High-density polyethylene biaxially stretched film with excellent strength characteristics and method for manufacturing same

Abstract

The present invention relates to a high-density polyethylene biaxially stretched film having excellent optical properties and a method for manufacturing same. Specifically, the method for manufacturing high-density polyethylene involves polymerizing ethylene and an α-olefin at a specific molar percentage ratio in the presence of a hybrid metallocene catalyst, thereby enabling the production of high-density polyethylene that has high processability suitable for biaxial stretching and that exhibits excellent optical properties after biaxial stretching. In addition, the high-density polyethylene can replace the base layer of conventional packaging materials, thereby enabling the production of a packaging material made of a single material and thus providing an environmentally friendly packaging material having an improved recyclability.

Description

High-density polyethylene biaxially oriented film with excellent optical properties and method for manufacturing the same

[0001] The present invention relates to a high-density polyethylene biaxially oriented film having excellent optical properties and a method for manufacturing the same.

[0002] Conventional packaging materials often use a mixture of various materials, such as polyethylene terephthalate (PET), nylon, or polyamide (PA) substrates within a polyethylene inner layer. These composite packaging materials complicate the recycling process, requiring the separation of individual materials. This complicates the process, increases processing costs, and reduces recycling rates. To address these environmental concerns, attempts have been made to use a single-material packaging material using biaxially oriented polyethylene (BOPE) as the substrate. However, biaxial stretching of standard polyethylene is difficult, and the resulting film is uneven, hindering its application to products. Furthermore, while biaxial stretching can increase tensile strength as the polymer chains of high-density polyethylene elongate and change their arrangement, it hinders the distribution of multiaxial stresses, making it vulnerable to impact. In particular, high-density polyethylene struggles to achieve impact strength comparable to that of low-density polyethylene due to its high crystallinity and crystal structure.

[0003] Related prior literature includes Korean Patent Publication No. 10-2018-0102541 (September 17, 2018).

[0004] The purpose of the present invention is to provide a high-density polyethylene having excellent optical properties and exhibiting high processability that allows biaxial stretching using a hybrid metallocene catalyst, and a method for producing the same.

[0005] Another object of the present invention is to provide a single-material packaging material by using the high-density polyethylene to replace existing materials such as polyethylene terephthalate (PET), nylon, and polyamide (PA) used as a base layer of packaging materials.

[0006] In the past, in order to simultaneously satisfy excellent impact strength and transparency while enabling the above biaxial stretching, a polymer with a wide molecular weight distribution was manufactured, or two or more polymers having different molecular weights were blended and used. The present invention enables biaxial stretching by using a specific hybrid metallocene catalyst and simultaneously controlling the concentration % ratio of ethylene and α-olefin to a specific ratio, and the impact strength after biaxial stretching is 1000 gf / cm. 2 The present invention aims to provide a method for manufacturing high-density polyethylene having excellent transparency and a haze of 25% or less.

[0007] 1. One aspect of the present invention relates to a method for producing high-density polyethylene. The method is a method for producing high-density polyethylene by injecting ethylene and α-olefin (alpha-olefin) into a reactor and polymerizing them under a hybrid metallocene catalyst including a transition metal compound represented by the following chemical formulas 1 to 3.

[0008] The biaxially oriented film having a thickness of 10 to 50 μm manufactured from the above high-density polyethylene has an impact strength of 1000 gf / cm according to ASTM D 3420. 2 A method for manufacturing high-density polyethylene is provided.

[0009] [Chemical Formula 1]

[0010]

[0011] [Chemical Formula 2]

[0012]

[0013] [Chemical Formula 3]

[0014]

[0015] In the above chemical formulas 1 to 3, M 1 Inland M 3 Each independently is titanium (Ti), zirconium (Zr) or hafnium (Hf), and X 1 Inland X 3 are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 alkynyl, C 6-20 Aryl, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamido, C 6-20 Arylamido or C 1-20 Alkylidene, R1 to R 46 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamido, substituted or unsubstituted C 6-20 Arylamido, substituted or unsubstituted C 1-20 Alkylidene, or substituted or unsubstituted C 1-20 It is a cylinder, R1 to R 10 , R 13 Inland R 44 are independently connected to adjacent groups, each of which is substituted or unsubstituted, saturated or unsaturated C 4-20 It can form a ring. Q 1 , Q 2 are each independently one of carbon (C), silicon (Si), germanium (Ge), or tin (Sn).

[0016] 2. In the above specific example, the hybrid metallocene catalyst may be a supported catalyst in which a transition metal compound and a cocatalyst are supported on a support.

[0017] 3. In the above 1 to 2 specific examples, the cocatalyst may be one or two or more selected from the group consisting of compounds represented by the following chemical formulas 4 to 6.

[0018] [Chemical Formula 4]

[0019]

[0020] [Chemical Formula 5]

[0021]

[0022] [Chemical Formula 6]

[0023] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0024] In the above chemical formulas 4 to 6,

[0025] n is an integer greater than or equal to 2, and R 47 Silver halogen, C 1-20 C substituted with an alkyl group or halogen 1-20 is an alkyl group,

[0026] D is aluminum (Al) or boron (B), and R 48 Inland R 50 are each independently halogen, C 1-20 C, a straight or branched chain alkyl group, substituted with halogen 1-20 alkyl group or C 1-20 is an alkoxy group,

[0027] L is a neutral or cationic Lewis base, [LH] + and [L] + is a Bronsted acid, Z is a group 13 element, and A is C 6-20 Aryl group of or C 1-20 is an alkyl group.

[0028] 4. In the above 1 to 3 specific examples, the carrier may be one or a mixture of two or more selected from the group consisting of silica, aluminum oxide, and magnesium oxide.

[0029] 5. In the above 1 to 4 specific examples, the α-olefin is C 4-20 It may be an α-olefin.

[0030] 6. In the above 1 to 5 specific examples, the high-density polyethylene manufacturing method may be a method of polymerizing α-olefin in a molar % ratio relative to ethylene of 0.4 or more and less than 0.5.

[0031] 7. In the above 1 to 6 specific examples, the high-density polyethylene manufacturing method may further include hydrogen to carry out the polymerization reaction, and when injecting hydrogen and α-olefin into the reactor, the ratio of the α-olefin flow rate to the hydrogen flow rate may be injected at a flow rate of 1:5 to 20.

