0 to 4.)

[0120] The method for producing high-density polyethylene using the above-mentioned hybrid metallocene catalyst can produce high-density polyethylene that is transparent and has high processability while exhibiting high mechanical properties such as sufficient heat resistance, impact strength, and hardness in just one process, and thus has the effect of providing a method for producing high-density polyethylene applicable to packaging materials.

[0121] As one embodiment of the present invention, in the chemical formula 1, R1 may be C3-C6 alkyl, R2 may be C1-C3 alkyl, X may be Cl, n may be an integer from 1 to 3, and m may be an integer from 0 to 2.

[0122] In another aspect of the present invention, the transition metal compound of the chemical formula 1 may be represented by the following chemical formula 4.

[0123] [Chemical Formula 4]

[0124]

[0125] The transition metal compound of the above chemical formula 4 has excellent catalytic activity and very fast chain mobility, so high-density polyethylene produced using a hybrid metallocene catalyst containing it can have excellent processability and stretchability, and the polymer film produced can have excellent transparency.

[0126] As one embodiment of the present invention, in the chemical formula 2, R3 and R4 are independently C2-C5 alkyl, and R a is C1-C3 alkylene, X is Cl, l is an integer from 1 to 2, and o1 can be an integer from 1 to 2.

[0127] In another aspect of the present invention, the transition metal compound of the above chemical formula 2 can be represented by the following chemical formula 5.

[0128] [Chemical Formula 5]

[0129]

[0130] A hybrid metallocene catalyst including a transition metal compound of the above chemical formula 5 may be preferred because it can exhibit high monomer incorporation during polymer production.

[0131] As one embodiment of the present invention, in the chemical formula 3, R5 is independently C2-C5 alkyl, and R b is C1-C3 alkylene, X is Cl, and o2 can be an integer from 1 to 2.

[0132] As another aspect of the present invention, the transition metal compound of the above chemical formula 3 may be represented by the following chemical formula 6.

[0133] [Chemical Formula 6]

[0134]

[0135] The hybrid metallocene catalyst including the transition metal compound of the above chemical formula 6 can exhibit high comonomer mixing and can produce high molecular weight, high density polyethylene during polymerization, and thus can improve the mechanical properties of the produced high density polyethylene resin, such as impact strength and flexural strength.

[0136] As one embodiment of the present invention, the hybrid metallocene catalyst may include the transition metal compounds of the chemical formulas 1 to 3 described above in a molar ratio of chemical formula 1: chemical formula 2: chemical formula 3 = 1: 0.2 to 3: 1 to 7.

[0137] For example, the molar ratio of the chemical formulas 1 to 3 includes the meaning that the molar ratio of chemical formula 2 to chemical formula 1 may be 1:0.2 to 3, and the molar ratio of chemical formula 3 to chemical formula 1 may be 1:1 to 7.

[0138] A hybrid metallocene catalyst containing a transition metal compound in a molar ratio within the above range can be preferred because it can produce a high-density polyethylene resin having both desirable processability and physical properties for application to the above-described packaging material or as a base film for a laminated packaging material during polymerization.

[0139] Specifically, when the hybrid metallocene catalyst comprises a transition metal compound of formulae 1 to 3 in a molar ratio within the above range, the high-density polyethylene produced can satisfy biaxial stretching characteristics and high processability, and at the same time, excellent heat resistance and excellent impact strength. In addition, the hybrid metallocene catalyst has excellent activity, so that stable operation is possible during the production of high-density polyethylene, and there is a process advantage in that high-density polyethylene can be continuously produced.

[0140] As one aspect of the present invention, the hybrid metallocene catalyst may be one in which the transition metal compound and cocatalyst described above are supported on a carrier.

[0141] Since the above-mentioned hybrid metallocene catalyst has the form of the above-mentioned hybrid supported catalyst, more stable polymerization and improved catalyst activity can be achieved during polymerization.

[0142] As one aspect of the present invention, the cocatalyst may be at least one selected from the group consisting of compounds represented by the following chemical formulas 7 to 9.

