Polyester resin, extrusion blow molded article comprising the same, and method for manufacturing thereof

Abstract

The present invention relates to a polyester resin having a melting point and zero shear viscosity controlled within a certain range, an extruded blow molded article having excellent processability and color characteristics including said polyester resin, and a method for manufacturing the same.

Description

Technology Field

[0001] The present invention relates to a polyester resin, an extruded blow-molded article containing the same, and a method for manufacturing the same. Background Technology

[0003] Polyester resins are manufactured by polymerizing dicarboxylic acid and diol components. Because they are eco-friendly and do not contain substances harmful to the human body, they are widely used in the manufacture of films, partitions, panels, packaging materials, and containers. In particular, among polyester resins, polyethylene terephthalate (PTE) resin is primarily used in the production of small or large containers for fruit drinks, soft drinks, carbonated beverages, and water.

[0004] These polyester resins have the melt viscosity required for sheet molding processes using injection and / or calender rolls, but their melt viscosity is relatively low for introduction into extrusion blow molding processes for container molding.

[0005] In this regard, the applicant disclosed an extrusion molded product using a copolymerized polyester resin in Korean Registered Patent No. 10-1222791, which relates to a copolymerized polyester resin having terephthalic acid, ethylene glycol, 1,4-cyclohexanedimethanol, polypropylene glycol bisphenol-A, and a polyfunctional monomer as main components, and a molded product using the same. However, the technology had a problem in that the manufacture of the copolymerized polyester resin required a reaction of monomers having a specific chemical formula.

[0006] Accordingly, there is a need to develop a technology that can improve processability by enabling the polyester resin to achieve the required level of moldability when introduced into the extrusion blow molding process for container forming, even without the reaction of specific monomers. Prior art literature

[0008] Korean Registered Patent No. 10-1222791 The problem to be solved

[0009] In order to solve the aforementioned conventional problems, the inventors conducted various studies, and as a result, it was confirmed that by controlling the zero shear viscosity and melting point to a specific range, it is possible to provide an excellent polyester resin that not only improves processability in the extrusion blow molding process but also has excellent color characteristics of the final molded product.

[0010] Therefore, the objective of the present invention is to provide a polyester resin with improved processability in the extrusion blow molding process and excellent characteristics of the final molded product.

[0011] In addition, another objective of the present invention is to provide an extruded blown-molded article with excellent color characteristics using the polyester resin.

[0012] In addition, another objective of the present invention is to provide a method for manufacturing an extrusion blow molded article with improved processability in an extrusion blow molding process using the polyester resin. means of solving the problem

[0014] To achieve the above objectives, the present invention provides a polyester resin comprising a dicarboxylic acid repeating unit derived from a dicarboxylic acid component and a diol repeating unit derived from a diol component, having a melting point (Tm) of 210 °C to 250 °C and a Zero Shear Viscosity (ZSV) of 70,000 Poise to 140,000 Poise.

[0015] In addition, the present invention provides an extrusion blow molded article comprising the polyester resin.

[0016] In addition, the present invention provides a method for manufacturing an extrusion blown-molded article, comprising the steps of: melting and transporting the polyester resin through a barrel; and discharging the molten polyester resin through a die to manufacture an extrusion blown-molded article. Effects of the invention

[0018] The polyester resin according to the present invention has improved processability in the extrusion blow molding process by controlling the zero shear viscosity and melting point to a specific range, and the color characteristics of the final molded product are excellent.

[0019] In addition, the extrusion blow molded article according to the present invention has excellent color characteristics by using the polyester resin.

[0020] In addition, the manufacturing method of the present invention utilizes the polyester resin to provide excellent processability in the extrusion blow molding process. Brief explanation of the drawing

[0022] FIG. 1 is a perspective view of an extrusion blow molding apparatus for manufacturing an extrusion blow molded article according to an embodiment of the present invention. FIG. 2 is a cross-sectional view of an extrusion blow molding equipment for manufacturing an extrusion blow molded product according to an embodiment of the present invention. FIG. 3 is an exemplary diagram showing the process of manufacturing an extrusion blow molded article according to an embodiment of the present invention. Specific details for implementing the invention

[0023] The present invention will be described in detail below with reference to the drawings. If it is determined that a detailed description of related known configurations or functions in this specification may obscure the essence of the invention, such detailed description will be omitted. Additionally, the sizes of each component in the drawings may be exaggerated or omitted for illustrative purposes and may differ from the actual sizes applied.

[0024] In this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0025] All numbers and expressions indicating the amounts of components, reaction conditions, etc. described in this specification should be understood as being modified by the term "about" in all cases unless otherwise specified.

[0026] In this specification, terms such as "first," "second," etc. are used to describe various components, and said components are not limited by said terms. These terms are used solely for the purpose of distinguishing one component from another.

[0027] Where a numerical range with a limited upper limit and a numerical range with a limited lower limit are described in this specification to exemplify the size, physical properties, etc. of a component, it should be understood that a numerical range combining these upper and lower limits is also included within the exemplary scope of the present invention.

[0028] In this specification, singular expressions should be interpreted to include the singular or plural as interpreted in context unless otherwise specified.

[0029] The present invention is not limited to the contents disclosed below, but can be modified in various forms as long as the essence of the invention is not altered.

[0031] polyester resin

[0032] A polyester resin according to an embodiment of the present invention comprises a dicarboxylic acid repeating unit derived from a dicarboxylic acid component and a diol repeating unit derived from a diol component, and is characterized by having a melting point (Tm) of 210 ℃ to 250 ℃ and a Zero Shear Viscosity (ZSV) of 70,000 Poise to 140,000 Poise.

