Polyethylene composition

Abstract

The present invention relates to a polyethylene composition comprising native polyethylene and recycled polyethylene [post consumer waste polyethylene (PCW PE)] and having improved resistance to environmental stress cracking and excellent mechanical properties.

Description

Technical Field

[0001] Cross - Reference to Related Applications

[0002] This application is based on and claims priority to Korean Patent Application Nos. 10-2023-0118439 and 10-2024-0121054, filed on September 6, 2023, and September 5, 2024, respectively, the disclosures of which are incorporated herein by reference in their entirety. Background Art

[0003] The demand for polyethylene resins is gradually increasing, and polyethylene resins are widely used in various fields.

[0004] In recent years, as people's attention to environmental issues has increased, relevant regulations have been continuously tightened to curb carbon dioxide emissions. In particular, as the problem of environmental pollution caused by the increasing use of plastics has become increasingly serious, regulations in the manufacturing stage, such as the mandatory use of recycled resins, are being strengthened, mainly in the United States. Therefore, manufacturers are required to add more than a predetermined amount of recycled resin when manufacturing resin molded products, etc., and an environmental protection grade is given according to the content of the recycled resin.

[0005] However, since the recycled resin has been processed, its properties have been changed by high-temperature processing. Therefore, compared with existing virgin resins, there are problems of significantly deteriorated impact strength, tensile strength, chemical resistance, and thermal stability. To solve this problem, attempts have been made to add more than a predetermined level of virgin resin to the composition containing the recycled resin. However, this requires an excessive amount of virgin resin to minimize the deterioration of mechanical properties, and the problem of deterioration of main properties such as environmental stress cracking resistance (ESCR) has not been solved. In addition, as the number of processing cycles increases, this problem becomes more serious. Summary of the Invention

[0006] Technical Problem

[0007] The present invention provides a polyethylene composition containing virgin polyethylene and post-consumer waste polyethylene (PCWPE), and having improved environmental stress cracking resistance and excellent mechanical properties.

[0008] Technical Solution

[0009] According to an embodiment of the present invention, there is provided a polyethylene composition comprising virgin polyethylene and post-consumer waste polyethylene (PCW PE), the polyethylene composition satisfying the following (a) to (d):

[0010] (a) The density is 0.949 g / cm 3 or more,

[0011] (b) The melt index (MI2.16 , for ASTM D 1238, at 190 °C and 2.16 kg, it is more than 0.25 g / 10 min,

[0012] (c) the complex viscosity (η*(ω500)) measured at a frequency (ω) of 500 rad / s is 600 Pa·s or less, and

[0013] (d) the environmental stress cracking resistance (ESCR) measured according to ASTM D 1693 (Condition B, F50, Igepal 10%) is 200 hours or more.

[0014] Advantageous Effects

[0015] According to the present invention, a polyethylene composition is provided, which comprises virgin polyethylene and post-consumer waste polyethylene (PCW PE), and at the same time, by optimizing the density, melt index and complex viscosity (η*(ω500)) and increasing the environmental stress cracking resistance (ESCR), it thus has improved environmental stress cracking resistance and excellent mechanical properties. Detailed Embodiments

[0016] In the present disclosure, the terms "first", "second", "third", etc. are used to describe various components, and these terms are only used to distinguish a specific component from other components.

[0017] In addition, the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention. Unless otherwise stated in the context, a singular expression may include a plural expression. In the present invention, it must be understood that the terms "comprising", "equipped with" or "having" in this specification are only used to indicate the presence of the effective features, quantities, steps, components or combinations thereof, and do not exclude the possibility of the prior existence or addition of one or more different features, quantities, steps, components or combinations thereof.

[0018] The term "about" or "substantially" is intended to have the meaning of a numerical value or range close with an allowable error, and is intended to prevent the accurate or absolute numerical value disclosed for understanding the present invention from being illegally or unfairly used by any unethical third party.

[0019] In the present invention, "parts by weight" is a relative concept of the ratio of the weights of other materials based on the weight of a specific material. For example, in a mixture containing 50 g of material A, 20 g of material B and 30 g of material C, based on 100 parts by weight of material A, the amounts of material B and material C are 40 parts by weight and 60 parts by weight, respectively.

[0020] In addition, "weight %" refers to an absolute concept of the percentage of the weight of a specific material based on the total weight. In the above mixture, based on the total weight of 100% of the mixture, the contents of Material A, Material B, and Material C are 50% by weight, 20% by weight, and 30% by weight, respectively. At this time, the sum of the contents of each component does not exceed 100% by weight.

[0021] Since the present invention can be variously modified and has various forms, specific embodiments of the present invention are illustrated by examples and described in detail. However, it is not intended to limit the present invention to the specific forms disclosed, and it should be understood that the present invention includes all modifications, equivalent forms, and alternative forms within the spirit and technical scope of the present invention.

[0022] Hereinafter, the present invention will be described in more detail.

[0023] According to an embodiment of the present invention, there is provided a polyethylene composition comprising virgin polyethylene and post-consumer waste polyethylene (PCW PE), which achieves high stacking strength and excellent mechanical properties when used as a blow-molded container, and also ensures excellent processability and high drop strength by optimizing the density and complex viscosity (η*(ω500)) and improving the environmental stress crack resistance (ESCR).

[0024] Specifically, the polyethylene composition of the present invention comprises virgin polyethylene and post-consumer waste polyethylene (PCW PE) and satisfies the following (a) to (d):

[0025] (a) The density is 0.949 g / cm 3 or more,

[0026] (b) The melt index (MI 2.16 , ASTM D 1238, 190 °C, 2.16 kg) is 0.25 g / 10 min or more,

[0027] (c) The complex viscosity (η*(ω500)) measured at a frequency (ω) of 500 rad / s is 600 Pa·s or less, and

[0028] (d) The environmental stress crack resistance (ESCR) measured according to ASTM D 1693 (Condition B, F50, Igepal 10%) is 200 hours or more.

[0029] Hereinafter, the polyethylene polymer of the present invention will be described in detail.

[0030] The polyethylene composition of the present invention is characterized in that it comprises virgin polyethylene and post-consumer waste polyethylene (PCWPE), and its density, melt index (MI 2.16) The complex viscosity (η*(ω500)) is optimized and the environmental stress cracking resistance (ESCR) is improved.

[0031] Specifically, the density of the polyethylene composition can be 0.949 g / cm 3 or more, for example 0.949 g / cm 3 or more up to 0.954 g / cm 3 or less. Even when the polyethylene composition of the present invention contains post-consumer waste polyethylene (PCW PE), excellent density can be ensured, so that sufficient stacking strength can be achieved when used as a blow molding container or the like.

[0032] By optimizing the melt index and the above density, the polyethylene composition of the present invention can ensure excellent processing performance and high drop strength at the same time.

[0033] The melt index (MI 2.16 , ASTM D 1238, 190 °C, 2.16 kg) of the polyethylene composition can be 0.25 g / 10 min or more, for example 0.25 g / 10 min to 0.8 g / 10 min. Preferably, the melt index (MI 2.16 , ASTM D 1238, 190 °C, 2.16 kg) of the polyethylene composition can be 0.7 g / 10 min or less, or 0.65 g / 10 min or less, or 0.6 g / 10 min or less, or 0.55 g / 10 min or less, or 0.5 g / 10 min or less, or 0.45 g / 10 min or less, or 0.42 g / 10 min or less, or 0.4 g / 10 min or less, or 0.38 g / 10 min or less, and 0.26 g / 10 min or more, or 0.27 g / 10 min or more, or 0.28 g / 10 min or more, or 0.29 g / 10 min or more. By having the above melt index (MI 2.16 ), the polyethylene composition of the present invention can ensure excellent mechanical properties, such as higher stacking strength, and excellent processing performance and higher drop strength at the same time.

[0034] In addition, the complex viscosity (η*(ω500)) of the polyethylene composition measured at a frequency (ω) of 500 rad / s may be 600 Pa·s or less, for example, 500 Pa·s or more and 600 Pa·s or less. Preferably, the complex viscosity (η*(ω500)) of the polyethylene composition measured at a frequency (ω) of 500 rad / s may be 585 Pa·s or less, 580 Pa·s or less, 575 Pa·s or less, 570 Pa·s or less, 568 Pa·s or less, 565 Pa·s or less, 562 Pa·s or less, or 560 Pa·s or less, and 505 Pa·s or more, 508 Pa·s or more, 510 Pa·s or more, 512 Pa·s or more, 515 Pa·s or more, 520 Pa·s or more, 525 Pa·s or more, 530 Pa·s or more, or 535 Pa·s or more. By having the above complex viscosity (η*(ω500)), the polyethylene composition of the present invention can ensure excellent mechanical properties, excellent processability, and high drop impact strength when used as a blow-molded container or the like.

[0035] In addition, the complex viscosity (η*(ω300)) of the polyethylene composition measured at a frequency of 300 rad / s may be 850 Pa·s or more, for example, 850 Pa·s or more and 980 Pa·s or less. Preferably, the complex viscosity (η*(ω300)) of the polyethylene composition measured at a frequency of 300 rad / s may be 852 Pa·s or more, 855 Pa·s or more, 858 Pa·s or more, 860 Pa·s or more, or 862 Pa·s or more, and 950 Pa·s or less, 920 Pa·s or less, or 900 Pa·s or less, 890 Pa·s or less, or 890 Pa·s or less.