[0143] [Chemical Formula 7]

[0144]

[0145] [Chemical Formula 8]

[0146]

[0147] [Chemical Formula 9]

[0148] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0149] (In the above chemical formulas 7 to 9, x is an integer greater than or equal to 2, R6 is halogen, C1-C 20 Alkyl or halogen-substituted C1-C 20alkyl, D is aluminum (Al) or boron (B), R7, R8 and R9 are each independently a halogen atom, straight or branched C1-C 20 Alkyl, halogen-substituted C1-C 20 Alkyl or C1-C 20 is an alkoxy group, L is a neutral or cationic Lewis base, [LH] + and [L] + is a Bronsted acid, Z is a group 13 element, and A is C6-C 20 Aryl or C1-C 20 It is alkyl.)

[0150] The compound represented by the above chemical formula 7 may be, for example, at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, but is not limited thereto.

[0151] The compound represented by the above chemical formula 8 may be, for example, at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, and tributylboron, but is not limited thereto.

[0152] The compound represented by the above chemical formula 9 is, for example, triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, trimethylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetrapentafluorophenylboron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, Trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, It may be at least one selected from the group consisting of triethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, triphenylcarbonium tetra(p-trifluoromethylphenyl)boron, and triphenylcarbonium tetrapentafluorophenylboron.

[0153] The above carrier is not particularly limited as long as it supports the transition metal compound and cocatalyst described above, but as an example, it may be at least one selected from the group consisting of silica, aluminum oxide, and magnesium oxide.

[0154] As one embodiment of the present invention, the hybrid metallocene catalyst may include 0.001 to 10 mmol, or 0.001 to 1 mmol, of three kinds of transition metal compounds comprising the chemical formulae 1 to 3 based on 1 g of the carrier, and may include 1 to 20 mmol, or 2 to 15 mmol, of a cocatalyst based on 1 g of the carrier, but is not necessarily limited thereto.

[0155] In one example, the carrier may have an average particle size of, but is not limited to, 10 to 250 μm, 10 to 150 μm, or 20 to 100 μm.

[0156] The micropore volume of the above carrier may be, but is not limited to, 0.1 to 10 ml / g, 0.5 to 5 ml / g, or 1.0 to 3.0 ml / g.

[0157] In one embodiment of the present invention, the method for producing high-density polyethylene may inject the hybrid metallocene catalyst into the reactor at a rate of 0.1 g / h or more, 0.5 g / h or more, 10 g / h or less, or 5 g / h or less, for example, 0.1 to 10 g / h or 0.5 to 5 g / h, but is not limited thereto.

[0158] In one aspect of the present invention, the method for producing the high-density polyethylene comprises adding the C4-C to the reactor. 20 α-olefin can be injected at 50 g / h or more, 100 g / h or more, 150 g / h or more, 1500 g / h or less, or 1000 g / h or less, for example, 50 to 1500 g / h, or 100 to 1000 g / h, but is not limited thereto.

[0159] In one aspect, the C4-C 20 α-olefin is C4-C of the high-density polyethylene resin described above. 20 Since it is the same as α-olefin, detailed explanation is omitted.

[0160] In one aspect of the present invention, the molar ratio of hydrogen / ethylene may be 0.01 or more, 0.1 or more, 10 or less, or 5% or less, and may be, for example, 0.01 to 10, 0.1 to 5, but is not limited thereto.

[0161] In one aspect of the present invention, the molar ratio of hexene / ethylene may be 0.01 or more, 0.1 or more, 10 or less, or 5 or less, for example, 0.01 to 10, 0.1 to 5, but is not limited thereto.

[0162] In one aspect of the present invention, ethylene and C4-C 20 Polymerization of α-olefins can be carried out at a temperature of 50 to 200°C, 60 to 100°C, or 60 to 90°C and a pressure of 1 to 50 bar, 1 to 30 bar, or any of the above values ​​and any value therebetween, but is not limited thereto, and it is to be understood that the polymerization temperature and pressure can be appropriately changed depending on the reactants and reaction conditions.

[0163] In one aspect of the present invention, ethylene and C4-C 20 Polymerization of α-olefins may be, but is not limited to, slurry-phase or gas-phase polymerization. When the polymerization is carried out in a liquid or slurry phase, a solvent may be further included, and specifically, the solvent may include propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, dichloroethane, chlorobenzene, etc., and these solvents may be mixed and used at a certain ratio, but are not limited thereto.