[0032] 8. In the above 1 to 7 specific examples, the high-density polyethylene manufacturing method may be a method of continuously gas-phase polymerizing ethylene and α-olefin in a fluidized bed reactor.

[0033] 9. In the above 1 to 8 specific examples, the high-density polyethylene manufacturing method may be a method of polymerizing ethylene and α-olefin at a temperature of 70 to 100°C.

[0034] 10. In the above specific examples 1 to 9, the biaxially oriented film may be manufactured by processing the high-density polyethylene into a sheet having a thickness of 1 mm and then stretching it at least 4 times in the machine direction (MD) and at least 4 times in the transverse direction (TD) at an elongation rate of 100% per second.

[0035] 11. Another aspect of the invention relates to high-density polyethylene. The high-density polyethylene is a high-density polyethylene obtained by polymerizing ethylene and α-olefin (alpha-olefin) under a hybrid metallocene catalyst including a transition metal compound represented by the following chemical formulas 1 to 3, wherein the molar ratio of α-olefin to ethylene is 0.4 or more and less than 0.5:

[0036] [Chemical Formula 1]

[0037]

[0038] [Chemical Formula 2]

[0039]

[0040] [Chemical Formula 3]

[0041]

[0042] In the above chemical formulas 1 to 3, M 1 Inland M 3 Each independently is titanium (Ti), zirconium (Zr) or hafnium (Hf), and X 1 Inland X 3 are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 alkynyl, C 6-20 Aryl, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamido, C 6-20 Arylamido or C 1-20 Alkylidene, R1 to R 46 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamido, substituted or unsubstituted C 6-20 Arylamido, substituted or unsubstituted C 1-20 Alkylidene, or substituted or unsubstituted C 1-20 It is a cylinder, R1 to R 10 , R 13 Inland R 44 are independently connected to adjacent groups, each of which is substituted or unsubstituted, saturated or unsaturated C 4-20 It can form a ring. Q 1 , Q 2 are each independently one of carbon (C), silicon (Si), germanium (Ge), or tin (Sn).

[0043] 12. In the above 11 specific examples, the high-density polyethylene can be subjected to biaxial stretching processing, and a high-density polyethylene sheet manufactured to a thickness of 1 mm can be stretched at least 4 times in the longitudinal direction (MD; machine direction) and at least 4 times in the transverse direction (TD; transverse direction) at an elongation rate of 100% per second.

[0044] 13. In the above 11 to 12 specific examples, the melt index (MI) of the high-density polyethylene measured at 190° C. under a load of 2.16 kg according to ASTM D1238 may be 0.1 to 0.5 g / 10 min.

[0045] 14. In the above 11 to 13 specific examples, the melt index (MI) of the high-density polyethylene measured at 190° C. under a load of 21.6 kg according to ASTM D1238 may be 1 to 20 g / 10 min.

[0046] 15. In the above 11 to 14 specific examples, the density of the high-density polyethylene is 0.941 g / cm 3 It could be something like this.

[0047] 16. In the above 11 to 15 specific examples, the number average molecular weight of the high-density polyethylene may be 6,000 to 10,000 g / mol.

[0048] 17. In the above 11 to 16 specific examples, the weight average molecular weight of the high-density polyethylene may be 140,000 to 200,000 g / mol.

[0049] 18. In the above 11 to 17 specific examples, the melting temperature (T) of the high-density polyethylene m ) may be between 120 and 150 ℃.

[0050] 19. Another aspect of the present invention relates to the high-density polyethylene biaxially oriented film. The film comprises the high-density polyethylene according to the specific examples 11 to 18.

[0051] 20. In the above 19 specific examples, the high-density polyethylene biaxially oriented film may have a thickness of 10 to 50 μm.

[0052] 21. In the above 19 to 20 specific examples, the impact strength of the high-density polyethylene biaxially oriented film according to ASTM D 3420 is 1000 gf / cm 2 It could be something like this.

[0053] 22. In the above 19 to 21 specific examples, the haze of the high-density polyethylene biaxially oriented film according to ASTM D 1003 may be 25% or less.

[0054] 23. Another aspect of the present invention relates to a packaging material. The packaging material comprises high-density polyethylene according to any of the above-mentioned embodiments 11 to 18.

[0055] 24. Another aspect of the present invention relates to a method for manufacturing a high-density polyethylene biaxially oriented film. The method may involve biaxially oriented a film made of high-density polyethylene and having a thickness of 500 to 5000 μm by at least four times in the machine direction (MD) and at least four times in the transverse direction (TD).

[0056] 25. In the above 24 specific examples, the biaxial stretching process may be performed at a temperature of 100 to 150°C.

[0057] 26. In the above 24 to 25 specific examples, the biaxial stretching process may be stretching in the width direction after stretching in the length direction at a speed of 100% elongation per second (s).

[0058] A method for producing high-density polyethylene according to one aspect of the present invention can produce high-density polyethylene having high processability that allows biaxial stretching processing and excellent impact strength and transparency after biaxial stretching processing by polymerizing ethylene and α-olefin at a specific concentration % ratio in the presence of a hybrid metallocene catalyst.

[0059] The biaxially oriented film manufactured from the above high-density polyethylene can replace the base layer of existing packaging materials, enabling the manufacture of single-material packaging materials, thereby providing an environmentally friendly packaging material with an improved recyclability rate.

[0060] The biaxially oriented film manufactured from the above high-density polyethylene has an impact strength of 1000 gf / cm 2 It can have values ​​above.

[0061] The present invention will be described in more detail below. However, the following specific examples or examples are merely references for explaining the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

[0062] Additionally, unless otherwise defined, 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 invention pertains. The terminology used herein is for the purpose of describing specific embodiments only and is not intended to be limiting.

[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] Additionally, unless otherwise specifically defined in the present invention, when a layer or member is said to be located “on” another layer or member, this includes not only cases where a layer or member is in contact with another layer or member, but also cases where another layer or another member exists between the two layers or two members.

[0066] 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 in the understanding of the present invention.

[0067] To address the difficulty of biaxially oriented polyethylene, which has hindered its application as a single packaging material, the present inventors devised a manufacturing method in which an appropriate ratio of ethylene and α-olefin is polymerized in the presence of a hybrid metallocene catalyst of a specific composition. The inventors discovered that this manufacturing method not only enables biaxial oriented processing, but also produces high-density polyethylene that possesses excellent impact strength and transparency, thereby completing the present invention.