[0036] In addition, the complex viscosity (η*(ω0.05)) of the polyethylene composition measured at a frequency of 0.05 rad / s may be 38000 Pa·s or more, for example, 38000 Pa·s or more and 53500 Pa·s or less. Preferably, the complex viscosity (η*(ω0.05)) of the polyethylene composition measured at a frequency of 0.05 rad / s may be 38200 Pa·s or more, 38350 Pa·s or more, 38500 Pa·s or more, 38900 Pa·s or more, 40000 Pa·s or more, 42000 Pa·s or more, or 45000 Pa·s or more, and 53000 Pa·s or less, 51500 Pa·s or less, 50000 Pa·s or less, 48000 Pa·s or less, or 45000 Pa·s or less.

[0037] By having the above-mentioned complex viscosities (η*(ω300) and η*(ω0.05)), the polyethylene composition of the present invention can simultaneously ensure excellent mechanical properties and excellent processability when used as a blow-molded container or the like.

[0038] The polyethylene composition of the present invention is characterized in that its density, melt index (MI 2.16 ) and complex viscosity (η*(ω500)) are optimized as described above, and the environmental stress cracking resistance (ESCR) is improved.

[0039] The environmental stress cracking resistance (ESCR) of the polyethylene composition measured according to ASTM D 1693 (Condition B, F50, Igepal 10%) is 200 hours or more, for example, 200 hours or more to 500 hours or less. Preferably, the ESCR of the polyethylene composition can be 203 hours or more, or 210 hours or more, or 215 hours or more, or 220 hours or more, or 250 hours or more, or 260 hours or more, or 270 hours or more, or 280 hours or more, and 400 hours or less, or 350 hours or less, or 320 hours or less, or 300 hours or less, or 288 hours or less. Due to the above-mentioned excellent ESCR performance, the polyethylene composition of the present invention can simultaneously ensure excellent mechanical properties, excellent processability and high drop impact strength when used as a blow-molded container or the like.

[0040] Specifically, the environmental stress cracking resistance (ESCR) refers to the time required for F50 (50% failure) measured for a 2-mm thick compression-molded sample at 50 °C under Condition B using a 10% Igepal CO-630 solution according to the ASTM D 1693-07 method.

[0041] By optimizing the density and complex viscosity (η*(ω500)) and improving the environmental stress cracking resistance (ESCR) as described above, even when the content of post-consumer waste polyethylene is increased, the polyethylene composition of the present invention can have excellent impact strength, tensile strength, chemical resistance and thermal stability close to those of virgin resin, so as to achieve high stacking strength and excellent mechanical properties when used as a blow-molded container or the like, while ensuring excellent processability and high drop strength.

[0042] At the same time, the polyethylene composition of the present invention contains virgin polyethylene and post-consumer waste polyethylene (PCW Pe), and contains polyethylene having an optimized low molecular weight region ratio while increasing the proportion of the high molecular weight region in the molecular structure and having the following density as the virgin resin to optimize the density and complex viscosity (η*(ω500)) and increase the above-mentioned environmental stress cracking resistance (ESCR).

[0043] Specifically, the virgin polyethylene can be a homopolymer of ethylene or a copolymer of ethylene / α-olefin, and can be one or more, or a dry blend of two or more of the above ethylene homopolymers and ethylene / α-olefin copolymers.

[0044] For example, when blending one or more or two or more of the above ethylene homopolymers and ethylene / α-olefin copolymers, the weight ratio of one or more ethylene homopolymers to one or more ethylene / α-olefin copolymers can be 1:99 to 99:1, or 5:95 to 95:5, or 10:90 to 90:10, or 15:85 to 85:15, or 20:80 to 80:20, or 25:75 to 75:25, or 30:70 to 70:30, or 35:65 to 65:35, or 40:60 to 60:40, or 45:55 to 55:45.

[0045] The α-olefin can be one or more selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and mixtures thereof.

[0046] For example, when the virgin polyethylene is a copolymer, based on 1 mol of ethylene, the content of α-olefin can be about 0.45 mol or less, or about 0.1 mol to about 0.45 mol, or about 0.4 mol or less, or about 0.2 mol to about 0.4 mol, or about 0.35 mol or less, or about 0.25 mol to about 0.35 mol.

[0047] Specifically, when the virgin polyethylene is a copolymer, 1-hexene can be used as the α-olefin copolymerized with ethylene.

[0048] Preferably, the virgin polyethylene can be an ethylene homopolymer without a separate copolymer, an ethylene / 1-hexene copolymer, or a dry blend of the above ethylene homopolymer and ethylene / 1-hexene copolymer.

[0049] Meanwhile, the virgin polyethylene can be high-density polyethylene (HDPE) with a density (ASTM D1505, 23 °C) satisfying 0.944 g / cm 3 or more or 0.944 g / cm 3 to 0.954 g / cm 3 .

[0050] More specifically, the density of the virgin polyethylene can be 0.945 g / cm 3 or more, or 0.946 g / cm 3 or more, and 0.954 g / cm 3 or less, or 0.953 g / cm 3As follows.

[0051] When the density of the virgin polyethylene satisfies the above range, the compatibility with post-consumer waste polyethylene can be improved, and when mixed with post-consumer waste polyethylene, the deterioration of main properties such as ESCR can be minimized without using an excessive amount of virgin polyethylene resin.

[0052] Meanwhile, in the GPC curve graph with logMw as the x-axis and dw / dlogMw as the y-axis, the integral value of the region where LogMw is 5.5 or more is 14% or less of the total integral value, or 5% or more to 14% or less.

[0053] Specifically, the integral value of the region where LogMw is 5.5 or more can be less than 14%, or 13.5% or less, or 13% or less to ensure excellent processing performance and high falling impact strength when mixing virgin polyethylene with post-consumer waste polyethylene. However, considering the high density and excellent mechanical properties after mixing with post-consumer waste polyethylene, the integral value of the region where LogMw is 5.5 or more can be 6% or more, or 8% or more, or 10% or more, or 11.0% or more.

[0054] By having the above integral value of the region where LogMw is 5.5 or more, the proportion of the high molecular weight region in the molecular structure of the virgin polyethylene can be increased, while improving mechanical properties such as environmental stress cracking resistance (ESCR), etc., and having excellent compatibility with post-consumer waste polyethylene.

[0055] In addition, the low molecular weight ratio (LogMw ≤ 4.5 / LogMw ≥ 6.0) of the virgin polyethylene is 15.5 or more or 15.5 to 50, which is calculated according to the following formula 1 based on the integral value of the region where LogMw is 4.5 or less (LogMw ≤ 4.5) relative to the total integral value and the integral value of the region where LogMw is 6.0 or more (LogMw ≥ 6.0) in the GPC curve graph with logMW as the x-axis and dw / dlogMw as the y-axis:

[0056] [Formula 1]

[0057] Low molecular weight ratio = Integral value of LogMw ≤ 4.5 region / Integral value of LogMw ≥ 6.0 region.

[0058] Among them, the low molecular weight content (logMw ≤ 4.5) and high molecular weight content (logMw ≥ 6.0) derived from the GPC curve represent the percentage values of the areas corresponding to each range relative to the total integral value of the GPC curve. The low molecular weight ratio (LogMw ≤ 4.5 / LogMw ≥ 6.0) of Formula 1 thus obtained represents the ratio of the low molecular weight content relative to the high molecular content as described above, without a separate unit.

[0059] When the low molecular weight ratio (LogMw ≤ 4.5 / LogMw ≥ 6.0) in the polyethylene molecular structure satisfies the above range, the compatibility and processing performance with post-consumer waste polyethylene can be improved.

[0060] Specifically, from the perspective of ensuring excellent processing performance and compatibility when polyethylene is mixed with post-consumer waste polyethylene, the low molecular weight ratio (LogMw ≤ 4.5 / LogMw ≥ 6.0) of virgin polyethylene can be 16 or more, or 18 or more, or 20 or more, or 21.5 or more, or 22 or more, or 23.5 or more, or 24 or more, or 24.5 or more. However, from the perspective of improving the mechanical properties of post-consumer waste polyethylene, the low molecular weight ratio (LogMw ≤ 4.5 / LogMw ≥ 6.0) of virgin polyethylene can be 48 or less, or 46 or less, or 45 or less, or 43 or less, or 42 or less, or 40 or less, or 38 or less, or 37.5 or less.

[0061] In addition, for polyethylene to satisfy the above low molecular weight ratio range (LogMw ≤ 4.5 / LogMw ≥ 6.0), among them, in the GPC curve graph with logMw as the x-axis and dw / dlogMw as the y-axis, the integral value (LogMw ≥ 6.0) of the area where the LogMw value is 6.0 or more relative to the total integral value can be 0.9% or more to 2.2% or less, or 1.0% or more to 2.0% or less, and the integral value (LogMw ≤ 4.5) of the area where the LogMw value is 4.5 or less relative to the total integral value can be 42% or more and 52% or less, or 44% or more to 50% or less.