[0164] Therefore, the method for producing the high-density polyethylene can produce high-density polyethylene suitable for packaging materials with only one polymerization process by using a hybrid metallocene catalyst containing three types of transition metal compounds.

[0165] Hereinafter, embodiments of the present invention will be further described with reference to specific experimental examples. The examples and comparative examples included in the experimental examples are merely illustrative of the present invention and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various modifications and variations of the examples are possible within the scope and technical spirit of the present invention, and it is also natural that such modifications and variations fall within the scope of the appended claims.

[0166] [Manufacturing Example 1]

[0167]

[0168] 6.9 g of a complex transition metal compound including transition metal compound A (tetramethylcyclopentadienyl)(n-butylcyclopentadienyl) zirconium dichloride), transition metal B (Diphenylmethylene-(3-butyl-cyclopentadienyl)(2,7-di-tert-butyl-9-fluorenyl)-zirconium(IV)-dichloride)) and transition metal C (Diphenylmethylene-(cyclopentadienyl)(2,7-di-tert-butyl-9-fluorenyl)-zirconium(IV)-dichloride)) having the above structure (the molar ratio of each transition metal compound was 1:0.5:2 for A:B:C) was mixed with 1.1 kg of a toluene solution containing 10 wt% methylaluminum oxane (MAO) to prepare a mixed solution having Al / Zr of 150, and stirred at room temperature for 1 hour to prepare a complex catalyst. It was manufactured.

[0169] 250 g of silica (XP2402) was placed in a reactor, 30 ml of purified toluene was added to prepare a silica slurry, and the composite catalyst was injected into the silica slurry and stirred in an oil bath at 75°C for 3 hours to prepare a metallocene catalyst solution. The metallocene catalyst solution was separated into solid and liquid, the supernatant was removed to isolate only the metallocene catalyst, which was washed three times with toluene and dried in a vacuum at 60°C for 10 hours to recover 230 g of a mixed metallocene catalyst in powder form.

[0170] [Manufacturing Example 2]

[0171] In Manufacturing Example 1, 7.5 g of the complex transition metal compound was included in the same manner as in Manufacturing Example 1, except that the transition metal compound composition ratio was included in a molar ratio of A:B:C = 1:1.7:7.

[0172] [Manufacturing Example 3]

[0173] In Manufacturing Example 1, 6.6 g of the complex transition metal compound was included in the same manner as in Manufacturing Example 1, except that the transition metal compound composition ratio was included in a molar ratio of A:B:C = 1:0.3:1.4.

[0174] [Comparative Manufacturing Example 1]

[0175] In Manufacturing Example 1, 6.7 g of the complex transition metal compound was included in the same manner as in Manufacturing Example 1, except that the transition metal compound composition ratio was included in a molar ratio of A:B:C = 1:0.04:2.

[0176] [Comparative Manufacturing Example 2]

[0177] In Manufacturing Example 1, 6.2 g of the complex transition metal compound was included in the same manner as in Manufacturing Example 1, except that the transition metal compound composition ratio was included in a molar ratio of A:B:C = 1:0.5:0.4.

[0178] [Comparative Manufacturing Example 3]

[0179] In the above Manufacturing Example 1, a composite transition metal compound was prepared in the same manner as Manufacturing Example 1, except that 1.8 g of the transition metal compound A and 5.0 g of the transition metal compound B were used to prepare the complex transition metal compound.

[0180] [Comparative Manufacturing Example 4]

[0181]

[0182] In the above Preparation Example 1, the composite catalyst was prepared in the same manner as in Preparation Example 1, except that a composite transition metal compound was prepared using 1.2 g of transition metal compound D (bis(n-propylcyclopentadienyl)zirconium chloride), 0.8 g of transition metal compound B (Diphenylmethylene-(3-butyl-cyclopentadienyl)(2,7-di-tert-butyl-9-fluorenyl zirconium(IV)-dichloride), and 3.8 g of transition metal compound E (dimethylsilylene)bis(2-methyl-4-phenylindenyl)zirconium dichloride).

[0183] [Comparative Manufacturing Example 5]

[0184]

[0185] In the above Manufacturing Example 1, 1.8 g of transition metal compound F (bis(iso-butylcyclopentadienyl)zirconium chloride), 0.8 g of transition metal compound B (Diphenylmethylene-(3-butyl-cyclopentadienyl)(2,7-di-tert-butyl-9-fluorenyl-zirconium(IV)-dichloride), and 3.8 g of transition metal compound E (dimethylsilylene)bis(2-methyl-4-phenylindenyl)zirconium dichloride) were used, except that the same process as Manufacturing Example 1 was used.