[0068] The present invention will be described below.

[0069] The present invention relates to a method for producing high-density polyethylene, which comprises injecting ethylene and α-olefin (alpha-olefin) into a reactor and polymerizing them under a hybrid metallocene catalyst comprising a transition metal compound represented by the following chemical formulas 1 to 3.

[0070] The biaxially oriented film having a thickness of 10 to 50 μm manufactured from the above high-density polyethylene has an impact strength of about 1000 gf / cm according to ASTM D 3420. 2 A method for manufacturing high-density polyethylene is provided.

[0071] [Chemical Formula 1]

[0072]

[0073] [Chemical Formula 2]

[0074]

[0075] [Chemical Formula 3]

[0076]

[0077] In the above chemical formulas 1 to 3, M 1 Inland M 3 Each independently is titanium (Ti), zirconium (Zr) or hafnium (Hf), and X 1 Inland X 3 are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 alkynyl, C6-20 Aryl, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamido, C 6-20 Arylamido or C 1-20 Alkylidene, R1 to R 46 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamido, substituted or unsubstituted C 6-20 Arylamido, substituted or unsubstituted C 1-20 Alkylidene, or substituted or unsubstituted C 1-20 It is a cylinder, R1 to R 10 , R 13 Inland R 44 are independently connected to adjacent groups, each of which is substituted or unsubstituted, saturated or unsaturated C 4-20 It can form a ring. Q 1 , Q 2 are each independently one of carbon (C), silicon (Si), germanium (Ge), or tin (Sn).

[0078] C above 1-20 Alkyl may be straight-chain, branched-chain or cyclic alkyl. Specifically, the C 1-20 Alkyl is C 1-20 Straight chain alkyl, C 1-10 Straight chain alkyl, C 1-5 Straight chain alkyl, C 3-20　 Branched or cyclic alkyl, C 3-15 Branched or cyclic alkyl, or C3-10 It may be a branched or cyclic alkyl. More specifically, it may have carbon number C. 1-20 Alkyl may be, but is not limited to, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, an iso-pentyl group, an n-hexyl group, or a cyclohexyl group.

[0079] C above 2-20 Alkenyl may be straight-chain, branched-chain or cyclic alkenyl. Specifically, the above C 2-20 Alkenyl is C 2-20 Straight-chain alkenyl, C 2-10 Straight-chain alkenyl, C 2-5 Straight-chain alkenyl, C 3-20 Branched-chain alkenyl, C 3-15 Branched-chain alkenyl, C 3-10 Branched-chain alkenyl, C 5-20 Cyclic alkenyl or C 5-10 It may be a cyclic alkenyl. More specifically, C 2-20 Alkenyl may be, but is not limited to, ethenyl, propenyl, butenyl, pentenyl, or cyclohexenyl.

[0080] C above 6-20 Aryl can mean a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon. Specifically, C 6-20 Aryl may be, but is not limited to, a phenyl group, a naphthyl group, or anthracenyl group.

[0081] C above 1-20 Alkyl C 6-20 Aryl may mean a substituent in which one or more hydrogens of aryl are replaced by alkyl. Specifically, the C 6-20 Alkylaryl may be, but is not limited to, methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, or cyclohexylphenyl.

[0082] C above 6-20 Aryl C1-20 Alkyl may mean a substituent in which one or more hydrogens of alkyl are replaced by aryl. Specifically, the above C 6-20 Arylalkyl may be, but is not limited to, benzyl, phenylpropyl, or phenylhexyl.

[0083] C above 1-20 Alkylamido may refer to a substituent in which one or more hydrogens of an amino group (-NH2) are replaced by alkyl. The alkyl is the aforementioned C 1-20 It may be the same as an example of alkyl. Specifically, the above C 1-20 Alkylamido may be, but is not limited to, methylamido, ethylamido, propylamido, butylamido, pentylamido, or hexylamido.

[0084] C above 6-20 Arylamido may refer to a substituent in which one or more hydrogens of an amino group (-NH2) are replaced by aryl. The aryl is the aforementioned C 6-20 It may be the same as the example of aryl. Specifically, the above C 6-20 Aryl amido may be, but is not limited to, N-phenylamido, N-naphthylamido, N-anthracenamido, N-phenyleneamido, or N-pyreneamido.

[0085] In the above alkylamido and arylamido, “amido” means an amino (-NH2) group bonded to a carbonyl group (C=O).

[0086] C above 1-20 Alkylidene may refer to a divalent aliphatic hydrocarbon group in which two hydrogen atoms are removed from one carbon atom of an alkyl group. Specifically, it may be ethylidene, propylidene, isopropylidene, butylidene, pentylidene, etc., but is not limited thereto.

[0087] In one embodiment, the transition metal compound represented by the above chemical formula 1 is wherein R1 and R3 to R5 are each independently hydrogen, straight-chain or branched C 1~4 Alkyl, and R2 is a straight or branched C 3~8Alkyl, R6 to R 10 are each independently hydrogen, straight-chain or branched C 1~4 It may be a transition metal compound containing an alkyl or phenyl group.

[0088] In one embodiment, the transition metal compound represented by the above chemical formula 2 is R 13 , R 14 , R 16 , R 17 , R 19 , R 20 , R 21 , R 22 and R 24 is hydrogen, and R 15 , R 18 , R 23 are each independently hydrogen, straight-chain or branched C 3~8 Alkyl, R 11 and R 12 are each independently hydrogen, straight-chain or branched C 1~4 It may be a transition metal compound containing an alkyl or phenyl group.

[0089] In one embodiment, the transition metal compound represented by the above chemical formula 3 is R 25 Inland R 29 , R 31 Inland R 33 , R 36 Inland R 38 and R 40 Inland R 44 is hydrogen, and R 30 , R 39 is hydrogen, straight or branched chain C 1~4 Alkyl, phenyl group, R 34 , R 35 are each independently hydrogen, straight-chain or branched C 1~4 Alkyl, R 45 and R 46 Each independently straight or branched C 1~6 It may be a transition metal compound having an alkyl or phenyl group.

[0090] In one embodiment, the transition metal compound represented by the above chemical formula 1 may be at least one of the transition metal compounds represented by the following chemical formulas 1-1 to 1-13, the transition metal compound represented by the above chemical formula 2 may be at least one of the transition metal compounds represented by the following chemical formulas 2-1 to 2-8, and the transition metal compound represented by the above chemical formula 3 may be at least one of the transition metal compounds represented by the following chemical formulas 3-1 to 3-7, but is not limited thereto.