[0062] In the polyethylene composition of the present invention, the virgin polyethylene has the low molecular weight ratio (LogMw ≤ 4.5 / LogMw ≥ 6.0) as described above, thereby optimizing the ratio of the low molecular weight region in the virgin polyethylene molecular structure to maintain excellent compatibility with post-consumer waste polyethylene and improve mechanical properties such as environmental stress cracking resistance (ESCR).

[0063] At the same time, as described above, by increasing the ratio of the high molecular weight region in the molecular structure while maintaining the ratio of the low molecular weight region, the virgin polyethylene can have an optimized molecular weight distribution (MWD, Mw / Mn).

[0064] Specifically, the molecular weight distribution (Mw / Mn) of virgin polyethylene can be 7 or more, or from 7 to 18. Preferably, the molecular weight distribution (Mw / Mn) of polyethylene can be 9 or more, or 10 or more, or 10.5 or more, or 11 or more, or 12 or more, and can also be 17.5 or less, or 17 or less, or 16 or less.

[0065] By having the above molecular weight distribution (Mw / Mn), while maintaining the proportion of the low molecular weight region, the proportion of the high molecular weight region in the molecular structure of virgin polyethylene can be increased, thereby maintaining excellent compatibility with post-consumer waste polyethylene while improving mechanical properties such as environmental stress crack resistance (ESCR).

[0066] For example, gel permeation chromatography (GPC) is used to determine the proportion of the region where the LogMw value is 5.0 or more or 4.0 or less in the GPC curve graph and the molecular weight distribution (MWD, polydispersity index). Specifically, they can be measured using the polystyrene calibration method of gel permeation chromatography (GPC, manufactured by Waters).

[0067] Here, the molecular weight distribution (MWD, polydispersity index) can be calculated by determining the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polyethylene and then dividing the weight-average molecular weight by the number-average molecular weight.

[0068] Specifically, PL-GPC220 manufactured by Waters can be used as the gel permeation chromatography (GPC) instrument, and a column with a length of 300 mm of Polymer Laboratories PLgel MIX-B can be used. At this time, the measurement temperature is 160 °C, 1,2,4-trichlorobenzene can be used as the solvent, and the flow rate is 1 mL / min. Using a GPC analyzer (PL-GP220), the polyethylene sample is pre-treated by dissolving it in 1,2,4-trichlorobenzene containing 0.0125% butylhydroxytoluene (BHT) at 160 °C for 10 hours, prepared at a concentration of 10 mg / 10 mL, and then 200 μL is fed. The Mw and Mn values can be obtained from the calibration curve formed using polystyrene standard samples. Nine polystyrene standard samples with weight-average molecular weights of 2000 g / mol, 10000 g / mol, 30000 g / mol, 70000 g / mol, 200000 g / mol, 700000 g / mol, 2000000 g / mol, 4000000 g / mol, and 10000000 g / mol can be used.

[0069] In addition, the weight-average molecular weight of virgin polyethylene can be from 100,000 g / mol to 500,000 g / mol. Preferably, the weight-average molecular weight of polyethylene can be 105,000 g / mol or more, 110,000 g / mol or more, or 115,000 g / mol or more, and 120,000 g / mol or less, 122,000 g / mol or less, or 125,000 g / mol or less. However, considering the compatibility with post-consumer waste polyethylene, the weight-average molecular weight can be 480,000 g / mol or less, or 450,000 g / mol or less, or 400,000 g / mol or less, or 350,000 g / mol or less, or 300,000 g / mol or less, or 250,000 g / mol or less, or 200,000 g / mol or less, or 180,000 g / mol or less, or 150,000 g / mol or less, or 140,000 g / mol or less.

[0070] By having the above weight-average molecular weight (Mw), the molecular weight distribution of virgin polyethylene can be optimized, and mechanical properties such as environmental stress crack resistance (ESCR) can be improved, and it has excellent compatibility with post-consumer waste polyethylene.

[0071] Meanwhile, as described above, in virgin polyethylene, the melt index can be optimized while optimizing the proportion of the high molecular weight region and the molecular weight distribution in the molecular structure.

[0072] The melt index (MI 2.16 , ASTM D 1238, 190 °C, 2.16 kg) of virgin polyethylene can be from 0.1 g / 10 min to 1.0 g / 10 min. Preferably, the melt index (MI 2.16 , ASTM D 1238, 190 °C, 2.16 kg) of polyethylene can be 0.12 g / 10 min or more, or 0.15 g / 10 min or more, or 0.2 g / 10 min or more, or 0.25 g / 10 min or more, or 0.3 g / 10 min or more, or 0.32 g / 10 min or more, or 0.35 g / 10 min or more, 0.4 g / 10 min or more, or 0.41 g / 10 min or more, and 0.98 g / 10 min or less, or 0.95 g / 10 min or less, or 0.9 g / 10 min or less, or 0.85 g / 10 min or less, or 0.8 g / 10 min or less, or 0.75 g / 10 min or less, or 0.72 g / 10 min or less, 0.7 g / 10 min or less, or 0.68 g / 10 min or less. By the above melt index (MI 2.16) can optimize the molecular weight distribution of polyethylene, improve mechanical properties such as environmental stress cracking resistance (ESCR), and have excellent compatibility with post-consumer waste polyethylene.

[0073] By having the above melt index, the molecular weight of virgin polyethylene can be optimized, mechanical properties such as environmental stress cracking resistance (ESCR) can be improved, and it has excellent compatibility with post-consumer waste polyethylene.

[0074] Meanwhile, measured using gel permeation chromatography (GPC)-Fourier transform infrared spectrometer (FTIR) at a temperature of 160 °C, the short-chain branches (SCB) per 1000 carbon atoms of virgin polyethylene is 3.0 or more. Here, the short-chain branch (SCB) content represents the branch content of 2 to 7 carbon atoms per 1000 carbon atoms (unit: branch / 1000C).

[0075] For example, the short-chain branch (SCB) content of virgin polyethylene can be measured by pretreating the sample with PL-SP260 in 1,2,4-trichlorobenzene containing 0.0125% BHT at 160 °C for 10 hours, and then using a PerkinElmer Spectrum 100 FT-IR connected to a high-temperature GPC (PL-GPC220) at 160 °C.

[0076] In addition, virgin polyethylene can have a broad ortho-comonomer distribution (BOCD) index of 1.60 or more, or 1.60 or more to 2.5 or less.

[0077] Specifically, the broad ortho-comonomer distribution (BOCD) index of virgin polyethylene can be 1.60 or more, which is calculated according to the following formula 2 by measuring the short-chain branch (SCB) content at the left and right boundaries of the middle 60% region except for the 20% regions at both the left and right ends in the total area of the GPC curve graph of polyethylene with logMw as the x-axis and dw / dlogMw as the y-axis:

[0078] [Formula 2]

[0079] BOCD = (SCB content on the high molecular weight side - SCB content on the low molecular weight side) / (LogMw value on the high molecular weight side - LogMw on the low molecular weight side).

[0080] In this regard, the SCB content on the high molecular weight side and the SCB content on the low molecular weight side refer to the SCB content values corresponding to 20% of the logMw for the high molecular weight side and the low molecular weight side regions, respectively. The high molecular weight side logMw and low molecular weight side logMw values are the logMw values corresponding to 20% of the total area of the curve with respect to the y-axis (dw / dlogMw) and the x-axis (logMw) obtained by GPC analysis for the high molecular weight and low molecular weight regions.

[0081] In the present invention, the virgin polyethylene is a semi-crystalline polymer and may include a crystalline part and an amorphous part. Specifically, the crystalline part may include lamellar crystals containing ethylene repeating units or α-olefin repeating units. More specifically, polymer chains containing ethylene repeating units or α-olefin repeating units are folded to form bundles, thereby forming crystalline blocks (or segments) in the form of lamellae. The lamellar crystals refer to the crystalline blocks in the form of lamellae, and the mechanical properties of the virgin polyethylene can be achieved through such lamellar crystals.

[0082] The ethylene repeating unit refers to the repeating unit contained in the homopolymer of ethylene monomer, and the α-olefin repeating unit may refer to the repeating unit contained in the homopolymer of α-olefin monomer. Specific examples of the α-olefin monomer are as described above.

[0083] Meanwhile, many lamellar crystals can also aggregate together to form spherulites that grow three-dimensionally, and at this time, the part other than the lamellar crystals corresponds to the amorphous part. This amorphous part mediates the binding between the lamellar crystals in the virgin polyethylene that forms spherulites. The elastic properties of the virgin polyethylene can be achieved through this amorphous part. In particular, as the binding between the lamellar crystals becomes stronger, the entire crystal is firmly bound together. Therefore, the physical properties of the virgin polyethylene, such as environmental stress crack resistance, can be improved.

[0084] In particular, the virgin polyethylene of the present invention has excellent environmental stress crack resistance due to its large lamellar crystal region area.

[0085] Here, the lamellar crystal region area represents the surface area of the lamellar crystal structure in the crystal structure of the virgin polyethylene, and as the surface area of the lamellar crystals increases, the part connecting the crystal structure also increases, so the crack resistance is more excellent.