[0186] [Example 1]

[0187] An ethylene / 1-hexene polymerization reaction was performed at 90°C using a continuous gas phase polymerization reactor consisting of a fluidized bed using the catalyst prepared in Manufacturing Example 1. The reaction conditions are described in Table 2 below.

[0188] [Example 2]

[0189] The same procedure as Example 1 was followed, except that the catalyst manufactured in Manufacturing Example 2 was used as the catalyst.

[0190] [Example 3]

[0191] The same procedure as Example 1 was followed, except that the catalyst manufactured in Manufacturing Example 3 was used as the catalyst.

[0192] [Example 4]

[0193] The same procedure was followed as in Example 1, except that the polymerization temperature was set at 80°C.

[0194] [Comparative Example 1]

[0195] The same procedure as Example 1 was followed, except that the catalyst manufactured in Comparative Manufacturing Example 1 was used as the catalyst.

[0196] [Comparative Example 2]

[0197] The same procedure as Example 1 was followed, except that the catalyst manufactured in Comparative Manufacturing Example 2 was used as the catalyst.

[0198] [Comparative Example 3]

[0199] The same procedure as Example 1 was followed, except that the catalyst manufactured in Comparative Manufacturing Example 3 was used as the catalyst.

[0200] [Comparative Example 4]

[0201] The same procedure as Example 1 was followed, except that the catalyst manufactured in Comparative Manufacturing Example 4 was used as the catalyst.

[0202] [Comparative Example 5]

[0203] The same procedure as Example 1 was followed, except that the catalyst manufactured in Comparative Manufacturing Example 5 was used as the catalyst.

[0204] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Polymerization temperature (℃) 90 90 90 80 90 90 90 90 90 Catalyst injection amount (g / hr) 1.7 1.69 1.67 1.7 2.11.2 0.9 1.85 2.3 Hydrogen injection amount (g / hr) 18.00 31.69 23.44 18.00 15.12 17.00 18.00 10.86 5.96 Hexene injection amount (g / hr) 176 500 278 176 34 85 49 700 35 33 46 Hydrogen / ethylene Molar ratio 1.141.531.341.140.840.771.090.290.09Hexene / ethylene molar ratio 0.460.440.410.460.790.471.010.930.87Polymer production (㎏ / h) 7.996.967.187.657.747.547.598.879.64

[0205] The physical properties of the polymers manufactured in the above examples and comparative examples were measured as follows, and the results are shown in Table 2.

[0206] (1) Melt Flow Ratio (MFR)

[0207] According to ASTM D 1238, the melting index was measured at 190 ℃ with a load of 21.6 kg and a load of 2.16 kg, respectively, and the ratio (MI 21.6 / MI 2.16 ) was calculated.

[0208] (2) Density

[0209] Density was measured according to ASTM D 1505.

[0210] (3) Molecular weight

[0211] Gel permeation chromatography-FTIR (GPC-FTIR) of Polymer Char's model GPC-6 was used. Measurements were made at 160°C, and trichlorobenzene was used as the solvent.

[0212] (4) Thermal characteristics

[0213] Measurements were made using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 200°C, maintained at that temperature for 5 minutes, cooled to 20°C, and then increased again, with the temperature rising and falling rates each controlled to 20°C / min.

[0214] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Transition metal compound combination ABCABCABCABCABCABCABDBEFBE Transition metal compound molar ratio 1:0.5:21:1.7:7 1:0.3:1.4 1:0.5:21:0.04:21:0.5:0.4 1:1.5 1:0.25:1.25 1:0.5:1 * MI0.5880.741.120.780.951.80.730.620.73 * MFI32.1131.8555.8747.4832.309016.3441.9070.80 *MFR54.6143.0449.8860.8734.005022.3867.5896.98Density(g / cm3)0.9430.9440.9410.9450.9560.9400.94140.94600.9456Mz(g / ㏖)430,300,455,400,336,20 0489,000388,200394,200412,000830,679792,108Mn(g / mol)5,4004,2003,5 004,9006,2005,40010,1006,1236,208Mw(g / mol)132,700125,30098,100133, 000134,70086,400156,600121,565116,840PDI24.5830.0828.4426.921.8 16.1215.4619.8518.82Tm(℃)126.88126.44126.31126.38133.70122.50127 .96127.33126.89Tc(℃)115.6114.64113.62114.97117.5112.8115.0116.02115.73Xc(%)57.7962.6360.0460.3874.0058.2185.2168.8468.63*2.16kg, MI measured at 190 ℃*21.kg, MFI measured at 190 ℃*MFR=MFI / MI