[0091] [Chemical Formula 1-1]

[0092]

[0093] [Chemical Formula 1-2]

[0094]

[0095] [Chemical Formula 1-3]

[0096]

[0097] [Chemical Formula 1-4]

[0098]

[0099] [Chemical Formula 1-5]

[0100]

[0101] [Chemical Formula 1-6]

[0102]

[0103] [Chemical Formula 1-7]

[0104]

[0105] [Chemical Formula 1-8]

[0106]

[0107] [Chemical Formula 1-9]

[0108]

[0109] [Chemical Formula 1-10]

[0110]

[0111] [Chemical Formula 1-11]

[0112]

[0113] [Chemical Formula 1-12]

[0114]

[0115] [Chemical Formula 1-13]

[0116]

[0117] [Chemical Formula 2-1]

[0118]

[0119] [Chemical Formula 2-2]

[0120]

[0121] [Chemical Formula 2-3]

[0122]

[0123] [Chemical Formula 2-4]

[0124]

[0125] [Chemical Formula 2-5]

[0126]

[0127] [Chemical Formula 2-6]

[0128]

[0129] [Chemical Formula 2-7]

[0130]

[0131] [Chemical Formula 2-8]

[0132]

[0133] [Chemical Formula 3-1]

[0134]

[0135] [Chemical Formula 3-2]

[0136]

[0137] [Chemical Formula 3-3]

[0138]

[0139] [Chemical Formula 3-4]

[0140]

[0141] [Chemical Formula 3-5]

[0142]

[0143] [Chemical Formula 3-6]

[0144]

[0145] [Chemical Formula 3-7]

[0146]

[0147] In one embodiment, the hybrid metallocene catalyst may contain 50 to 200 parts by weight, 70 to 100 parts by weight, or 80 to 90 parts by weight of the transition metal compound represented by the chemical formula 2, and 200 to 500 parts by weight, 250 to 450 parts by weight, or 300 to 400 parts by weight of the transition metal compound represented by the chemical formula 3, based on 100 parts by weight of the transition metal compound represented by the chemical formula 1, but is not limited thereto.

[0148] In one aspect, the hybrid metallocene catalyst may be a supported catalyst in which a transition metal compound and a cocatalyst are supported on a support.

[0149] In one embodiment, the cocatalyst may be one or more selected from the group consisting of compounds represented by the following chemical formulas 4 to 6.

[0150] [Chemical Formula 4]

[0151]

[0152] [Chemical Formula 5]

[0153]

[0154] [Chemical Formula 6]

[0155] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0156] In the above chemical formulas 4 to 6,

[0157] n is an integer greater than or equal to 2, and R 47 Silver halogen, C 1-20 C substituted with an alkyl group or halogen 1-20 is an alkyl group,

[0158] D is aluminum (Al) or boron (B), and R 48 Inland R 50 are each independently halogen, C 1-20 C, a straight or branched chain alkyl group, substituted with halogen 1-20 alkyl group or C 1-20 is an alkoxy group,

[0159] L is a neutral or cationic Lewis base, [LH] + and [L] + is a Bronsted acid, Z is a group 13 element, and A is C 6-20 Aryl group of or C 1-20 is an alkyl group.

[0160] The cocatalyst compound represented by the above chemical formula 4 may be any one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, but is not limited thereto.

[0161] The cocatalyst compound represented by the above chemical formula 5 may be an organic aluminum or boron compound, and examples thereof include, but are not limited to, 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, tributylboron, and the like.

[0162] The co-catalyst compound represented by the above chemical formula 6 may be a compound in which a cation such as ammonium, phosphonium, anilinium, or carbonium is combined with an organometallic compound having boron or aluminum as a central metal, and examples thereof include 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, triethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, triphenylcarbonium tetra(p-trifluoromethylphenyl)boron, triphenylcarbonium tetrapentafluorophenylboron, etc., but are not limited thereto.

[0163] In one embodiment, the support may be capable of supporting both a transition metal compound and a cocatalyst compound, and may include a material containing a hydroxyl group on its surface. Specifically, a material having a hydroxyl group and a siloxane group on its surface, from which moisture is removed, and thus having enhanced reactivity, may be used.

[0164] The support may be, for example, one or a mixture of two or more selected from the group consisting of silica, aluminum oxide, and magnesium oxide. Specifically, silica, silica-alumina, and silica-magnesia dried at high temperature may be used as the support, and these may typically contain oxides, carbonates, sulfates, and nitrates such as Na2O, K2CO3, BaSO4, and Mg(NO3)2. In addition, these may include carbon, zeolite, magnesium chloride, and the like. However, the support is not limited to these, and is not particularly limited as long as it can support a transition metal compound and a cocatalyst compound.

[0165] The average particle size of the above-mentioned carrier may be about 10 to 250 ㎛, about 10 to 150 ㎛, or about 20 to 100 ㎛, but is not limited thereto.

[0166] The micropore volume of the above-mentioned carrier is about 0.1 to 10 cm 3 / g, about 0.5 to 5 cm 3 / g, about 1.0 to 3.0 cm 3 / g may be, but is not limited to.

[0167] The specific surface area of ​​the above-mentioned carrier may be about 1 to 1,000 m2 / g, about 100 to 800 m2 / g, or about 200 to 600 m2 / g, but is not limited thereto.

[0168] In one embodiment, the α-olefin is C 4-20 , C 4-12It may be an α-olefin. The α-olefin may be, for example, one or a mixture of two or more selected from the group consisting of 1-butene, 3-methyl-1-butene, 1-pentene, 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, but is not limited thereto. As a specific example, the α-olefin may be 1-hexene, but is not necessarily limited thereto.

[0169] In one embodiment, the polymerization may be performed at a molar ratio of α-olefin to ethylene of about 0.40 or more and less than 0.50, for example, about 0.42 to 0.48, about 0.44 to 0.46, and a high-density polyethylene manufactured at a molar ratio of α-olefin to ethylene of the above range can be biaxially stretched and can have excellent impact strength and transparency after biaxially stretching, thereby better achieving the purpose of the present invention.

[0170] In one embodiment, the mol% ratio may be a ratio measured by gas chromatography (GC). For example, the mol% ratio of α-olefin to ethylene may be a value obtained by dividing the mol% concentration of α-olefin measured by GC by the mol% concentration of ethylene.