[0086] The lamellar crystal region area of the virgin polyethylene obtained by the following formula 3 can be 710×10 10 cm 2 / mol or more, or 710×10 10 cm 2 / mol or more to 1150×10 10 cm 2 / mol or less:

[0087] [Formula 3]

[0088] Lamellar region area (cm 2 / mol) = (V 比容 / Lw) × Mw × Tc

[0089] In Formula 3,

[0090] V 比容 represents the specific volume of polyethylene crystals (cm 3 / g),

[0091] Mw represents the weight-average molecular weight of polyethylene (g / mol), which is measured using gel permeation chromatography (GPC),

[0092] Tc represents the crystallinity of polyethylene (%), which is measured using differential scanning calorimetry (DSC), and

[0093] Lw represents the thickness of the lamellar crystal structure of polyethylene (cm), which is measured using differential scanning calorimetry (DSC).

[0094] Specifically, the literature value of the specific volume (V 比容 ) of polyethylene crystals is 1 cm 3 / g. Additionally, the weight-average molecular weight (Mw) of polyethylene can be the value measured by polystyrene conversion using gel permeation chromatography (GPC, manufactured by Waters Corporation) as described above. Furthermore, the crystallinity (Tc) of polyethylene can be the value (%) measured by DSC analysis based on the melting enthalpy under the conditions of a heating / cooling rate of 10 °C / min within the range from -50 °C to 200 °C. Additionally, the thickness (Lw) of the lamellar crystal structure of polyethylene is a value (cm) measured based on the SSA experiment using a DSC device. For example, in the SSA experiment, the polymer is completely melted and cooled to the melting point (Tm), offset by +5 °C, then annealed while cooling to Tm start - 5 °C, and then a second heating is performed to calculate the thickness (Lw, weight average) of the lamellar crystal structure.

[0095] Preferably, the lamellar region area of virgin polyethylene can be 712 × 10 10 cm 2 / mol or more, or 715 × 10 10 cm 2 or more, or 720 × 10 10 cm 2 / mol or more.

[0096] Meanwhile, in the polyethylene composition of an embodiment of the present invention, the above-mentioned virgin polyethylene can be prepared using various catalysts. Preferably, it can be prepared using a catalyst composition containing a metallocene compound, but it is not limited thereto.

[0097] For example, virgin polyethylene can be prepared by introducing hydrogen in the presence of a catalyst composition containing a first metallocene compound represented by the following Chemical Formula 1 and a second metallocene compound represented by the following Chemical Formula 2:

[0098] [Chemical Formula 1]

[0099] (Cp 1 R a ) n (Cp 2 R b )M 1 Z 1 3-n

[0100] In Chemical Formula 1,

[0101] M 1 is a Group 4 transition metal;

[0102] Cp 1 and Cp 2 are each a cyclopentadienyl group substituted or unsubstituted with a C 1-20 hydrocarbon;

[0103] R a and R b are the same or different from each other and are each independently hydrogen, a C 1-20 alkyl group, a C 1-20 alkoxy group, a C 2-20 alkoxyalkyl group, a C 6-20 aryl group, a C 6-20 aryloxy group, a C 2-20 alkenyl group, a C 7-40 alkylaryl group, a C 7-40 arylalkyl group, a C 8-40 arylalkenyl group, a C 2-20 alkynyl group, or a C 2-20 heteroaryl group containing one or more heteroatoms selected from N, O, and S,

[0104] Z 1 is a halogen, a C 1-20 alkyl group, a C 2-20 alkenyl group, a C 7-40 alkylaryl group, a C 7-40 arylalkyl group, a C 6-20 aryl group, a substituted or unsubstituted C 1-20 alkylene group, a substituted or unsubstituted amino group, a C 2-20Alkyl alkoxy or C 7-40 Aryl alkoxy; and

[0105] n is 1 or 0;

[0106] [Chemical formula 2]

[0107]

[0108] In Chemical formula 2,

[0109] C 1 Is any one of the ligands represented by the following Chemical formulas 3 to 6,

[0110] [Chemical formula 3]

[0111]

[0112] [Chemical formula 4]

[0113]

[0114] [Chemical formula 5]

[0115]

[0116] [Chemical formula 6]

[0117]

[0118] In Chemical formulas 3 to 6,

[0119] R 1 To R 6 Are the same as or different from each other, and are each independently hydrogen, C 1-30 Alkyl, C 1-30 Alkoxy, C 2-30 Alkoxyalkyl, C 6-30 Aryl, C 6-30 Aryloxy, C 2-30 Alkenyl, C 2-30 Alkynyl, C 3-30 Cycloalkyl, C 7-40 Alkylaryl, C 8-40 Alkenylaryl, C 8-40 Alkynylaryl, C 7-40 Arylalkyl, C 8-40 Arylalkenyl, or C 8-40 Arylalkynyl,

[0120] M is Ti, Zr or Hf,

[0121] Z is -O-, -S-, -NR 7 -, or -PR 7 -;

[0122] R 7 is hydrogen, C 1-30 alkyl, C 6-30 aryl, C 2-30 alkenyl, C 2-30 alkynyl, C 3-30 cycloalkyl, C 7-40 alkylaryl, C 8-40 alkenylaryl, C 8-40 alkynylaryl, C 7-40 arylalkyl, C 8-40 arylalkenyl, C 8-40 arylalkynyl, C 1-30 alkoxysilyl, C 6-30 aryloxysilyl, C 1-30 alkylsilyl, or C 1-30 silylalkyl,

[0123] X 1 and X 2 are the same as or different from each other and are each independently halogen, C 1-30 alkyl, C 2-30 alkenyl, C 7-30 alkylaryl, C 7-30 arylalkyl, C 6-20 aryl, substituted or unsubstituted C 1-30 alkylene, substituted or unsubstituted amino, C 2-30 alkylalkoxy or C 7-30 arylalkoxy,

[0124] T is

[0125] T 1 C, Si, Ge, Sn or Pb,

[0126] Y 1 is hydrogen, C 1-30 alkyl, C 1-30 alkoxy, C 2-30 alkoxyalkyl, C 6-30 aryl, C 6-30 aryloxy, C 2-30 alkenyl, C 2-30 alkynyl, C 3-30 cycloalkyl, C 7-40 alkylaryl, C 8-40 alkenylaryl, C 8-40 alkynylaryl, C 7-40 arylalkyl, C 8-40 arylalkenyl, or C 8-40 arylalkynyl, silyl(-SiH 3 ), C 1-30 alkoxysilyl, C2-30 alkoxyalkylsilyl, C 6-30 aryloxysilyl, C 1-30 haloalkyl, C 6-30 haloaryl, or -NR 9 R 10 ,

[0127] Y 2 is C 2-30 alkoxyalkyl, or C 7-40 aryloxyalkyl, and

[0128] R 9 and R 10 are each independently hydrogen, C 1-30 alkyl, C 6-30 aryl, C 2-30 alkenyl, C 2-30 alkynyl, C 3-30 cycloalkyl, C 7-40 alkylaryl, C 8-40 alkenylaryl, C 8-40 alkynylaryl, C 7-40 arylalkyl, C 8-40 arylalkenyl, or C 8-40 arylalkynyl, or are linked together to form an alicyclic or aromatic ring.

[0129] In this document, unless otherwise specified, the following terms can be defined as follows.

[0130] Halogen can be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0131] C 1-30 alkyl can be a straight-chain alkyl, a branched-chain alkyl, or a cycloalkyl. Specifically, C 1-20 alkyl can be C 1-15 a straight-chain alkyl; C 1-10 a straight-chain alkyl; C 1-5 a straight-chain alkyl; C 3-20 a branched-chain alkyl or a cycloalkyl; C 3-15 a branched-chain alkyl or a cycloalkyl; or C 3-10 a branched-chain alkyl or a cycloalkyl. More specifically, C 1-20 alkyl can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, or cyclohexyl, etc.

[0132] C 2-30 alkenyl can be a straight-chain alkenyl, a branched-chain alkenyl, or a cycloalkenyl. Specifically, C 2-30 alkenyl can be C 2-20 a straight-chain alkenyl, C 2-10 a straight-chain alkenyl, C 2-5 a straight-chain alkenyl, C3-20 branched alkenyl, C 3-15 branched alkenyl, C 3-10 branched alkenyl, C 5-20 cycloalkenyl or C 5-10 cycloalkenyl. More specifically, C 2-20 the alkenyl may be vinyl, propenyl, butenyl, pentenyl, cyclohexenyl, etc.

[0133] C 6-30 The aryl may be a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. Specifically, C 6-30 the aryl may be phenyl, naphthyl, anthracenyl, etc.

[0134] C 7-40 The alkylaryl may include substituents in which one or more hydrogens of the aryl are substituted by alkyl. Specifically, C 7-40 the alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, tert-butylphenyl, cyclohexylphenyl, etc.

[0135] C 7-40 The arylalkyl may include substituents in which one or more hydrogens of the alkyl are substituted by aryl. Specifically, C 7-40 the arylalkyl may be benzyl, phenylpropyl or phenylhexyl, etc.

[0136] C 1-20 The alkoxy may include methoxy, ethoxy, phenoxy, cyclohexyloxy, etc., but is not limited thereto.

[0137] C 2-20 The alkoxyalkyl may be a functional group in which one or more hydrogens of the alkyl as described above are substituted by alkoxy. Specifically, it may include alkoxyalkyl such as methoxymethyl, methoxyethyl, ethoxymethyl, isopropoxymethyl, isopropoxyethyl, isopropoxyhexyl, tert-butoxymethyl, tert-butoxyethyl or tert-butoxyhexyl, etc.; or aryloxyalkyl such as phenoxyhexyl, etc., but is not limited thereto.