[0033] The above polyester resin may have a melting point (Tm, °C) of 210 °C or higher, 211 °C or higher, 212 °C or higher, 213 °C or higher, 214 °C or higher, 215 °C or higher, and may have a melting point of 250 °C or lower, 249 °C or lower, 248 °C or lower, 247 °C or lower, 246 °C or lower, or 245 °C or lower. For example, the polyester resin has a melting point (Tm, °C) of 210 °C to 250 °C, 211 °C to 249 °C, 212 °C to 248 °C, 213 °C to 247 °C, 214 °C to 246 °C, 215 °C to 216 °C, 215 °C to 230 °C, 215 °C to 232 °C, 215 °C to 234 °C, 215 °C to 237 °C, 228 °C to 230 °C, 228 °C to 232 °C, 228 °C to 234 °C, 228 °C to 237 °C, 228 °C to 245 °C, 231 °C to 232 °C, It may be 231 ℃ to 234 ℃, 231 ℃ to 237 ℃, 231 ℃ to 245 ℃, 232 ℃ to 234 ℃, 232 ℃ to 237 ℃, 232 ℃ to 245 ℃, 235 ℃ to 237 ℃, 235 ℃ to 245 ℃, 244 ℃ to 245 ℃, or 215 ℃ to 245 ℃. As the melting point (Tm, ℃) of the polyester resin satisfies the above range, the barrel temperature (T barrel , °C) and die temperature (T die Control of , ℃) becomes easier, and through this, processability is increased, which can improve the quality of the molded product.

[0034] Meanwhile, the Young's shear viscosity (ZSV, Poise) of the above polyester resin may be 70,000 Poise or higher and 140,000 Poise or lower. For example, the Young's shear viscosity (ZSV, Poise) of the polyester resin is 70,000 Poise to 98,000 Poise, 70,000 Poise to 101,000 Poise, 70,000 Poise to 113,000 Poise, 70,000 Poise to 126,000 Poise, 97,000 Poise to 98,000 Poise, 97,000 Poise to 101,000 Poise, 97,000 Poise to 113,000 Poise, 97,000 Poise to 126,000 Poise, 97,000 Poise to 140,000 Poise, 99,000 Poise to 101,000 Poise, 99,000 Poise to It may be 113,000 Poise, 99,000 Poise to 126,000 Poise, 99,000 Poise to 140,000 Poise, 112,000 Poise to 113,000 Poise, 112,000 Poise to 126,000 Poise, 112,000 Poise to 140,000 Poise, 124,000 Poise to 126,000 Poise, 124,000 Poise to 140,000 Poise, 139,000 Poise to 140,000 Poise, or 70,000 Poise to 140,000 Poise. When the Zero Shear Viscosity (ZSV, Poise) of the above polyester resin falls within the corresponding range, processability or moldability is enhanced when manufacturing a molded product using the polyester resin. Additionally, when the Zero Shear Viscosity (ZSV, Poise) of the above polyester resin falls within the corresponding range, the quality of the molded product can be improved, such as by lowering the yellowness of the final product.

[0035] The above polyester resin may have an intrinsic viscosity (@35 ℃) of 0.93 dl / g or more or 0.94 dl / g or more, and may be 1.33 dl / g or less, 1.32 dl / g or less, 1.31 dl / g or less, 1.30 dl / g or less, 1.29 dl / g or less, 1.28 dl / g or less, 1.27 dl / g or less, 1.26 dl / g or less, or 1.25 dl / g or less. For example, the polyester resin has an intrinsic viscosity of 0.93 dl / g to 1.33 dl / g, 0.93 dl / g to 1.32 dl / g, 0.93 dl / g to 1.31 dl / g, 0.93 dl / g to 1.30 dl / g, 0.93 dl / g to 1.29 dl / g, 0.94 dl / g to 1.28 dl / g, 0.94 dl / g to 1.27 dl / g, 0.94 dl / g to 0.99 dl / g, 0.94 dl / g to 0.99 dl / g, 0.94 dl / g to 1.03 dl / g, 0.94 dl / g to 1.1 dl / g, 0.94 dl / g to 1.15 dl / g, 0.97 dl / g to 0.99 dl / g, 0.97 dl / g to 1.03 dl / g, 0.97 dl / g to 1.1 dl / g, 0.97 dl / g to 1.15 dl / g, 0.97 dl / g to 1.25 dl / g, 1.01 dl / g to 1.03 dl / g, 1.01 dl / g to 1.1 dl / g, 1.01 dl / g to 1.15 dl / g, 1.01 dl / g to 1.25 dl / g, 1.08 dl / g to 1.1 It may be dl / g, 1.08 dl / g to 1.15 dl / g, 1.08 dl / g to 1.25 dl / g, 1.13 dl / g to 1.15 dl / g, 1.13 dl / g to 1.25 dl / g, 1.24 dl / g to 1.25 dl / g, or 0.94 dl / g to 1.25 dl / g. As the intrinsic viscosity of the polyester resin is within the above-mentioned range, the melt strength increases, allowing for the molding of larger-sized containers and improving the quality of the molded product.

[0037] Dicarboxylic acid component

[0038] The above dicarboxylic acid component may include a first dicarboxylic acid component selected from the group consisting of terephthalic acid and derivatives thereof. At this time, the content of the first dicarboxylic acid repeating unit derived from the first dicarboxylic acid component included in the polyester resin may be 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol% based on the total mol% of the dicarboxylic acid repeating units. For example, the content of the first dicarboxylic acid repeating unit derived from the first dicarboxylic acid component may be 50 mol% to 100 mol%, 60 mol% to 100 mol%, 70 mol% to 100 mol%, 80 mol% to 100 mol%, 90 mol% to 100 mol%, or 94 mol% to 100 mol% based on the total mol% of the dicarboxylic acid repeating unit.

[0039] The above dicarboxylic acid component may include a second dicarboxylic acid component selected from the group consisting of isophthalic acid and derivatives thereof. The content of the second dicarboxylic acid repeating unit derived from the above second dicarboxylic acid component is not particularly limited, but based on the total mole% of the dicarboxylic acid repeating unit, it may be included in an amount of 0 mole% or more, 1 mole% or more, 2 mole% or more, 3 mole% or more, 4 mole% or more, and 50 mole% or less, 40 mole% or less, 30 mole% or less, 20 mole% or less, 10 mole% or less, or 6 mole% or less. For example, the content of the second dicarboxylic acid repeating unit derived from the second dicarboxylic acid component may be included in an amount of 0 mol% to 50 mol%, 0 mol% to 40 mol%, 0 mol% to 30 mol%, 0 mol% to 20 mol%, 0 mol% to 10 mol%, or 0 mol% to 6 mol% based on the total mol% of the dicarboxylic acid repeating unit.