[0171] In one embodiment, the method for producing high-density polyethylene further includes a polymerization reaction by including hydrogen, and when injecting hydrogen and α-olefin into the reactor, the ratio of α-olefin flow rate to hydrogen flow rate may be injected at a flow rate of about 1:5 to 20, about 1:7 to 15, or about 1:10 to 15, and the above flow rate range enables biaxial stretching processing, and high-density polyethylene having excellent impact strength and transparency even after biaxial stretching can be produced, thereby better achieving the purpose of the present invention. For example, in a pilot scale, a volume of 0.25 m 3 Hydrogen may be injected into the fluidized bed reactor at a flow rate of about 1 to 20 g / hr, about 5 to 15 g / hr, or about 7 to 10 g / hr, and about α-olefin may be injected at a flow rate of about 50 to 200 g / hr, about 80 to 150 g / hr, or about 100 to 150 g / hr, while satisfying the above flow rate ratio.

[0172] In one embodiment, the method for producing high-density polyethylene may be a method for continuously polymerizing ethylene and α-olefin in a fluidized bed reactor, wherein one or more fluidized bed reactors may be provided in series. When the fluidized bed reactor is used for the vapor phase polymerization, the produced high-density polyethylene is preferably capable of biaxial stretching processing and has excellent impact strength and transparency after biaxial stretching processing, but is not limited thereto.

[0173] In one embodiment, the method for producing high-density polyethylene may be a method for polymerizing ethylene and α-olefin at a temperature of about 70 to 100°C, about 80 to 95°C, or about 85 to 95°C. Under the temperature conditions in the above range, it may be possible to produce high-density polyethylene with a molar ratio of α-olefin to ethylene of about 0.4 or more and less than 0.5. In addition, the produced high-density polyethylene is capable of biaxial stretching processing and has excellent impact strength and transparency after biaxial stretching processing, which is preferred, but is not limited thereto.

[0174] Another aspect of the present invention provides high-density polyethylene polymerized with ethylene and α-olefin (alpha-olefin) under a hybrid metallocene catalyst including a transition metal compound represented by the following chemical formulae 1 to 3.

[0175] [Chemical Formula 1]

[0176]

[0177] [Chemical Formula 2]

[0178]

[0179] [Chemical Formula 3]

[0180]

[0181] The contents of the above chemical formulas 1 to 3 are the same as those described above, so their description is omitted.

[0182] In one embodiment, the high-density polyethylene can be biaxially stretched, and a high-density polyethylene sheet manufactured to a thickness of 1 mm can be stretched in a longitudinal direction (MD; machine direction) by about 4 times or more, but not particularly limited to about 10 times or less, or about 8 times or less, and in a transverse direction (TD; transverse direction) by about 4 times or more, but not particularly limited to about 15 times or less, or about 10 times or less, at an elongation rate of 100% per second. When the high-density polyethylene is biaxially stretched, it can have excellent optical properties even after processing, and can be applied as a base layer of a packaging material.

[0183] Furthermore, if the film formation is uneven during biaxial stretching of polyethylene, its application to products is difficult. Therefore, when the high-density polyethylene is stretched evenly in both directions during biaxial stretching, opaque lines are not formed, and stretching defects due to breakage do not occur, it may be advantageous for application as a packaging material base layer.

[0184] In one embodiment, the melt index (MI) of the high-density polyethylene measured at 190° C. under a load of 2.16 kg according to ASTM D1238 may be about 0.1 to 0.5 g / 10 min, about 0.2 to 0.4 g / 10 min, or about 0.2 to 0.3 g / 10 min, and a high-density polyethylene having a melt index in the above range is preferred because it has excellent biaxial stretching processability, but is not limited thereto.

[0185] In one embodiment, the melt index (MI) of the high-density polyethylene measured at 190° C. under a load of 21.6 kg according to ASTM D1238 may be about 1 to 20 g / 10 min, about 3 to 15 g / 10 min, or about 5 to 10 g / 10 min, and a high-density polyethylene having a melt index in the above range is preferred due to its excellent biaxial stretching processability, but is not limited thereto.

[0186] In one embodiment, the melt flow rate (MFR) of the high-density polyethylene measured at 190° C. according to ASTM D1238 may be about 20 to 60 g / 10 min, about 30 to 50 g / 10 min, or about 40 to 45 g / 10 min, and a high-density polyethylene having a melt flow index in the above range is preferred due to its superior biaxial stretching processability, but is not limited thereto. The MFR is a value calculated by MI (21.6 kg) / MI (2.16 kg) = MFR at 190° C. under a load of 21.6 and a load of 2.16 of the high-density polyethylene.

[0187] In one embodiment, the density of the high-density polyethylene is about 0.941 to 0.965 g / cm 3 , about 0.942 to 0.960 g / cm 3 , about 0.945 to 0.955 g / cm 3 It may be that high-density polyethylene having a density in the above range is preferred because it has excellent biaxial stretching processability and can have excellent impact strength and transparency after biaxial stretching, but is not limited thereto.

[0188] In one embodiment, the number average molecular weight of the high-density polyethylene may be about 6,000 to 10,000 g / mol, about 7,000 to 9,000 g / mol, or about 8,000 to 8,500 g / mol. High-density polyethylene having a number average molecular weight within the above range may have excellent mechanical strength and flowability, thus facilitating biaxial stretching processing, and may have excellent impact strength and transparency after biaxial stretching processing, and is therefore preferred, but is not limited thereto.

[0189] In one embodiment, the weight average molecular weight of the high-density polyethylene may be about 140,000 to 200,000 g / mol, about 150,000 to 180,000 g / mol, or about 160,000 to 170,000 g / mol. High-density polyethylene having a weight average molecular weight within the above range may have excellent strength and toughness, and may be applied as a packaging material base layer material, and may be easily subjected to biaxial stretching processing, and may have excellent impact strength and transparency after biaxial stretching processing, and is therefore preferred, but is not limited thereto.

[0190] In one embodiment, the polydispersity index (PDI) of the high-density polyethylene may be about 15 to 30, or about 17 to 25.

[0191] In one aspect, the melting temperature (T) of the high-density polyethylene m ) may be about 120 to 150 ℃, about 130 to 140 ℃, or about 130 to 135 ℃, and high-density polyethylene in the above melting temperature range may have excellent biaxial stretching processability and may have excellent impact strength and durability, so it may be preferred.