[0138] C 1-20 alkylsilyl or C 1-20 alkoxysilyl may be a functional group in which one to three hydrogens of -SiH 3 are substituted by one to three of the above alkyl or alkoxy groups. Specifically, it may include alkylsilyl such as methylsilyl, dimethylsilyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl or dimethylpropylsilyl, etc.; alkoxysilyl such as methoxysilyl, dimethoxysilyl, trimethoxysilyl or dimethoxyethoxysilyl, etc.; alkoxyalkylsilyl such as methoxydimethylsilyl, diethoxymethylsilyl or dimethoxypropylsilyl, etc., but is not limited thereto.

[0139] C 1-20 A silylalkyl is a functional group in which one or more hydrogens of the alkyl as described above are substituted with silyl. Specifically, it may include -CH 2 -SiH 3 , methylsilylmethyl, dimethylethoxysilylpropyl, etc., but is not limited thereto.

[0140] The sulfonate group has a structure of -O-SO 2 -R', where R' can be C 1-20 alkyl. Specifically, the C 1-20 sulfonate group may include a methanesulfonate group, a phenylsulfonate group, etc., but is not limited thereto.

[0141] A heteroaryl is a C 2-20 heteroaryl including one or more of N, O, and S as heteroatoms. Specific examples thereof may include xanthenyl, thioxanthenyl, thiophenyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuryl, phenanthrolinyl, isoxazolyl, thiadiazolyl, phenothiazinyl, or dibenzofuryl, etc., but is not limited thereto.

[0142] The above substituents may optionally be substituted with one or more substituents selected from the group consisting of the following groups within the range where the same or similar effects as the desired effect are exhibited: hydroxyl; halogen; alkyl, alkenyl, aryl, or alkoxy; alkyl, alkenyl, aryl, or alkoxy including one or more heteroatoms of Groups 14 to 16; silyl; alkylsilyl or alkoxysilyl; phosphino; phosphide; sulfonate; and sulfone.

[0143] In the present disclosure, "two adjacent substituents are connected to each other to form an alicyclic or aromatic ring" means that the atoms of the two substituents and the atoms connected to the two substituents are connected to each other to form a ring. Specifically, for -NR 9 R 10 wherein R 9 and R 10 are connected to each other to form an alicyclic ring, piperidinyl, etc. can be taken as an example. For -NR 9 R 10 wherein R 9 and R 10 are connected to each other to form an aromatic ring, pyrrolyl, etc. can be taken as an example.

[0144] Group 4 transition metals may be titanium (Ti), zirconium (Zr), hafnium (Hf), etc., but are not limited thereto.

[0145] For example, the first metallocene compound represented by Chemical Formula 1 is a non-crosslinked compound containing Cp 1 and Cp 2 ligands. Cp 1 and Cp 2 ligands may be the same or different and are each cyclopentadienyl, and may be substituted with more than 1, or 1 to 3 C 1-10 alkyl groups.

[0146] In addition, Cp 1 and Cp 2 ligands can easily control the properties of the olefin polymer to be prepared, such as chemical structure, molecular weight, molecular weight distribution, mechanical properties, transparency, etc., for example, by controlling the steric hindrance effect according to the type of substituted functional group. Specifically, Cp 1 and Cp 2 ligands may be substituted with R a and R b respectively. In this regard, R a and R b are the same or different from each other, and each independently is hydrogen, C 1-20 alkyl, C 2-20 alkoxyalkyl, C 7-40 arylalkyl, or C 2-12 heteroaryl containing one or more heteroatoms selected from N, O, and S. More specifically, C 1-10 alkyl, C 2-10 alkoxyalkyl, C 7-20 arylalkyl, or C 4-12 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O, and S.

[0147] M 1 Z 1 3-n is present between the Cp 1 and Cp 2 ligands, and M 1 Z 1 3-n can affect the storage stability of the metal complex. To more effectively ensure the effect, Z 1 can each independently be a halogen or C 1-20 alkyl, more specifically, each independently is F, Cl, Br, or I. In addition, M 1 can be Ti, Zr, or Hf; Zr or Hf; or Zr.

[0148] The first metallocene compound may be a compound having Chemical Formula 1, wherein Cp1 and Cp 2 are each an unsubstituted or substituted cyclopentadienyl group, R a and R b are each independently hydrogen, C 1-10 alkyl, C 2-10 alkoxyalkyl, or C 7-20 arylalkyl, and at least one of R a and R b is an alkoxyalkyl substituent, such as tert-butoxyhexyl, and more specifically, -(CH 2 )n-OR (wherein R is a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and n is an integer from 2 to 4).

[0149] The first metallocene compound represented by Chemical Formula 1 may be, for example, any one of the compounds represented by the following structural formulas, but is not limited thereto:

[0150]

[0151] In addition, the second metallocene compound may include: an aromatic cyclic compound containing thiophene and a base compound containing a Group 14 or 15 element as different ligands, and may have different ligands crosslinked by -T-, and a structure in which (X 1 )(X 2 ) is present between different ligands.

[0152] Specifically, in Chemical Formula 2, M may be Ti, Zr, or Hf, and more specifically Ti.

[0153] R 1 to R 4 may each independently be hydrogen or C 1-20 alkyl, and more specifically, hydrogen or methyl.

[0154] R 5 and R 6 may each independently be C 1-10 alkyl, and more specifically, R 5 and R 6 may both be methyl.

[0155] Z may be -NR 7 -, wherein R 7 may be C 1-10 alkyl, and more specifically, C 3-10 branched alkyl, such as tert-butyl.

[0156] In addition, T is T 1 is C or Si, Y 1 is C 1-20 alkyl, C 1-20 alkoxy, C2-20 alkoxyalkyl, C 6-20 aryl, C 7-30 alkylaryl, C 7-30 arylalkyl, C 6-20 aryloxy, or C 7-30 aryloxyalkyl, Y 2 is C 2-20 alkoxyalkyl, or C 7-30 aryloxyalkyl, more specifically, Y 1 can be any one of methyl, ethyl, n-propyl and n-butyl, Y 2 is C 2-20 alkoxyalkyl, or C 7-30 aryloxyalkyl, more specifically, Y 2 can be any one of methoxymethyl, methoxyethyl, ethoxymethyl, isopropoxymethyl, isopropoxyethyl, isopropoxyhexyl, tert-butoxymethyl, tert-butoxyethyl, tert-butoxyhexyl and phenoxyhexyl.

[0157] X 1 and X 2 can each independently be halogen or C 1-20 alkyl, more specifically, chlorine.

[0158] For example, the second metallocene compound can be exemplified by compounds represented by the following Chemical Formulas 2a to 2d:

[0159] [Chemical Formula 2a]

[0160]

[0161] [Chemical Formula 2b]

[0162]

[0163] [Chemical Formula 2c]

[0164]

[0165] [Chemical Formula 2d]

[0166]

[0167] In Chemical Formulas 2a to 2d, R 1 to R 7 , M, X 1 , X 2 , T 1 , Y 1 and Y 2 are the same as those defined above.

[0168] Specifically, in the chemical formulas 2a to 2d of the second metallocene compound, M is Ti, Zr or Hf, more specifically Ti; R 1 to R 4 are each independently hydrogen, or a C 1-20 alkyl group, more specifically hydrogen or methyl; R 5 and R 6 are each independently a C 1-10 alkyl group, more specifically, R 5 and R 6 are both methyl; R 7 is a C 1-10 alkyl group, more specifically a C 3-10 branched alkyl group, such as tert-butyl; T 1 is C or Si, Y 1 is a C 1-20 alkyl group, a C 1-20 alkoxy group, a C 2-20 alkoxyalkyl group, a C 6-20 aryl group, a C 7-30 alkylaryl group, a C 7-30 arylalkyl group, a C 6-20 aryloxy group, or a C 7-30 aryloxyalkyl group, Y 2 is a C 2-20 alkoxyalkyl group, or a C 7-30 aryloxyalkyl group, more specifically Y 1 is any one of methyl, ethyl, n-propyl, and n-butyl, Y 2 is a C 2-20 alkoxyalkyl group, or a C 7-30 aryloxyalkyl group, more specifically, Y 2 is any one of methoxymethyl, methoxyethyl, ethoxymethyl, isopropoxymethyl, isopropoxyethyl, isopropoxyhexyl, tert-butoxymethyl, tert-butoxyethyl, tert-butoxyhexyl, and phenoxyhexyl, X 1 and X 2 are each independently a halogen or a C 1-20 alkyl group, more specifically chlorine.

[0169] In particular, specific examples of the second metallocene compound may be exemplified by compounds having the following structures, but are not limited thereto:

[0170]

[0171] Meanwhile, the content ratio of the first metallocene compound and the second metallocene compound in the catalyst composition may be a molar ratio of 1:1.1 to 1:5, more specifically, above 1:1.1, or above 1:1.2, or above 1:1.3, and below 1:5, or below 1:3.

[0172] In addition, the catalyst composition may further comprise a support, in which case, the first metallocene compound and the second metallocene compound may be used in a state supported on the support.