[0040] The above dicarboxylic acid component may include one or more third dicarboxylic acid components selected from the group consisting of dimethyl isophthalate, phthalic acid, dimethyl phthalate, phthalic anhydride, 2,6-naphthalene dicarboxylic acid, dimethyl 2,6-naphthalene dicarboxylate, diphenyl dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, dimethyl 1,4-cyclohexane dicarboxylate, dimethyl 1,3-cyclohexane dicarboxylate, sebacic acid, succinic acid, isodecylic succinic acid, maleic acid, maleic anhydride, fumaric acid, adipic acid, glutaric acid, and azelaic acid. The content of the second dicarboxylic acid repeating unit derived from the third dicarboxylic acid component is not particularly limited, but based on the total mole% of the dicarboxylic acid repeating unit, it may be 0 mole% to 30 mole%, 0 mole% to 25 mole%, 0 mole% to 20 mole%, 0 mole% to 15 mole%, 0 mole% to 10 mole%, or 0 mole% to 5 mole%.

[0042] Dior ingredients

[0043] The above diol component may include ethylene glycol as the first diol component. The content of the first diol repeating unit derived from the above first diol component may be 50 mol% to 100 mol%, 55 mol% to 100 mol%, 60 mol% to 100 mol%, 65 mol% to 100 mol%, 70 mol% to 100 mol%, 75 mol% to 100 mol%, 80 mol% to 100 mol%, or 85 mol% to 100 mol%, based on the total mol% of the above diol repeating units.

[0044] The above polyester resin may have repeating units derived from a diol component other than ethylene glycol in an amount of 2 mol% to 15 mol% based on the total number of moles of diol repeating units. For example, the above polyester resin may have repeating units derived from a diol component other than ethylene glycol in an amount of 2 mol% to 14 mol%, 2 mol% to 13 mol%, 2 mol% to 12 mol%, 2 mol% to 11 mol%, or 2 mol% to 10 mol% based on the total number of moles of diol repeating units.

[0045] The above diol component may include one or more second diol components selected from the group consisting of diethylene glycol, isosorbide, cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol. The polyester resin may have repeating units derived from the second diol component in an amount of 2 mol% to 15 mol%, 2 mol% to 14 mol%, 2 mol% to 13 mol%, 2 mol% to 12 mol%, 2 mol% to 11 mol%, or 2 mol% to 10 mol% based on the total molar amount of diol repeating units.

[0046] The above diol components are BHET, regenerated BHET, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-methylene-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-isopropyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, 3-methyl-2,4-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 4-(hydroxymethyl)cyclohexylmethyl, 4-(hydroxymethyl)cyclohexanecarboxylate, It may include one or more third diol components selected from the group consisting of 4-(4-(hydroxymethyl)cyclohexylmethoxymethyl)cyclohexylmethanol and mixtures thereof. The content of the third diol repeating unit derived from the third diol component is not particularly limited, but may be 0 mol% to 99 mol%, 0 mol% to 98 mol%, 0 mol% to 95 mol%, or 0 mol% to 90 mol% based on the total mol% of the diol repeating units.

[0048] Extrusion blow molded product

[0049] The extrusion blow molded article according to an embodiment of the present invention is characterized by comprising the polyester resin.

[0050] An extrusion blow molded article according to an embodiment of the present invention may have an extrusion blow molding index according to Formula 1 below of 5 to 30. For example, the extrusion blowing according to an embodiment of the present invention has an extrusion blowing molding index according to Formula 1 below of 5 to 30, 6 to 29, 7 to 28, 8 to 27, 9 to 27, 10 to 26, 10 to 25, 10 to 12, 10 to 14, 10 to 15, 10 to 16, 10 to 17, 10 to 18, 10 to 24, 12 to 14, 12 to 15, 12 to 16, 12 to 17, 12 to 18, 12 to 24, 13 to 15, 13 to 16, 13 to 17, 13 to 18, 13 to 24, 14 to 16, 14 to 17, 14 to 18, 14 to It may be 24, 15 to 17, 15 to 18, 15 to 24, 16 to 18, 16 to 24, 22 to 24, or 11 to 23.

[0051] [Equation 1]

[0052]

[0054] In the above Equation 1, the T barrel is the temperature (°C) of the barrel conveying the polyester resin during molding processing, and the T die is the temperature (°C) of the die that discharges the polyester resin during molding processing, ZSV is the zero shear viscosity (Poise) of the polyester resin, and Tm is the melting point (°C) of the polyester resin.

[0055] The above barrel temperature (T barrel , °C) and die temperature (T dieThe difference (, ℃) may be 1 ℃ or more, 2 ℃ or more, 3 ℃ or more, 4 ℃ or more, 5 ℃ or more, 6 ℃ or more, 7 ℃ or more, 8 ℃ or more, 9 ℃ or more, 10 ℃ or more, 11 ℃ or more, 12 ℃ or more, 13 ℃ or more, 14 ℃ or more, 15 ℃ or more, 16 ℃ or more, 17 ℃ or more, 18 ℃ or more, 19 ℃ or more, 20 ℃ or more, 21 ℃ or more, 22 ℃ or more, 23 ℃ or more, 24 ℃ or more, or 25 ℃ or more, and may be 60 ℃ or less, 59 ℃ or less, 58 ℃ or less, 57 ℃ or less, 56 ℃ or less, 55 ℃ or less, 54 ℃ or less, 53 ℃ or less, 52 ℃ or less, 51 ℃ It may be 50 ℃ or lower. For example, the barrel temperature (T barrel , °C) and die temperature (T die The difference of , ℃) is 1 ℃ to 60 ℃, 5 ℃ to 60 ℃, 10 ℃ to 60 ℃, 15 ℃ to 60 ℃, 20 ℃ to 55 ℃, 24 ℃ to 26 ℃, 24 ℃ to 31 ℃, 24 ℃ to 36 ℃, 24 ℃ to 41 ℃, 24 ℃ to 51 ℃, 29 ℃ to 31 ℃, 29 ℃ to 36 ℃, 29 ℃ to 41 ℃, 29 ℃ to 51 ℃, 34 ℃ to 36 ℃, 34 ℃ to 41 ℃, 34 ℃ to 51 ℃, 39 ℃ to 41 ℃, 39 ℃ to 51 ℃, 49 ℃ to 51 ℃ or It may be 25 ℃ to 50 ℃. The barrel temperature (T barrel , °C) and die temperature (T die As the difference in (°C) is within the above-mentioned range, the transparency and melt strength of the polyester resin can be increased.