[0192] In one aspect, the crystallization temperature (T) of the high-density polyethylene c) may be about 100 to 130°C, about 110 to 120°C. High-density polyethylene in the above crystallization temperature range may have excellent thermal properties and processability, and may also have excellent impact strength and transparency, so that the purpose of the present invention can be well achieved.

[0193] Another aspect of the present invention provides a high-density polyethylene biaxially oriented film comprising the high-density polyethylene.

[0194] In one embodiment, the high-density polyethylene biaxially oriented film may have a thickness of about 10 to 50 μm, about 10 to 30 μm, or about 15 to 20 μm, and a film having the above thickness range is preferred as a packaging material base layer because it can have excellent impact strength and transparency, but is not limited thereto.

[0195] In one embodiment, the impact strength of the high-density polyethylene biaxially oriented film according to ASTM D 342 is about 1000 gf / cm. 2 It may be more than that, and the lower limit is not specifically limited, but it is about 1100 gf / cm 2 , about 1200 gf / cm 2 , approximately 1300gf / cm 2 It can be more than 1600 gf / cm, but the upper limit is not specifically limited. 2 , 1550 gf / cm 2 It may be less than 1000 to 1600 gf / cm. For example, 2 , 1100 to 1550 gf / cm 2 , 1200 to 1550 gf / cm 2 A high-density polyethylene biaxially oriented film having the above impact strength range is preferred because it can have excellent mechanical strength, but is not limited thereto.

[0196] In one embodiment, the haze of the high-density polyethylene biaxially oriented film according to ASTM D 1003 may be about 25% or less, about 23% or less, or about 20% or less, and the lower limit is not particularly limited, but may be about 5% or more, about 7% or more, or about 10% or more, and may be any value between the above values. For example, it may be about 5 to 25%, about 7 to 23%, or about 10 to 20%. A high-density polyethylene biaxially oriented film having the above haze range is preferred because it can have excellent optical properties.

[0197] Another aspect of the present invention provides a packaging material manufactured from a high-density polyethylene biaxially oriented film including the high-density polyethylene.

[0198] In one aspect, the packaging material may be a single-material packaging material in which the substrate layer, which was conventionally made of polyethylene terephthalate, nylon, polyamide, etc., is replaced with a high-density polyethylene biaxially oriented film according to one aspect of the present invention.

[0199] Another aspect of the present invention provides a method for manufacturing a high-density polyethylene biaxially oriented film comprising the high-density polyethylene, wherein a film having a thickness of 500 to 5000 μm made of high-density polyethylene is biaxially oriented in a longitudinal direction (MD; machine direction) by about 4 times or more, but not particularly limited to about 10 times or less, but not particularly limited to about 8 times, and in a transverse direction (TD; transverse direction) by about 4 times or more, but not particularly limited to about 15 times or less, but not particularly limited to about 10 times.

[0200] In one embodiment, the biaxial stretching process may be performed at a temperature of about 100 to 150°C.

[0201] In one embodiment, the biaxial stretching process may be a process of stretching in the longitudinal direction and then stretching in the transverse direction at a rate of 100% elongation per second (s). For example, the temperature may be about 110 to 140°C or about 120 to 130°C.

[0202] As an example of biaxial stretching processing, the high-density polyethylene may be manufactured into a 10 cm × 10 cm, 1 mm sheet using a compressor, and then the manufactured sheet may be heated in an oven at 120 to 130°C for 100 to 300 seconds, and then stretched in MD at a rate of 100% elongation per second (s) and then stretched in TD. The biaxial stretching processing may be performed using a KARO 5.0 biaxial stretching device from Bruckner, but is not limited thereto.

[0203] The present invention will be described in more detail based on the following examples and comparative examples. However, the following examples and comparative examples are merely illustrative examples for further explaining the present invention, and the present invention is not limited by the following examples and comparative examples.

[0204]

[0205] measurement method

[0206] 1. Method for measuring the molar ratio of α-olefin to ethylene

[0207] The molar concentrations of ethylene and α-olefin were measured using gas chromatography (PGC5000; ABB), and the molar % ratio was calculated using the following formula. At this time, the carrier gas of the gas chromatography column was hydrogen, and the temperature condition was measured at 190 ℃.

[0208] [Calculation formula]

[0209] Mole% ratio = α-olefin molar concentration (mol%) / ethylene molar concentration (mol%)

[0210] 2. Measurement of melt index (MI) and melt flow rate (MFR)

[0211] The melt index and melt flow rate of high-density polyethylene were measured under load conditions of 2.16 kg and 21.6 kg at 190 °C according to ASTM D1238.

[0212] 3. Density measurement

[0213] The density of high-density polyethylene was measured according to ASTM D1505.

[0214]

[0215] 4. Measurement of number average molecular weight, weight average molecular weight, and z-average molecular weight

[0216] Measurements were made at 160°C using GPC-FTIR (GPC-6; Polymer char) equipment, using PL gel Olexis as the column, polystyrene as the standard material, and trichlorobenzene as the solvent.

[0217]

[0218] 5. Melting temperature (T m ) and crystallization temperature (T c ) measurement

[0219] Measurements were made using a differential scanning calorimeter (DSC2920; TA instrument). Specifically, high-density polyethylene 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 10°C / min.

[0220]

[0221] 6. Biaxial stretching processing

[0222] A high-density polyethylene sheet measuring 10 cm in width, 10 cm in length, and 1 mm in thickness was manufactured at 190°C using a compressor, and then heated in an oven at 120 to 125°C for 300 seconds. Thereafter, the sheet was stretched in the machine direction (MD) at a rate of 100% elongation per second (s) and then in the transverse direction (TD) using a biaxial stretching device (KARO 5.0; Bruckner).

[0223]

[0224] 7. Haze measurement

[0225] According to ASTM D 1003, a biaxially oriented film specimen with a thickness of 18 ㎛ was measured five times using a haze measuring device (A-4725; Haze Gard Plus), and the average value was reported.

[0226]

[0227] 8. Film thickness measurement

[0228] According to ASTM D 4417, the film thickness was measured 10 times using a film measuring device (SP-SP1570; TQC) and the average value was used.