[0173] Specific examples of the support include silica, alumina, magnesia, silica-alumina, or silica-magnesia, etc. Generally, these supports may further contain oxides, carbonates, sulfates, and nitrates, such as Na 2 O, K 2 CO 3 , BaSO 4 and Mg(NO 3 ) 2 etc.

[0174] In addition, in terms of improving high activity and process stability, the catalyst composition may further comprise a cocatalyst. The cocatalyst may specifically be an alkylaluminoxane cocatalyst, such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc.

[0175] In the polyethylene composition according to an embodiment of the present invention, the above-mentioned virgin polyethylene is prepared by polymerizing ethylene using the above-mentioned catalyst composition, and the polymerization process may be carried out by a single-peak (or single-modal) polymerization process, in which the polymerization is carried out using a single catalyst in a single reactor under a single polymerization reaction condition. More specifically, it is carried out in a single-loop slurry reactor in the presence of the above-mentioned mixed supported catalyst.

[0176] In this regard, the polymerization temperature may be from 25°C to 500°C, preferably from 25°C to 200°C, more preferably from 50°C to 150°C. Additionally, the polymerization pressure may be from 1 Kgf / cm 2 to 100 Kgf / cm 2 , preferably from 1 Kgf / cm 2 to 50 Kgf / cm 2 , more preferably from 5 Kgf / cm 2 to 30 Kgf / cm 2 .

[0177] Meanwhile, the polyethylene composition of the present invention includes post-consumer waste polyethylene (PCW PE) and the above-mentioned virgin polyethylene.

[0178] Specifically, the polyethylene composition of the present invention may contain 10% to 90% by weight of post-consumer waste polyethylene (PCW PE). Specifically, from the perspective of enhancing the inhibitory effect on carbon dioxide emissions of the polyethylene composition and reducing costs, the content of post-consumer waste polyethylene (PCW PE) may be 20% by weight or more, or 30% by weight or more, or 35% by weight or more, or 40% by weight or more, or 45% by weight or more, or 50% by weight or more, or 55% by weight or more. In addition, from the perspective of improving the mechanical properties of the polyethylene composition, such as impact strength, tensile strength, chemical resistance, and thermal stability, etc., while minimizing the content of virgin resin, the content of post-consumer waste polyethylene (PCW PE) may be 85% by weight or less, or 80% by weight or less, or 75% by weight or less, or 70% by weight or less, or 65% by weight or less, or 60% by weight or less.

[0179] The melt index (MI 2.16 , measured at 190 °C under a load of 2.16 kg) of post-consumer waste polyethylene (PCW PE) is 0.10 g / 10 min to 0.3 g / 10 min. Specifically, it is 0.12 g / 10 min to 0.28 g / 10 min, or 0.13 g / 10 min to 0.25 g / 10 min, or 0.15 g / 10 min to 0.2 g / 10 min.

[0180] The characteristics of post-consumer waste polyethylene (PCW PE) may be that the density is 0.951 g / cm 3 to 0.953 g / cm 3 .

[0181] The environmental stress cracking resistance (ESCR) of post-consumer waste polyethylene (PCW PE) measured according to ASTM D 1693 (Condition B, F50, Igepal 10%) may be 40 hours to 50 hours.

[0182] In the polyethylene composition of the present invention, post-consumer waste polyethylene is used together with the above-mentioned virgin polyethylene, and the density and complex viscosity (η*(ω500)) are optimized and the environmental stress cracking resistance (ESCR) is improved, thereby manufacturing a molded product having excellent processing performance and high mechanical properties.

[0183] In particular, even when the content of post-consumer waste polyethylene increases, the polyethylene composition of the present invention can still ensure excellent impact strength, tensile strength, chemical resistance, and thermal stability close to those of virgin resin.

[0184] Specifically, a polyethylene composition is made into a disk specimen with a diameter of 50 mm and a thickness of 2 mm by an injection molding machine, and a weight is dropped onto the disk specimen with a falling energy of 4.2 J. When measuring the number of drops until cracks appear, the falling impact strength can be more than 7 times.

[0185] The flexural modulus of the polyethylene composition measured according to ASTM D 790 method can be 13000 kf / cm 2 or more, or 13500 kf / cm 2 to 14800 kgf / cm 2 . Preferably, in terms of achieving mechanical properties and impact resistance when used as a blow molding container, the flexural modulus of the polyethylene composition can be 13100 kf / cm 2 or more, or 13200 kf / cm 2 or more, or 13300 kgf / cm 2 or more, or 13400 kgf / cm 2 or more, or 13500 kgf / cm 2 or more. However, in order to achieve excellent processability when the polyethylene composition is used as a blow molding container, the flexural modulus can be 14700 kgf / cm 2 or less, or 14600 kgf / cm 2 or less, or 14500 kgf / cm 2 or less, or 14300 kgf / cm 2 or less, or 14000 kgf / cm 2 or less, or 13900 kgf / cm 2 or less, or 13800 kgf / cm 2 or less, or 13700 kgf / cm 2 or less, or 13600 kgf / cm 2 or less.

[0186] Hereinafter, preferred exemplary embodiments will be provided to better understand the present invention. However, the following exemplary embodiments are provided only for easier understanding of the present invention, but the content of the present invention is not limited thereto.

[0187] <Example>

[0188] Example 1: Preparation of Polyethylene Composition

[0189] 50% by weight of virgin polyethylene and 50% by weight of post-consumer waste polyethylene (PCW PE) are dry-blended and extruded through a twin-screw extruder to prepare a polyethylene composition (PCR composite).

[0190] The melt index MI of the post-consumer waste polyethylene (Baeksan Natural product from Baeksan Plastic Co., Ltd.) used this time 2.16 (Measured according to ASTM D 1238 at 190 °C and a load of 2.16 kg (Condition E)) is from about 0.15 g / 10 min to about 0.2 g / 10 min, and the density (measured according to ASTM D 1505 standard) is from about 0.951 g / cm 3 to about 0.953 g / cm 3 , and the ESCR (F50 (50% failure) time measured according to ASTM D 1693 using a 10% Igepal CO-630 solution at a temperature of 50 °C) is from about 40 hours to about 50 hours.

[0191] In addition, for the virgin polyethylene used this time, 15 kg / h of isobutane and 33 kg / h of ethylene are injected, 195 ppm or 200 ppm of hydrogen and 0.8 wt% or 2.2 wt% of comonomer (1-hexene) are used, and in the presence of a catalyst (the molar ratio of the first metallocene compound to the second metallocene compound = 1:1.3, where the first metallocene compound (1) and the second metallocene compound (2) are mixed and supported on a silica carrier (Grace Davison, SP2212)), the copolymerization process is carried out in a single-slurry loop reactor, and then through a solvent removal device and a dryer. The resulting powdered high-density ethylene / 1-hexene copolymer is dry-blended to prepare a powdered high-density virgin polyethylene (HDPE). The specific physical properties of the virgin polyethylene prepared in this way are shown in Table 1 below.

[0192]

[0193] Example 2: Preparation of a polyethylene composition

[0194] A polyethylene composition (PCR composite) is prepared in the same manner as in Example 1, except that polyethylene values with the physical properties shown in Table 1 below are used as the virgin polyethylene and used together with the above post-consumer waste polyethylene (Baeksan Natural product from Baeksan Plastic Co., Ltd.) to prepare the polyethylene composition of Example 2.

[0195] The virgin polyethylene used this time is prepared in the same manner as in Example 1, except that homopolymerization is carried out using 230 ppm of hydrogen and 2.0 wt% of comonomer (1-hexene) to prepare a powdered high-density virgin polyethylene (HDPE).

[0196] Example 3: Preparation of a polyethylene composition

[0197] A polyethylene composition (PCR composite) was prepared in the same manner as in Example 1, except that a polyethylene value having the physical properties shown in Table 1 below was used as the virgin polyethylene and used together with the above post-consumer waste polyethylene (Baeksan Natural product of Baeksan Plastic Co., Ltd.) to prepare the polyethylene composition of Example 3.

[0198] The virgin polyethylene used this time was prepared in the same manner as in Example 1, except that homopolymerization was carried out using 145 ppm of hydrogen and 1.7 wt% of comonomer (1-hexene), and then dry-blended with an ethylene homopolymer-based high-density polyethylene product (ME9180 product of LG Chem Ltd.) having a density of 0.958 g / cm 3 and a melt index (MI 2.16 ) of 18 g / 10 min to prepare a powdered high-density virgin polyethylene (HDPE).

[0199] Comparative Example 1: Preparation of Polyethylene Composition

[0200] A polyethylene composition (PCR composite) was prepared in the same manner as in Example 1, except that a polyethylene resin having the physical properties shown in Table 2 below was used as the virgin polyethylene and used together with the above post-consumer waste polyethylene (Baeksan Natural product of Baeksan Plastic Co., Ltd.) to prepare the polyethylene composition of Comparative Example 1.

[0201] The virgin polyethylene used this time was prepared in the same manner as in Example 1, except that homopolymerization was carried out using 222 ppm of hydrogen and 0.8 wt% of comonomer (1-hexene) to prepare a powdered high-density virgin polyethylene (HDPE).

[0202] Comparative Example 2: Preparation of Polyethylene Composition

[0203] A polyethylene composition (PCR composite) was prepared in the same manner as in Example 1, except that a polyethylene resin having the physical properties shown in Table 2 below was used as the virgin polyethylene and used together with the above post-consumer waste polyethylene (Baeksan Natural product of Baeksan Plastic Co., Ltd.) to prepare the polyethylene composition of Comparative Example 2.