[0056] The extrusion blow molded article according to an embodiment of the present invention can be used as a packaging container, a food container, a beverage container, or a cosmetic container.

[0058] Method for manufacturing extrusion blow molded products

[0059] A method for manufacturing an extrusion blow molded article according to another embodiment of the present invention comprises the steps of: melting and transporting a polyester resin through a barrel (100); and discharging the molten polyester resin through a die (200) to manufacture an extrusion blow molded article.

[0060] A method for manufacturing an extrusion blow molded article according to another embodiment of the present invention can be performed using an extrusion blow molding machine shown in FIGS. 1 and 2. Specifically, FIG. 1 is a schematic perspective view of an extrusion blow molding machine, and FIG. 2 is a schematic cross-sectional view of an extrusion blow molding machine.

[0061] As illustrated in FIG. 1, the apparatus may include a barrel (100) for melting and transporting polyester resin, a head and die (200) for discharging polyester resin received from the barrel (100), and a mold (300) for shaping the polyester resin discharged from the head and die (200) to produce a molded product. The mold (300) has an internal space of a certain shape and size. Meanwhile, a hopper (H) for receiving polyester resin may be provided at the starting point of the barrel. The head and die (200) may form a parison (P), and the mold (300) forms the parison (P) into the internal space to form a molded product.

[0062] Specifically, as illustrated in FIG. 2, the barrel (100) has a first flow path (110) inside, and polyester resin can be transported through the rotation of a screw (120) inside the first flow path (110). Additionally, a heater (130) is provided on the outer surface of the first flow path (110) to transport the polyester resin in a molten state. Meanwhile, the head and die (200) may have a second flow path (210) formed inside, and the second flow path (210) is connected to the first flow path (110) so that polyester resin is discharged. The temperature of the head and die (200) can be controlled to adjust the transparency and melt strength of the polyester resin. The second flow path (210) may be provided with an inducing member (220) that induces the formation of a parison (P), and the inducing member (220) may have a cylindrical shape. Molten polyester resin may flow between the outer surface of the inducing member (220) and the inner surface of the second flow path (210) to form a parison (P). Meanwhile, the die (200) may be provided with a blowing means (230). A blowing pipe (231) may be connected to the blowing means (230), and the blowing pipe (231) may extend to the end of the second flow path (210). The blowing pipe (231) serves to inject air into the interior of the parison (P) to form the parison (P) so that it comes into contact with the inner wall of the mold (300). Meanwhile, the extrusion blow molding equipment may be equipped with a controller (C) adjacent to the barrel (100) or the head and die (200), and the controller (C) controls the discharge speed and discharge pressure of the polyester resin and measures and controls the temperature of the barrel (100) and the head and die (200).

[0063] A method for manufacturing an extrusion blow molded article according to another embodiment of the present invention may have an extrusion blow molding index according to Formula 1 below of 5 to 30. For example, a method for manufacturing an extrusion blow molded article according to another embodiment of the present invention comprises an extrusion blow molding index according to Formula 1 below, wherein the extrusion blow molding index is 5 to 30, 6 to 29, 7 to 28, 8 to 27, 9 to 27, 10 to 26, 10 to 25, 10 to 12, 10 to 14, 10 to 15, 10 to 16, 10 to 17, 10 to 18, 10 to 24, 12 to 14, 12 to 15, 12 to 16, 12 to 17, 12 to 18, 12 to 24, 13 to 15, 13 to 16, 13 to 17, 13 to 18, 13 to 24, 14 to 16, 14 to 17, 14 to It may be 18, 14 to 24, 15 to 17, 15 to 18, 15 to 24, 16 to 18, 16 to 24, 22 to 24, or 11 to 23.

[0064] [Equation 1]

[0065]

[0067] In the above Equation 1, the T barrel is the temperature (°C) of the barrel conveying the polyester resin during molding processing, and the T die is the temperature (°C) of the die that discharges the polyester resin during molding processing, ZSV is the zero shear viscosity (Poise) of the polyester resin, and Tm is the melting point (°C) of the polyester resin.

[0068] The above barrel temperature (T barrel,℃) is 215 ℃ or higher, 216 ℃ or higher, 217 ℃ or higher, 218 ℃ or higher, 219 ℃ or higher, 220 ℃ or higher, 221 ℃ or higher, 222 ℃ or higher, 223 ℃ or higher, 224 ℃ or higher, 225 ℃ or higher, 226 ℃ or higher, 227 ℃ or higher, 228 ℃ or higher, 229 ℃ or higher, 230 ℃ or higher, 231 ℃ or higher, 232 ℃ or higher, 233 ℃ or higher, 234 ℃ or higher, 235 ℃ or higher, 236 ℃ or higher, 237 ℃ or higher, 238 ℃ or higher, 239 ℃ or higher, 240 ℃ or higher, 241 ℃ or higher, 242 ℃ or higher, 243 ℃ or higher, 244 ℃ or higher, or It may be 245 ℃ or higher, and may be 290 ℃ or lower, 289 ℃ or lower, 288 ℃ or lower, 287 ℃ or lower, 286 ℃ or lower, 285 ℃ or lower, 284 ℃ or lower, 283 ℃ or lower, 282 ℃ or lower, 281 ℃ or lower, 280 ℃ or lower, 279 ℃ or lower, 278 ℃ or lower, 277 ℃ or lower, 276 ℃ or lower, 275 ℃ or lower, 274 ℃ or lower, 273 ℃ or lower, 272 ℃ or lower, 271 ℃ or lower, 270 ℃ or lower, 269 ℃ or lower, 268 ℃ or lower, 267 ℃ or lower, 266 ℃ or lower, or 265 ℃ or lower. For example, the barrel temperature (T barrel, ℃) may be 215 ℃ to 290 ℃, 220 ℃ to 290 ℃, 240 ℃ to 250 ℃, 245 ℃ to 255 ℃, 255 ℃ to 260 ℃, 260 ℃ to 265 ℃, 244 ℃ to 246 ℃, 244 ℃ to 251 ℃, 244 ℃ to 261 ℃, 244 ℃ to 265 ℃, 249 ℃ to 251 ℃, 249 ℃ to 261 ℃, 249 ℃ to 265 ℃, 259 ℃ to 261 ℃, 259 ℃ to 265 ℃, 264 ℃ to 265 ℃, or 245 ℃ to 265 ℃. The above barrel temperature (T barrel As , ℃) is controlled within the above range, the quality of the molded product can be improved.