[0215] The polyethylene polymers manufactured in the above examples and comparative examples were extruded as follows to manufacture films, and the physical properties of the films are listed in Table 3 below.

[0216] (5) Method for manufacturing polyethylene film

[0217] The polyethylene polymers of Examples 1 to 4 and Comparative Examples 1 to 5 were extruded at 245°C using a L / D 42DML 25mm twin-screw extruder. The die temperature was maintained at 265°C. The T-DIE was adjusted to a size of 30 to 35 cm and a thickness of 770 to 780 μm to manufacture a film.

[0218] (6) Sequential biaxial stretching processing

[0219] Biaxial stretching processing was performed using SDB's Model name PS002 equipment. First, a 10cm X 10cm 1mm sheet sample was manufactured using a press at 190℃. The manufactured sheet was heated in an oven at 120-125℃ for 300s, then stretched in the MD (machine direction) at a speed of 200% / s, and then stretched in the TD (traverse direction).

[0220] (7) Simultaneous biaxial stretching processing

[0221] Biaxial stretching processing was performed using Burckner's Model KARO 5.0 equipment. A 9cm x 9cm specimen was manufactured using a polymer. The manufactured specimen was simultaneously stretched in both the machine direction (MD) and traverse direction (TD) at a rate of 200% / s under heated conditions of 120 to 130°C.

[0222] (8) Haze measurement

[0223] Five measurements were taken per specimen according to ASTM D 1003, and the average value was reported.

[0224] (9) Clarity measurement

[0225] Five measurements were taken per specimen according to ASTM D 1003, and the average value was reported.

[0226] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Simultaneous Biaxial Elongation MD X TD 7X77X77X77X7 Fail Thickness (㎛) 14.9 9.0 9.4 14.9 Fail Haze (%) 9.2 7.4 19.2 9.2 Fail Clarity (%) 96.2 198.4 89.6 95.3 Fail Impact Strength (gf) 389 206 181 397 Fail Sequential Biaxial Elongation Thickness (㎛) 15.2 3.4 8.2 15.4 Fail MD X TD4

[0227] Referring to Tables 1 to 3, Examples 1 to 4, by including a hybrid metallocene catalyst comprising a transition metal compound of Chemical Formula 1 to 3, produced polyolefin resins by polymerizing ethylene and α-olefin had a high density of 0.94 g / cm3 or higher, and were all capable of high-magnification biaxial stretching. However, it was confirmed that the high-density polyethylene polymers produced by Comparative Examples 3 to 5, which were produced using a catalyst other than the specific catalyst mixture of the present invention, were broken and could not be stretched. Comparative Examples 1 and 2 included the transition metal compounds of Chemical Formula 1 to 3 of the present invention, but when the ratio of Chemical Formula 1: Chemical Formula 2: Chemical Formula 3 was not satisfied, stretching was impossible, resulting in breakage or tearing during stretching and making processing impossible. Therefore, it was confirmed that such biaxial stretching characteristics were exhibited by producing a high-density polyethylene polymer using the hybrid metallocene catalyst of the present invention including a specific ratio.

[0228] Above, although an embodiment has been described in detail through examples and experimental examples, the scope of an embodiment is not limited to a specific example, and should be interpreted in accordance with the appended patent claims.

Claims

1. Ethylene and C4-C under a mixed metallocene catalyst including a transition metal compound of the following chemical formulas 1 to 3 20 A method for producing high-density polyethylene by polymerizing α-olefin, A method for producing high-density polyethylene, wherein the above hybrid metallocene catalyst is included in a molar ratio of Chemical Formula 1: Chemical Formula 2: Chemical Formula 3 = 1: 0.2 to 3: 1 to 7. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In the above chemical formulas 1 to 3, R1, R2, R3, R4 and R5 are independently C1-C6 alkyl, R a and R b are each independently C1-C6 alkylene, X is a halogen, n and m are integers from 0 to 5, l is an integer from 1 to 4, o1 and o2 are integers from 0 to 4.