[0204] The virgin polyethylene used this time was prepared in the same manner as in Example 1, except that homopolymerization was carried out using 145 ppm of hydrogen and 1.7 wt% of comonomer (1-hexene) to prepare a powdered high-density virgin polyethylene (HDPE).

[0205] Comparative Example 3: Preparation of Polyethylene Composition

[0206] The polyethylene composition (PCR composite) was prepared in the same manner as in Example 1, except that a polyethylene resin having the physical properties shown in Table 2 below was used as the virgin polyethylene and used together with the above post-consumer waste polyethylene (Baeksan Natural product of Baeksan Plastic Co., Ltd.) to prepare the polyethylene composition of Comparative Example 3.

[0207] The virgin polyethylene used this time was prepared in the same manner as in Example 1, except that homopolymerization was carried out using 222 ppm of hydrogen and 0.8 wt% of comonomer (1-hexene), and then dry blended with a high-density polyethylene product (ME8000 product of LG Chem, Ltd.) having a density of 0.957 g / cm 3 and a melt index (MI 2.16 ) of 8 g / 10 min to prepare a powdered high-density virgin polyethylene (HDPE).

[0208] Comparative Example 4: Preparation of polyethylene composition

[0209] The polyethylene composition (PCR composite) was prepared in the same manner as in Example 1, except that a polyethylene resin having the physical properties shown in Table 2 below was used as the virgin polyethylene and used together with the above post-consumer waste polyethylene (Baeksan Natural product of Baeksan Plastic Co., Ltd.) to prepare the polyethylene composition of Comparative Example 4.

[0210] The virgin polyethylene used at this time was a dry blend of an ethylene / 1-hexene copolymer-based high-density polyethylene product (SP988 product of LG Chem, Ltd.) having a density of 0.941 g / cm 3 and a melt index (MI 2.16 ) of 0.6 g / 10 min and an ethylene homopolymer-based high-density polyethylene product (ME6000 product of LG Chem, Ltd.) having a density of 0.961 g / cm 3 and a melt index (MI 2.16 ) of 5.5 g / 10 min to prepare a powdered high-density virgin polyethylene (HDPE).

[0211] Comparative Example 5: Preparation of polyethylene composition

[0212] The polyethylene composition (PCR composite) was prepared in the same manner as in Example 1, except that a polyethylene resin having the physical properties shown in Table 2 below was used as the virgin polyethylene and used together with the above post-consumer waste polyethylene (Baeksan Natural product of Baeksan Plastic Co., Ltd.) to prepare the polyethylene composition of Comparative Example 5.

[0213] The virgin polyethylene used this time was prepared in the same manner as in Example 1, except that homopolymerization was carried out using 240 ppm of hydrogen and 2.9 wt% of comonomer (1-hexene), and then dry-blended with a high-density polyethylene product (SP988 product of LG Chem Ltd.) having a density of 0.941 g / cm 3 , melt index (MI 2.16 ) of 0.6 g / 10 min to prepare powdered high-density virgin polyethylene (HDPE).

[0214] Comparative Example 6: Preparation of Polyethylene Composition

[0215] A polyethylene composition (PCR composite) was prepared in the same manner as in Example 1, except that a polyethylene resin having the physical properties shown in Table 2 below was used as the virgin polyethylene and used together with the above post-consumer waste polyethylene (Baeksan Natural product of Baeksan Plastic Co., Ltd.) to prepare the polyethylene composition of Comparative Example 6.

[0216] The virgin polyethylene used this time was prepared in the same manner as in Example 1, except that copolymerization was carried out using 240 ppm or 222 ppm of hydrogen and 2.9 wt% or 0.8 wt% of comonomer (1-hexene) respectively, and then the resulting ethylene / 1-hexene copolymer was dry-blended to prepare powdered high-density virgin polyethylene (HDPE).

[0217] <Experimental Example>

[0218] The physical properties of the virgin polyethylene (HDPE) used in the examples and comparative examples and the polyethylene compositions (PCR composites) prepared therefrom were evaluated by the following methods, and the measurement results are shown in Tables 1 and 2 below.

[0219] (1) Density

[0220] The density (g / cm 3 ) of the virgin polyethylene (HDPE) and the polyethylene composition (PCR composite) was measured according to the American Society for Testing and Materials (ASTM) D 1505 standard.

[0221] (2) Weight-average molecular weight and molecular weight distribution (PDI, polydispersity index, Mw / Mn) analyzed by GPC and the proportion of LogMw (above 5.5 and low molecular weight)

[0222] For virgin polyethylene (HDPE), the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer were measured by gel permeation chromatography (GPC, manufactured by Waters), and the molecular weight distribution (PDI, Mw / Mn) was determined by dividing the weight-average molecular weight by the number-average molecular weight.

[0223] Specifically, PL-GPC220 from Waters was used as the gel permeation chromatography (GPC) instrument, and a column with a length of 300 mm of PLgel MIX-B from Polymer Laboratories was used. At this time, the measurement temperature was 160 °C, the solvent was 1,2,4-trichlorobenzene, and the flow rate was 1 mL / min. Using a GPC analyzer (PL-GP220), each polymer sample in the examples and comparative examples was dissolved in 1,2,4-trichlorobenzene containing 0.0125% butylhydroxytoluene (BHT) at 160 °C for 10 hours for pretreatment, prepared at a concentration of 10 mg / 10 mL, and then 200 μL was fed. The Mw and Mn values were obtained using a calibration curve formed by polystyrene standard specimens. Nine polystyrene standards with weight-average molecular weights of 2000 g / mol, 10000 g / mol, 30000 g / mol, 70000 g / mol, 200000 g / mol, 700000 g / mol, 2000000 g / mol, 4000000 g / mol, and 10000000 g / mol were used.

[0224] In addition, in the logarithmic plot of the weight-average molecular weight of virgin polyethylene (HDPE) determined by GPC analysis, that is, in the GPC curve graph with logMW as the x-axis and dw / dlogMw as the y-axis, the ratio (LogMw≥5.5, unit: %) of the integral value of the area where the LogMw value is 5.5 or more to the total integral value was calculated and shown in Table 1 and Table 2 below. Further, in the same manner as above, the integral value of the area where the LogMw value is 6.0 or more (LogMw≥6.0, unit: %) and the integral value of the area where the LogMw value is 4.5 or less (LogMw≤4.5, unit: %) with respect to the total integral value in the GPC curve graph were obtained, and the low molecular weight ratio was calculated according to the following formula 1 and shown in Table 1 and Table 2 below:

[0225] [Formula 1]

[0226] Low molecular weight ratio = Integral value of the LogMw≤4.5 region / Integral value of the LogMw≥6.0 region.

[0227] In this regard, the low molecular weight content (logMw ≤ 4.5) and high molecular weight content (logMw ≥ 6.0) derived from the GPC curve represent the percentage values of the areas corresponding to each range relative to the total integral value in the GPC curve.

[0228] (3) SCB

[0229] For virgin polyethylene (HDPE), the SCB ( / 1000TC) is measured at 160 °C using a GPC-FTIR instrument.

[0230] Specifically, the sample is pretreated by melting in 1,2,4-trichlorobenzene containing 0.0125% BHT at 160 °C for 10 hours using a PL-SP260, and then measured at 160 °C using a PerkinElmer Spectrum100FT-IR connected to a high-temperature GPC (PL-GPC220).

[0231] (4) BOCD

[0232] In the logarithmic plot of the weight-average molecular weight (Mw) of virgin polyethylene (HDPE) measured by the above GPC analysis, that is, in the GPC curve with logMW as the x-axis and dw / dlogMw as the y-axis, the content of short-chain branches (SCB) at the left and right boundaries of the central 60% region is measured by excluding the regions at both ends of 20% each from the total area, and BOCD is calculated according to Equation 2 below:

[0233] [Equation 2]

[0234] BOCD = (SCB content on the high molecular weight side - SCB content on the low molecular weight side) / (LogMw value on the high molecular weight side - LogMw on the low molecular weight side).

[0235] In this regard, the SCB content on the high molecular weight side and the SCB content on the low molecular weight side refer to the SCB content values at logMw corresponding to 20% of the regions on the high molecular weight side and the low molecular weight side, respectively. The LogMw values on the high molecular weight side and the low molecular weight side are the logMw values corresponding to 20% of the total area of the curves with respect to the y-axis (dw / dlogMw) and the x-axis (logMw) obtained by GPC analysis for the high molecular weight and low molecular weight regions.

[0236] (5) Lamellar area

[0237] The lamellar area (×10 10 cm 2 / mol) for virgin polyethylene (HDPE) is calculated according to Equation 3 below.

[0238] [Equation 3]

[0239] Lamellar region area (cm 2 / mol) = (V 比容 / Lw) × Mw × Tc

[0240] In Equation 3,

[0241] V 比容 represents the specific volume of polyethylene crystals (cm 3 / g),

[0242] Mw represents the weight-average molecular weight of polyethylene (g / mol), which is measured using gel permeation chromatography (GPC),

[0243] Tc represents the crystallinity of polyethylene (%), which is measured using differential scanning calorimetry (DSC),

[0244] Lw represents the thickness of the lamellar crystal structure of polyethylene (cm), which is measured using differential scanning calorimetry (DSC).