[0069] The above die temperature (T die , ℃) may be 180 ℃ or higher, 181 ℃ or higher, 182 ℃ or higher, 183 ℃ or higher, 184 ℃ or higher, 185 ℃ or higher, 186 ℃ or higher, 187 ℃ or higher, 188 ℃ or higher, 199 ℃ or higher, 190 ℃ or higher, 191 ℃ or higher, 192 ℃ or higher, 193 ℃ or higher, 194 ℃ or higher, 195 ℃ or higher, 196 ℃ or higher, 197 ℃ or higher, 198 ℃ or higher, 199 ℃ or higher, and 200 ℃ or higher, and may be 280 ℃ or lower, 279 ℃ or lower, 278 ℃ or lower, 277 ℃ or lower, 276 ℃ or lower, 275 ℃ or lower, 274 ℃ or lower, 273 ℃ or lower, 272 ℃ or less, 271 ℃ or less, 270 ℃ or less, 269 ℃ or less, 268 ℃ or less, 267 ℃ or less, 266 ℃ or less, 265 ℃ or less, 264 ℃ or less, 263 ℃ or less, 262 ℃ or less, 261 ℃ or less, 260 ℃ or less, 259 ℃ or less, 258 ℃ or less, 257 ℃ or less, 256 ℃ or less, 255 ℃ or less, 254 ℃ or less, 253 ℃ or less, 252 ℃ or less, 251 ℃ or less, 250 ℃ or less, 249 ℃ or less, 248 ℃ or less, 247 ℃ or less, 246 ℃ or less, 245 ℃ or less, 244 ℃ or less, 243 ℃ or less, 242 ℃ or less, It may be 241 ℃ or lower, 240 ℃ or lower, 239 ℃ or lower, 238 ℃ or lower, 237 ℃ or lower, 236 ℃ or lower, 235 ℃ or lower, 234 ℃ or lower, 233 ℃ or lower, 232 ℃ or lower, 231 ℃ or lower, or 230 ℃ or lower. For example, the die temperature (T die, ℃) is 180 ℃ to 280 ℃, 180 ℃ to 270 ℃, 195 ℃ to 205 ℃, 200 ℃ to 210 ℃, 205 ℃ to 215 ℃, 210 ℃ to 220 ℃, 215 ℃ to 225 ℃, 220 ℃ to 225 ℃, 225 ℃ to 230 ℃, 199 ℃ to 201 ℃, 199 ℃ to 211 ℃, 199 ℃ to 216 ℃, 199 ℃ to 221 ℃, 199 ℃ to 226 ℃, 199 ℃ to 230 ℃, 209 ℃ to 211 ℃, 209 ℃ to 216 ℃, The die temperature (T) may be 209 ℃ to 221 ℃, 209 ℃ to 226 ℃, 209 ℃ to 230 ℃, 214 ℃ to 216 ℃, 214 ℃ to 221 ℃, 214 ℃ to 226 ℃, 214 ℃ to 230 ℃, 219 ℃ to 221 ℃, 219 ℃ to 226 ℃, 219 ℃ to 230 ℃, 224 ℃ to 226 ℃, 224 ℃ to 230 ℃, 229 ℃ to 230 ℃, or 200 ℃ to 230 ℃. die As , ℃) is controlled within the above-mentioned range, it can lead to an improvement in the quality of the molded product.

[0070] According to the method for manufacturing an extrusion blow molded article of the present invention, the die temperature (T die The absolute value of the difference between the melting point (Tm, °C) and the polyester resin (Tm, °C) may be 0 °C to 30 °C. Specifically, the method for manufacturing an extrusion blow molded article according to an embodiment of the present invention is as follows: T die and Tm can satisfy the following Equation 2.

[0071] [Equation 2]

[0072] 0 ℃ ≤ │T die - Tm│ ≤ 30 ℃

[0073] Specifically, the above die temperature (T dieThe absolute value of the difference between the die temperature (Tm, °C) and the melting point of the polyester resin (Tm, °C) can be from 0 °C to 30 °C. For example, the die temperature (T die The absolute value of the difference between the melting point (Tm, °C) of the polyester resin and the melting point (Tm, °C) is 0 °C to 10 °C, 5 °C to 15 °C, 10 °C to 20 °C, 15 °C to 25 °C, 0 °C to 2 °C, 0 °C to 5 °C, 0 °C to 9 °C, 0 °C to 12 °C, 0 °C to 16 °C, 0 °C to 17 °C, 0 °C to 20 °C, 0 °C to 30 °C, 3 °C to 5 °C, 3 °C to 9 °C, 3 °C to 12 °C, 3 °C to 16 °C, 3 °C to 17 °C, 3 °C to 20 °C, 3 °C to 30 °C, 7 °C to 9 °C, 7 ℃ to 12 ℃, 7 ℃ to 16 ℃, 7 ℃ to 17 ℃, 7 ℃ to 20 ℃, 7 ℃ to 30 ℃, 10 ℃ to 12 ℃, 10 ℃ to 16 ℃, 10 ℃ to 17 ℃, 10 ℃ to 20 ℃, 10 ℃ to 30 ℃, 14 ℃ to 16 ℃, 14 ℃ to 17 ℃, 14 ℃ to 20 ℃, 14 ℃ to 30 ℃, 15 ℃ to 17 ℃, 15 ℃ to 20 ℃, 15 ℃ to 30 ℃, 18 ℃ to 20 ℃, 18 ℃ to 30 ℃, 29 ℃ to 30 ℃, or 20 ℃ to 30 ℃ There is. Die temperature (T die As the absolute value of the difference between the melting point (Tm, °C) and the polyester resin (Tm, °C) is within the above range, the extrusion blow moldability is improved, and the quality of the final molded product can be improved.