[0229]

[0230] 9. Impact strength measurement

[0231] According to ASTM D 3420, the biaxially oriented film specimens were measured five times using a film impact tester (Spencer Impact Tester; Thwing Albert Instrument Company) and the average value was calculated.

[0232] [Manufacture of hybrid metallocene catalysts]

[0233] [Manufacturing example]

[0234] [Chemical Formula 1-1]

[0235]

[0236] [Chemical Formula 2-1]

[0237]

[0238] [Chemical Formula 3-1]

[0239]

[0240] In a glove box, 1.4 g of a transition metal compound represented by the chemical formula 1-1, 1.2 g of a transition metal compound represented by the chemical formula 2-1, and 4.2 g of a transition metal compound represented by the chemical formula 3-1 were added to 1,100 g of a solution containing 10 wt% methylaluminoxane in toluene, and stirred at room temperature (23°C) for 1 hour to prepare a transition metal compound solution.

[0241] After adding 30 ml of purified toluene to 250 g of silica (XPO-2402) to prepare a silica slurry, the transition metal compound solution was injected 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, and only the metallocene catalyst was isolated, which was then washed three times with toluene and dried in a vacuum at 60°C for 10 hours to obtain 230 g of a hybrid supported catalyst in the form of a free-flowing powder.

[0242] [Comparative Manufacturing Example 1]

[0243] [Chemical Formula 1-13]

[0244]

[0245] [Chemical Formula 2-1]

[0246]

[0247] [Chemical Formula 7]

[0248]

[0249] In a glove box, 1.8 g of a transition metal compound represented by the above chemical formula 1-13, 1.6 g of a transition metal compound represented by the chemical formula 2-1, and 2.8 g of a transition metal compound represented by the chemical formula 7 were added to 1,100 g of a solution containing 10 wt% methylaluminoxane in toluene, and stirred at room temperature (23°C) for 1 hour to prepare a transition metal compound solution.

[0250] After adding 30 ml of purified toluene to 250 g of silica (XPO-2402) to prepare a silica slurry, the transition metal compound solution was injected and stirred in an oil bath at 25°C for 3 hours to prepare a metallocene catalyst solution. The metallocene catalyst solution was separated into solid and liquid, the supernatant was removed, and only the metallocene catalyst was isolated, which was then washed three times with toluene and dried in a vacuum at 25°C for 10 hours to obtain 230 g of a hybrid supported catalyst in the form of a free-flowing powder.

[0251] [Comparative Manufacturing Example 2]

[0252] [Chemical Formula 8]

[0253]

[0254] [Chemical Formula 2-1]

[0255]

[0256] [Chemical Formula 3-1]

[0257]

[0258] In a glove box, 1.4 g of a transition metal compound represented by the above chemical formula 8, 1.2 g of a transition metal compound represented by the chemical formula 2-1, and 4.2 g of a transition metal compound represented by the chemical formula 3-1 were added to 1,100 g of a solution containing 10 wt% methylaluminoxane in toluene, and stirred at room temperature (23°C) for 1 hour to prepare a transition metal compound solution.

[0259] After adding 30 ml of purified toluene to 250 g of silica (XPO-2402) to prepare a silica slurry, the transition metal compound solution was injected 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, and only the metallocene catalyst was isolated, which was then washed three times with toluene and dried in a vacuum at 60°C for 10 hours to obtain 230 g of a hybrid supported catalyst in the form of a free-flowing powder.

[0260] [Examples and Comparative Examples]

[0261] Using the catalyst manufactured in the above manufacturing example, a volume of 0.25 m 3 Continuous gas phase polymerization of ethylene and 1-hexene was performed in a fluidized bed reactor. The reaction conditions of Example 1 and Comparative Examples 1 to 5 are described in Table 1 below.

[0262] [Comparative Example 6] CHNA-8380 (Hanwha Solutions) high-density polyethylene

[0263] [Comparative Example 7] SURPASS TX150-A (NOVA) high-density polyethylene

[0264] Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Catalyst Manufacturing Example Manufacturing Example Manufacturing Example Manufacturing Example Comparative Manufacturing Example 1 Comparative Manufacturing Example 2 Ethylene injection pressure (kg / cm) 2 )14.3513.7014.0814.2614.4414.15Polymerization temperature (℃)90.1380.0489.8289.9389.9189.94Static (kV)-0.97 ± 0.92-0.50 ± 1.20-0.62 ± 1.20-0.92 ± 0.93-0.94±0.26-0.24 ± 1.51Catalyst injection (g / h)1.002.400.501.001.000.80Hydrogen injection (g / h)9.8512.5019.721.022.9919.611-Hexene injection (g / h)1361602512801000515Hydrogen / ethylene Mole % ratio 0.40 0.76 0.84 0.88 1.26 0.84 1-hexene / ethylene mole % ratio (R H)0.450.500.640.761.070.48Production per hour (kg / h)7.546.788.739.158.818.88PE produced per hour (kgPE / kgCat.hr)3,0152,8246,9853,6608,81111,102

[0265] Table 2 below shows the measured properties of polyethylene in examples and comparative examples. In Table 2 below, “impossible” indicates cases where the elongation length, film thickness, and haze could not be measured due to fracture during elongation.

[0266] Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 MI (2.16 kg, 190℃) 0.21 1.20.6 1.07 0.59 1.46 0.74 1.4 MFI (21.6 kg, 190℃) 8.88 55 27.74 1.45 27.74 10 2.74 8.5 1 19 MFR 4 2.3 18.34 6.13 8.84 6.86 7 0.31 6 5 8 5 Density (g / mL) 0.94 5 0.94 7 0.94 5 0.94 6 0.94 10.94 20.94 5 0.94 5 Mn (g / mol) 8,33 7 8,67 15,1395,9155,5432,2478,3657,167Mw(g / mol)161,35282,729135,090188,0021 18,965102,825105,05099,201PDI19.359.5426.2919.9521.4645.7612.613.84Tm (℃)129.6130.6127.8128.1125.45123.07115.3128.8Tc (℃)116.9116.8115.9115.3113.3112.7127.7114.9MD(x) × TD(x)5X9Non-contact5X95X94X75X95X95X9Impact strength (gf / cm 2 )1475687.2672209124730961Thickness (㎛)201717119.21615Haze (%)19.316.414.626209.511.4

[0267] In the above Tables 1 and 2, the high-density polyethylene of Example 1 manufactured with a molar ratio of ethylene / 1-hexene of 0.4 or more and less than 0.5 not only enables biaxial stretching to 5×9 (MD × TD), but also has a strength of 1000 gf / cm after biaxial stretching. 2 It was confirmed that it has the above impact strength and a Haze value of about 20%. As described above, the present invention has been described through specific matters and limited examples, but these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and those skilled in the art to which the present invention pertains can make various modifications and variations from this description.