[0245] Here, the specific volume of polyethylene (V 比容 ) takes 1 cm 3 / g as the literature value. Additionally, the weight-average molecular weight of polyethylene (Mw) is the value measured by polystyrene conversion using gel permeation chromatography (GPC, manufactured by Waters Corporation) as described above. Furthermore, the crystallinity of polyethylene (Tc) is the value (%) measured by DSC analysis based on the melting enthalpy under the conditions of a heating / cooling rate of 10 °C / min in the range from -50 °C to 200 °C. Additionally, the thickness of the lamellar crystal structure of polyethylene (Lw) is the value (cm) measured based on the SSA experiment using a DSC device. At this time, in the SSA experiment, the polymer is completely melted and cooled to the melting point (Tm), offset by +5 °C, then annealed while cooling to Tm start - 5 °C, and then reheated for the second time to calculate the thickness of the lamellar crystal structure (Lw, weight average).

[0246] The values measured using the above method are approximated to the nearest 10 10 and are shown in Table 1 below as the lamellar region area of virgin polyethylene (cm 2 / mol).

[0247] (6) Complex viscosity

[0248] The complex viscosity (500 rad / s, Pa·s) of the polyethylene composition (PCR complex) is measured using an ARES-G2 instrument at 190 °C and 500 rad / s.

[0249] (7) Drop impact

[0250] Disks were manufactured based on a polyethylene composition (PCR composite) using the following method, weights were dropped onto the disks, the number of cracks appearing in the disks was measured, and it was expressed as the drop impact (number of times) in Tables 1 and 2 below.

[0251] 7-1. Manufacture of Drop Impact Disks

[0252] - The disks were manufactured using an injection molding machine and were manufactured by injecting the PCR composite after setting a temperature gradient of above 210 °C to below 230 °C.

[0253] - Disk dimensions (Φ50 mm, thickness 2 mm).

[0254] 7-2. Drop Impact Test

[0255] - The disk was fixed using an Instron 9450 (impact drop tower) product, and the weight was dropped, and the number of cracks appearing was measured (the drop energy was fixed at 4.2 J).

[0256] (8) ESCR

[0257] According to the ASTM D 1693-07 method, the time of F50 (50% failure) of a 2-mm-thick compression-molded sample of polyethylene composition (PCR composite) was measured using a 10% Igepal Co-630 solution under Condition B at a temperature of 50 °C, and it was expressed as ESCR (hours) in Tables 1 and 2 below.

[0258] (9) Melt Index

[0259] According to the American Society for Testing and Materials standard ASTM D 1238 (Condition E), the melt index (MI 2.16 ) of virgin polyethylene (high-density polyethylene) and polyethylene composition (PCR composite) was measured under a load of 190 °C and 2.16 kg, and it was expressed in terms of the weight (g) of the polymer that melted and extruded in 10 minutes.

[0260] (10) Flexural Modulus

[0261] The flexural modulus (Kgf / cm 2 ) of the polyethylene composition (PCR composite) was measured according to the ASTM D 790 method.

[0262] [Table 1]

[0263]

[0264] [Table 2]

[0265]

[0266] Based on the results in Table 1, it was confirmed that the polyethylene compositions of Examples 1 to 3 of the present invention had excellent effects. Specifically, even when 50 wt% of post-consumer waste polyethylene (PCW PE) was mixed, the density and complex viscosity (η*(ω500)) were optimized, and the polyethylene compositions of Examples 1 to 3 of the present invention with improved environmental stress cracking resistance (ESCR) achieved excellent effects of high stacking strength and excellent mechanical properties while ensuring excellent processability and high drop strength when used as blow molded containers.

[0267] In contrast, referring to Table 2, Comparative Examples 1 to 6 could not ensure mechanical properties that could simultaneously achieve high stacking strength, excellent processability, and relatively high drop impact strength. Specifically, Comparative Example 1 showed that the LogMw of virgin polyethylene (HDPE) ≥ 5.5 and the low molecular weight ratio decreased, and the viscosity and drop impact of the polyethylene composition (PCR composite) decreased. In addition, Comparative Example 2 showed that the density of virgin polyethylene (HDPE), LogMw ≥ 5.5, and the low molecular weight ratio decreased, and the density, viscosity, and drop impact strength of the polyethylene composition (PCR composite) decreased. Comparative Example 3 showed that the LogMw of virgin polyethylene (HDPE) ≥ 5.5, SCB, BOCD, and lamellar area decreased, and both the drop impact strength and ESCR of the polyethylene composition (PCR composite) decreased. In addition, in Comparative Example 4, the BOCD and lamellar area of virgin polyethylene (HDPE) decreased, and the ESCR of the polyethylene composition (PCR composite) decreased, resulting in a problem of long-term deterioration of physical properties when used as a blow molded container. Comparative Examples 5 and 6 showed that the density of virgin polyethylene (HDPE) decreased, and the density of the polyethylene composition (PCR composite) decreased, so it was difficult to achieve sufficient stacking strength when used as a blow molded container.

Claims

1. A polyethylene composition comprising virgin polyethylene and post-consumer waste polyethylene (PCW PE), wherein the polyethylene composition satisfies the following (a) to (d): (a) Density: 0.949 g / cm 3 above, (b) Melt index (MI) 2.16 ,ASTM D 1238,190℃,2.16kg) is 0.25g / 10min or more, (c) a complex viscosity (η*(ω500)) measured at a frequency (ω) of 500 rad / s of 600 Pa·s or less, and (d) Environmental stress crack resistance (ESCR) measured according to ASTM D 1693 (Condition B, F50, Igepal 10%) is 200 hours or more.

2. The polyethylene composition according to claim 1, wherein The polyethylene composition has a density of (a) 0.949 g / cm 3 Up to 0.954g / cm 3 .

3. The polyethylene composition according to claim 1, wherein (b) melt index (MI) of the polyethylene composition 2.16 ,ASTM D 1238,190℃,2.16kg) is 0.25g / 10min to 0.8g / 10min.

4. The polyethylene composition according to claim 1, wherein (c) complex viscosity (η*(ω500)) of the polyethylene composition is 500 Pa·s to 600 Pa·s.

5. The polyethylene composition according to claim 1, wherein The polyethylene composition has (d) environmental stress crack resistance (ESCR) of 200 hours to 500 hours.

6. The polyethylene composition according to claim 1, wherein The virgin polyethylene is an ethylene homopolymer or an ethylene / α-olefin copolymer.

7. The polyethylene composition according to claim 6, wherein The α-olefin is one or more selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and mixtures thereof.

8. The polyethylene composition according to claim 1, wherein The density of the virgin polyethylene is 0.944 g / cm 3 above.

9. The polyethylene composition according to claim 1, wherein In the GPC curve of the virgin polyethylene with logMw as the x-axis and dw / dlogMw as the y-axis, the integral value of the region where LogMw is 5.5 or more is less than 14% of the total integral value.

10. The polyethylene composition according to claim 1, wherein The low molecular weight ratio (LogMw≤4.5 / LogMw≥6.0) of the virgin polyethylene is above 15.5, which is obtained by W In the GPC curve with dw / dlogMw as the x-axis and dw / dlogMw as the y-axis, the integral value of the region where LogMw is 6.0 or more relative to the total integral value (LogMw ≥ 6.0) and the integral value of the region where LogMw is 4.5 or less relative to the total integral value (LogMw ≤ 4.5) are calculated according to the following formula 1: [Formula 1] Low molecular weight ratio = integrated value in the region of LogMw≤4.5 / integrated value in the region of LogMw≥6.

0.

11. The polyethylene composition according to claim 1, wherein The melt index (MI) of the virgin polyethylene measured at 190°C and a load of 2.16 kg according to ASTM D1238 2.16 ) is 0.1g / 10min to 1.0g / 10min.

12. The polyethylene composition according to claim 1, wherein The virgin polyethylene has an SCB ( / 1000TC) per 1000 carbon atoms of 3.0 or more as measured at 160° C. using a GPC-FTIR spectrometer.

13. The polyethylene composition according to claim 1, wherein The virgin polyethylene has a broad orthogonal comonomer distribution (BOCD) index of 1.60 or more.

14. The polyethylene composition according to claim 1, wherein The lamella area of ​​the original polyethylene is 710×10 10 cm 2 / mol or above.

15. The polyethylene composition of claim 1, comprising 10 to 90 wt% post-consumer waste polyethylene (PCW PE).

16. The polyethylene composition according to claim 1, wherein The melt index (MI) of the post-consumer waste polyethylene (PCW PE) was measured according to ASTM D 1238 at 190°C and a load of 2.16 kg. 2.16 ) is 0.15g / 10min to 0.2g / 10min.

17. The polyethylene composition according to claim 1, wherein The density of the post-consumer waste polyethylene (PCW PE) is 0.951 g / cm 3 Up to 0.953g / cm 3 .

18. The polyethylene composition according to claim 1, wherein The post-consumer waste polyethylene (PCW PE) has an environmental stress crack resistance (ESCR) of 40 to 50 hours measured according to ASTM D 1693 (Condition B, F50, Igepal 10%).

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