[0074] According to the method for manufacturing an extrusion blow molded article of the present invention, the barrel temperature (T barrel, The temperature (°C) may be 5 to 40°C higher than the melting point (Tm, °C) of the polyester resin. Specifically, the method for manufacturing an extrusion blow molded article according to an embodiment of the present invention is as follows: the T barrel This can satisfy Equation 3 below.

[0075] [Equation 3]

[0076] Tm + 5 ≤ T barrel ≤ Tm + 40

[0077] Specifically, the barrel temperature (T barrel, The temperature (°C) may be 5°C to 40°C higher than the melting point (Tm,°C) of the polyester resin. For example, the barrel temperature (T barrel, ℃) is a temperature 5 to 10 ℃ higher than the melting point (Tm, ℃) of the polyester resin, a temperature 10 to 15 ℃ higher, a temperature 15 to 20 ℃ higher, a temperature 20 to 25 ℃ higher, a temperature 25 to 30 ℃ higher, a temperature 30 to 35 ℃ higher, a temperature 35 to 40 ℃ higher, a temperature 4 to 6 ℃ higher, a temperature 4 to 15 ℃ higher, a temperature 4 to 17 ℃ higher, a temperature 4 to 22 ℃, a temperature 4 to 30 ℃ higher, a temperature 4 to 33 ℃ higher, a temperature 4 to 35 ℃ higher, a temperature 13 to 15 ℃ higher, a temperature 13 to 17 ℃ higher, and a temperature 13 to 22 ℃ higher. ℃, 13 ℃ to 30 ℃ higher temperature, 13 ℃ to 33 ℃ higher temperature, 13 ℃ to 35 ℃ higher temperature, 15 ℃ to 17 ℃ higher temperature, 15 ℃ to 22 ℃, 15 ℃ to 30 ℃ higher temperature, 15 ℃ to 33 ℃ higher temperature, 15 ℃ to 35 ℃ higher temperature, 20 ℃ to 22 ℃, 20 ℃ to 30 ℃ higher temperature, 20 ℃ to 33 ℃ higher temperature, 20 ℃ to 35 ℃ higher temperature, 28 ℃ to 30 ℃ higher temperature, 28 ℃ to 33 ℃ higher temperature, 28 ℃ to 35 ℃ higher temperature, 21 ℃ to 33 ℃ higher temperature, 31 ℃ to 35 ℃ higher temperature, 34 ℃ to 35 It may have a temperature higher than ℃ or a temperature 5 to 35 ℃ higher. The barrel temperature (T barrel,The quality of the final molded product can be improved as the temperature (Tm, °C) is controlled to the above range based on the melting point (Tm, °C) of the polyester resin.

[0078] According to the method for manufacturing an extrusion blow molded article of the present invention, the die temperature (T die , ℃) may have a temperature of -30 ℃ to 20 ℃ based on the melting point (Tm, ℃) of the polyester resin. Specifically, the method for manufacturing an extrusion blow molded article according to an embodiment of the present invention is as follows: T die A can satisfy the following Equation 4.

[0079] [Equation 4]

[0080] Tm - 30 ≤ T die ≤ Tm + 20

[0081] Specifically, the above die temperature (T die The temperature (Tm, °C) can range from -30 °C to 20 °C based on the melting point (Tm, °C) of the polyester resin. For example, the die temperature (T die, ℃) refers to temperatures of -30 ℃ to -20 ℃, -25 ℃ to -15 ℃, -20 ℃ to -10 ℃, -15 ℃ to -5 ℃, -10 ℃ to 0 ℃, -5 ℃ to +5 ℃, 0 ℃ to +10 ℃, +5 ℃ to +15 ℃, or +10 ℃ to +20 ℃, -30 ℃ to -29 ℃, -30 ℃ to -18 ℃, -30 ℃ to -15 ℃, -30 ℃ to -14 ℃, -30 ℃ to -10 ℃, -30 ℃ to -7 ℃, based on the melting point (Tm, ℃) of the polyester resin. Temperatures of -30 ℃ to -3 ℃, temperatures of -30 ℃ to -0 ℃, temperatures of -20 ℃ to -18 ℃, temperatures of -20 ℃ to -15 ℃, temperatures of -20 ℃ to -14 ℃, temperatures of -20 ℃ to -10 ℃, temperatures of -20 ℃ to -7 ℃, temperatures of -20 ℃ to -3 ℃, temperatures of -20 ℃ to -0 ℃, temperatures of -17 ℃ to -15 ℃, temperatures of -17 ℃ to -14 ℃, temperatures of -17 ℃ to -10 ℃, temperatures of -17 ℃ to -7 ℃, temperatures of -17 ℃ to -3 ℃, temperatures of -17 ℃ to -0 ℃, temperatures of -16 ℃ to -14 ℃, temperatures of -16 ℃ to -10 ℃, temperatures of -16 ℃ to -7 ℃, -16 The die temperature (T) may have a temperature of ℃ to -3 ℃, a temperature of -16 ℃ to -0 ℃, a temperature of -12 ℃ to -10 ℃, a temperature of -12 ℃ to -7 ℃, a temperature of -12 ℃ to -3 ℃, a temperature of -12 ℃ to -0 ℃, a temperature of -9 ℃ to -7 ℃, a temperature of -9 ℃ to -3 ℃, a temperature of -9 ℃ to -0 ℃, a temperature of -9 ℃ to -0 ℃, a temperature of -5 ℃ to -3 ℃, a temperature of -5 ℃ to -0 ℃, a temperature of -2 ℃ to -0 ℃, or a temperature of -30 ℃ to -1 ℃. dieAs the temperature (Tm, °C) is controlled to the above range based on the melting point (Tm, °C) of the polyester resin, the crystallinity of the polyester resin is lowered, which can increase the melt pressure of the extruder.