2. In paragraph 1, C4-C above 20 A method for producing high-density polyethylene, wherein the α-olefin is a C5-C8 α-olefin.

3. In paragraph 1, A method for producing high-density polyethylene, wherein the above chemical formula 1 is chemical formula 4, chemical formula 2 is chemical formula 5, and chemical formula 3 is chemical formula 6. [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] 4. In paragraph 1, The above method for producing high-density polyethylene is a method for producing high-density polyethylene, wherein the polymerization temperature is 60 to 90°C.

5. In paragraph 1, A method for producing high-density polyethylene, wherein the above hybrid metallocene catalyst is a supported catalyst in which a transition metal compound and a cocatalyst are supported on a carrier.

6. In paragraph 5, A method for producing high-density polyethylene, wherein the cocatalyst is at least one selected from the group consisting of compounds represented by chemical formulas 7 to 9. [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] [LH] + [Z(A)4] - or [L] + [Z(A)4] - In the above chemical formulas 7 to 9, x is an integer greater than or equal to 2, R6 is halogen, C1-C 20 C1-C substituted with alkyl or halogen 20 It is alkyl, D is aluminum (Al) or boron (B), R7, R8 and R9 are independently a halogen atom, straight or branched C1-C 20 C1-C substituted with alkyl and halogen 20 Alkyl or C1-C 20 It is an alkoxy group, L is a neutral or cationic Lewis base, [LH] + and [L] + is Mount Bronsted, Z is a group 13 element, A is C6-C 20 Aryl or C1-C 20 It's alkyl.

7. In paragraph 5, A method for producing high-density polyethylene, wherein the carrier is at least one selected from the group consisting of silica, aluminum oxide, and magnesium oxide.

8. Ethylene and C4-C in the presence of a hybrid catalyst 20 A high-density polyethylene resin manufactured by polymerizing α-olefin, wherein the high-density polyethylene resin has a density of 0.94 g / cm3 or more, a PDI of 25 or more, and is capable of being stretched 4 times or more in the MD (Machine Direction) at a speed of 200 % / s at 120 to 130°C and then sequentially biaxially stretched 4 times or more in the TD (Transverse Direction), or of being simultaneously biaxially stretched 4x4 times or more in the MD (Machine Direction) and TD (Transverse Direction).

9. In paragraph 8, The above hybrid metallocene catalyst is a high-density polyethylene resin comprising a transition metal compound of the following chemical formulas 1 to 3. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In the above chemical formulas 1 to 3, R1, R2, R3, R4 and R5 are independently C1-C6 alkyl, R a and R b are each independently C1-C6 alkylene, X is a halogen, n and m are integers from 0 to 5, l is an integer from 1 to 4, o1 and o2 are integers from 0 to 4.

10. In paragraph 9, A high-density polyethylene resin comprising the above hybrid metallocene catalyst in a molar ratio of Chemical Formula 1: Chemical Formula 2: Chemical Formula 3 = 1: 0.2 to 3: 1 to 7.

11. In paragraph 8, C4-C above 20 α-Olefin is a high-density polyethylene resin that is a C5-C8 α-olefin.

12. In paragraph 8, The above high-density polyethylene resin is a high-density polyethylene resin having an MFR (Melt Flow Rate) of 40 or more.

13. In paragraph 8, The above high-density polyethylene resin is a high-density polyethylene resin having a crystallinity (Xc) of 70% or less.

14. A high-density polyethylene film containing the high-density polyethylene resin of Article 8.

15. In paragraph 14, The above high-density polyethylene film is a high-density polyethylene film having a haze of 25% or less as measured according to ASTM D1003.

16. In paragraph 14, The above high-density polyethylene film is a high-density polyethylene film having a transparency of 70% or more as measured according to ASTM D1003.

17. In paragraph 14, The above high-density polyethylene film is a high-density polyethylene film having an impact strength of 120 gf or more as measured according to ASTM D1709.

18. A packaging material manufactured from a film selected from any one of items 14 to 17.

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