[0268] Therefore, the idea of ​​the present invention should not be limited to the described embodiments, and all things that are equivalent or equivalent to the following claims as well as the claims are considered to fall within the scope of the idea of ​​the present invention.

Claims

1. A method for producing high-density polyethylene by injecting ethylene and α-olefin (alpha-olefin) into a reactor and polymerizing them under a hybrid metallocene catalyst including a transition metal compound represented by the following chemical formulas 1 to 3. The biaxially oriented film having a thickness of 10 to 50 μm manufactured from the above high-density polyethylene has an impact strength of 1000 gf / cm according to ASTM D 3420. 2 A method for manufacturing high-density polyethylene. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In the above chemical formulas 1 to 3, M 1 Inland M 3 Each independently is titanium (Ti), zirconium (Zr) or hafnium (Hf), and X 1 Inland X 3 are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 alkynyl, C 6-20 Aryl, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamido, C 6-20 Arylamido or C 1-20 Alkylidene, R1 to R 46 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamido, substituted or unsubstituted C 6-20 Arylamido, substituted or unsubstituted C 1-20 Alkylidene, or substituted or unsubstituted C 1-20 It is a cylinder, R1 to R 10 , R 13 Inland R 44 are independently connected to adjacent groups, each of which is substituted or unsubstituted, saturated or unsaturated C 4-20 It can form a ring. Q 1 , Q 2 are each independently one of carbon (C), silicon (Si), germanium (Ge), or tin (Sn).

2. 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 support.

3. In paragraph 2, A method for producing high-density polyethylene, wherein the cocatalyst is one or more selected from the group consisting of compounds represented by the following chemical formulas 4 to 6. [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [LH] + [Z(A)4] - or [L] + [Z(A)4] - In the above chemical formulas 4 to 6, n is an integer greater than or equal to 2, and R 47 Silver halogen, C 1-20 C substituted with an alkyl group or halogen 1-20 is an alkyl group, D is aluminum (Al) or boron (B), and R 48 Inland R 50 are each independently halogen, C 1-20 C, a straight or branched chain alkyl group, substituted with halogen 1-20 alkyl group or C 1-20 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 C 6-20 Aryl group of or C 1-20 is an alkyl group.

4. In paragraph 2, A method for producing high-density polyethylene, wherein the carrier is one or a mixture of two or more selected from the group consisting of silica, aluminum oxide, and magnesium oxide.

5. In paragraph 1, The above α-olefin is C 4-20 A method for producing high-density polyethylene which is an α-olefin.

6. In paragraph 1, The above high-density polyethylene manufacturing method is a high-density polyethylene manufacturing method in which the molar ratio of α-olefin to ethylene is polymerized to be 0.4 or more and less than 0.

5.

7. In paragraph 1, The above high-density polyethylene manufacturing method further includes hydrogen to carry out a polymerization reaction, and when injecting hydrogen and α-olefin into a reactor, the ratio of α-olefin flow rate to hydrogen flow rate is injected at a flow rate of 1:5 to 20.

8. In paragraph 1, The above high-density polyethylene manufacturing method is a high-density polyethylene manufacturing method in which ethylene and α-olefin are continuously subjected to a gas phase polymerization reaction in a fluidized bed reactor.

9. High-density polyethylene polymerized with ethylene and α-olefin (alpha-olefin) under a hybrid metallocene catalyst including a transition metal compound represented by the following chemical formulas 1 to 3, wherein the molar ratio of α-olefin to ethylene is 0.4 or more and less than 0.5: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In the above chemical formulas 1 to 3, M 1 Inland M 3 Each independently is titanium (Ti), zirconium (Zr) or hafnium (Hf), and X 1 Inland X 3 are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 alkynyl, C 6-20 Aryl, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamido, C 6-20 Arylamido or C 1-20 Alkylidene, R1 to R 46 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamido, substituted or unsubstituted C 6-20 Arylamido, substituted or unsubstituted C 1-20 Alkylidene, or substituted or unsubstituted C 1-20 It is a cylinder, R1 to R 10 , R 13 Inland R 44 are independently connected to adjacent groups, each of which is substituted or unsubstituted, saturated or unsaturated C 4-20 It can form a ring. Q 1 , Q 2 are each independently one of carbon (C), silicon (Si), germanium (Ge), or tin (Sn).

10. In paragraph 9, The above high-density polyethylene can be subjected to biaxial stretching, and a high-density polyethylene sheet manufactured to a thickness of 1 mm can be stretched at least four times in the longitudinal direction (MD; machine direction) and at least four times in the transverse direction (TD; transverse direction) at an elongation rate of 100% per second.

11. In paragraph 9, High-density polyethylene having a melt index (MI) of 0.1 to 0.5 g / 10 min, measured at 190°C under a load of 2.16 kg according to ASTM D1238.

12. In paragraph 9, High-density polyethylene having a melt index (MI) of 1 to 20 g / 10 min, measured at 190°C under a load of 21.6 kg according to ASTM D1238.

13. In paragraph 9, The density of the above high-density polyethylene is 0.941 g / cm 3 High density polyethylene, which is ideal.

14. In paragraph 9, High-density polyethylene having a number average molecular weight of 6,000 to 10,000 g / mol.

15. In paragraph 9, High-density polyethylene having a weight average molecular weight of 140,000 to 200,000 g / mol.

16. A high-density polyethylene biaxially oriented film comprising any one of the high-density polyethylenes selected from items 9 to 15.

17. In paragraph 16, The above high-density polyethylene biaxially oriented film is a high-density polyethylene biaxially oriented film having a thickness of 10 to 50 μm.

18. In paragraph 16, The impact strength of the above high-density polyethylene biaxially oriented film according to ASTM D 3420 is 1000 gf / cm 2 High-density polyethylene biaxially oriented film.

19. In paragraph 16, A high-density polyethylene biaxially oriented film having a haze of 25% or less according to ASTM D 1003.

20. A packaging material manufactured from a high-density polyethylene biaxially oriented film containing any one of the high-density polyethylene selected from items 9 to 15.

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