[0082] Meanwhile, the step of manufacturing the extrusion blow molded product may include a process of forming a parison (a), a process of closing the mold (b), and a process of injecting air (c), as illustrated in FIG. 3. In the process of forming the parison (a), polyester resin transferred to the second flow path (210) is introduced between the outer surface of the guiding member (220) and the inner surface of the second flow path (210) to form a parison (P). Subsequently, in the process of closing the mold (b), the molds (300) on both sides of the formed parison (P) are closed so that the parison (P) is introduced into the internal space of the mold (300). Subsequently, in the process of injecting air (c), air is injected into the interior of the parison (P) through a blower pipe (231) connected to a blower means (230). Accordingly, the parison (P) expands outward and comes into contact with the edge of the internal space provided in the mold (300), thereby forming a certain shape. After going through the above process, the parison (P) is cut and the mold (300) is opened to obtain an extrusion blow molded product.

[0084] Form for carrying out the invention

[0085] <Example 1>

[0086] 4259.0 g of terephthalic acid (TPA), 2067.9 g of ethylene glycol (EG), 110.8 g of 1,4-cyclohexanedimethanol (CHDM), and 112.4 g of isosorbide (ISB) were mixed and added. Subsequently, 12.8 g of germanium (Ge) catalyst was added as a catalyst, 3.6 g of phosphoric acid as a stabilizer, and 0.010 g of blue toner and 0.005 g of red toner were added as colorants.

[0087] Subsequently, nitrogen is injected into the reactor containing the above composition so that the pressure in the reactor is 1.8 kgf / cm² relative to atmospheric pressure. 2 The reactor was subjected to a high pressurization state (absolute pressure: 1495.6 mmHg). The reactor temperature was then raised from room temperature to 200°C over 60 minutes, maintained at 200°C for 2 hours, and then raised again to 250°C over 5 hours. Subsequently, the esterification reaction was carried out at 250°C for 0.5 hours. During this process, byproducts were discharged through a column and a condenser. Once the esterification reaction was complete, the nitrogen inside the pressurized reactor was purged to lower the reactor pressure to atmospheric pressure, and the product of the esterification reaction was transferred to a 7L capacity reactor capable of vacuum reaction.

[0088] (2) Polycondensation reaction

[0089] Subsequently, the pressure of the reactor containing the product of the esterification reaction was reduced from atmospheric pressure to 5.0 Torr (absolute pressure: 5 mmHg) over 30 minutes, and simultaneously the temperature of the reactor was increased to 260 ℃ over 1 hour. Then, the pressure of the reactor was maintained at 1.0 Torr (absolute pressure: 1.0 mmHg) or lower to carry out the polycondensation reaction. At this time, the stirring speed was set fast at the beginning of the polycondensation reaction, but as the polycondensation reaction progressed, the stirring force weakened due to the increase in the viscosity of the reactants or the temperature of the reactants rose above the set temperature, at which point the stirring speed was appropriately adjusted. The polycondensation reaction was carried out until the intrinsic viscosity (IV) of the mixture (molten material) inside the reactor reached 0.70 dl / g or higher. After the polycondensation reaction was completed, the vacuum was broken using nitrogen gas, and the mixture was discharged outside the reactor to solidify with a cooling liquid and then granulated to an average weight of about 10 mg to 20 mg. Next, the polyester resin was introduced into a solid-state polymerization reactor, and the temperature of the solid-state reactor was gradually raised to 205°C under a nitrogen atmosphere, after which the solid-state polymerization reaction was carried out at 205°C. When the solid-state viscosity (IV) of the reactant in the solid-state polymerization reactor reached 1.02 dl / g, the reactant was discharged from the solid-state polymerization reactor to produce a polyester resin (copolymer).

[0091] <Example 2>

[0092] 2539.5 g of terephthalic acid (TPA), 1138.2 g of ethylene glycol (EG), and 110.1 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) were mixed and added. Subsequently, 1.6 g of antimony (Sb) catalyst was added as a catalyst, 2.2 g of phosphoric acid as a stabilizer, and 0.009 g of blue toner and 0.006 g of red toner were added as colorants.

[0093] Subsequently, the esterification reaction was performed at 3.0 kgf / cm² relative to atmospheric pressure. 2 A polyester resin (copolymer) was prepared through the same process as in Example 1, except that the process was carried out at 260 ℃ under high pressure, the polycondensation reaction was carried out at 265 ℃ until the intrinsic viscosity (IV) was 0.75 dl / g or higher, and the solid phase polymerization reaction was carried out at 210 ℃ until the solid phase occupancy viscosity (IV) reached 0.98 dl / g.

[0095] <Example 3>

[0096] 2311.7 g of terephthalic acid (TPA), 992.9 g of ethylene glycol (EG), 180.5 g of 1,4-cyclohexanedimethanol (CHDM), and 101.7 g of isosorbide (ISB) were mixed and added. Subsequently, 5.4 g of germanium (Ge) catalyst was added as a catalyst, 3.0 g of phosphoric acid as a stabilizer, and 0.011 g of blue toner and 0.001 g of red toner were added as colorants.

[0097] Subsequently, the esterification reaction was performed at 2.3 kgf / cm² relative to atmospheric pressure. 2 A polyester resin (copolymer) was prepared through the same process as in Example 1, except that the process was carried out at 270°C under a high pressure condition until the intrinsic viscosity (IV) reached 0.68 dl / g or higher, and the solid phase polymerization reaction was carried out at 195°C until the solid phase occupancy viscosity (IV) reached 0.94 dl / g.

[0099] <Example 4>

[0100] 3285.4 g of terephthalic acid (TPA), 172.9 g of isophthalic acid (IPA), and 1937.5 g of ethylene glycol (EG) were mixed and added. Subsequently, 15.4 g of germanium (Ge) catalyst was added as a catalyst, 0.9 g of phosphoric acid as a stabilizer, and 0.020 g of blue toner and 0.006 g of red toner were added as colorants.

[0101] Subsequently, the esterification reaction was performed at 1.5 kgf / cm² relative to atmospheric pressure. 2 A polyester resin (copolymer) was prepared through the same process as in Example 1, except that the process was carried out at 250°C under a high pressure condition, the polycondensation reaction was carried out at 270°C until the intrinsic viscosity (IV) was 0.65 dl / g or higher, and the solid phase polymerization reaction was carried out at 210°C until the solid phase occupancy viscosity (IV) reached 1.25 dl / g.

[0103] <Example 5>

[0104] 3819.7 g of terephthalic acid (TPA), 243.8 g of isophthalic acid (IPA), and 2048.9 g of ethylene glycol (EG) were mixed and added. Subsequently, 6.0 g of germanium (Ge) catalyst was added as a catalyst, 2.7 g of phosphoric acid as a stabilizer, 0.672 g of cobalt acetate as a colorant, 0.016 g of blue toner, and 0.002 g of red toner were added.

[0105] Subsequently, the esterification reaction was performed at 2.5 kgf / cm² relative to atmospheric pressure. 2 A polyester resin (copolymer) was prepared through the same process as in Example 1, except that the process was carried out at 265 ℃ under high pressure, the polycondensation reaction was carried out at 275 ℃ until the intrinsic viscosity (IV) was 0.60 dl / g or higher, and the solid phase polymerization reaction was carried out at 200 ℃ until the solid phase occupancy viscosity (IV) reached 1.09 dl / g.

[0107] <Example 6>

[0108] 3026.7 g of terephthalic acid (TPA) and 1638.8 g of ethylene glycol (EG) were mixed and added. Subsequently, 3.6 g of germanium (Ge) catalyst was added as a catalyst, 1.3 g of phosphoric acid as a stabilizer, 0.480 g of cobalt acetate as a colorant, 0.009 g of blue toner, and 0.004 g of red toner were added.

[0109] Subsequently, the esterification reaction was performed at 2.5 kgf / cm² relative to atmospheric pressure. 2 A polyester resin (copolymer) was prepared through the same process as in Example 1, except that the process was carried out at 265 ℃ under a high pressure condition, the polycondensation reaction was carried out at 275 ℃, and the solid polymerization reaction was carried out at 200 ℃ until the solid occupancy viscosity (IV) reached 1.14 dl / g.

[0111] <Comparative Example 1>

[0112] 2572.2 g of terephthalic acid (TPA), 1200.9 g of ethylene glycol (EG), 1227.2 g of 1,4-cyclohexanedimethanol (CHDM), and 90.5 g of isosorbide (ISB) were mixed and added. Subsequently, 4.7 g of germanium (Ge) catalyst was added as a catalyst, and 2.1 g of phosphoric acid was added as a stabilizer.

[0113] Subsequently, a polyester resin (copolymer) was prepared through the same process as in Example 1, except that the esterification reaction was carried out at 260 ℃ and the polycondensation reaction was carried out at 270 ℃ until the intrinsic viscosity (IV) was 0.80 dl / g or higher, but the solid-state polymerization reaction was not carried out.

[0115] <Comparative Example 2>

[0116] 3250.1 g of terephthalic acid (TPA), 1638.8 g of ethylene glycol (EG), and 422.9 g of 1,4-cyclohexanedimethanol (CHDM) were mixed and added. Subsequently, 1.0 g of germanium (Ge) catalyst was added as a catalyst, and 0.3 g of phosphoric acid was added as a stabilizer.

[0117] Subsequently, the esterification reaction was performed at 2.3 kgf / cm² relative to atmospheric pressure. 2A polyester resin (copolymer) was prepared by following the same process as in Example 1, except that the polycondensation reaction was carried out at 255 ℃ under high pressure and at 265 ℃ until the intrinsic viscosity (IV) was 0.75 dl / g or higher, but the solid-state polymerization reaction was not carried out.

[0119] <Comparative Example 3>

[0120] 3793.4 g of terephthalic acid (TPA), 1714.4 g of ethylene glycol (EG), and 197.4 g of 1,4-cyclohexanedimethanol (CHDM) were mixed and added. Subsequently, 8.6 g of germanium (Ge) catalyst was added as a catalyst, and 3.3 g of phosphoric acid was added as a stabilizer.

[0121] Subsequently, the esterification reaction was performed at 1.5 kgf / cm² relative to atmospheric pressure. 2 A polyester resin (copolymer) was prepared by following the same process as in Example 1, except that the polycondensation reaction was carried out at 263 ℃ under high pressure and at 275 ℃ until the intrinsic viscosity (IV) was 0.75 dl / g or higher, but the solid-state polymerization reaction was not carried out.

[0123] <Comparative Example 4>

[0124] 2711.3 g of terephthalic acid (TPA) and 1343.3 g of ethylene glycol (EG) were mixed and added. Subsequently, 10.2 g of germanium (Ge) catalyst was added as a catalyst and 4.6 g of phosphoric acid was added as a stabilizer.

[0125] Subsequently, the esterification reaction was performed at 1.7 kgf / cm² relative to atmospheric pressure. 2A polyester resin (copolymer) was prepared through the same process as in Example 1, except that the process was carried out at 263 ℃ under a high pressure condition, the polycondensation reaction was carried out at 280 ℃ until the intrinsic viscosity (IV) was 0.55 dl / g or higher, and the solid phase polymerization reaction was carried out at 215 ℃ until the solid phase occupancy viscosity (IV) reached 0.95 dl / g.

[0127] <Comparative Example 5>

[0128] 2965.5 g of terephthalic acid (TPA), 60.5 g of isophthalic acid (IPA), and 1469.3 g of ethylene glycol (EG) were mixed and added. Subsequently, 13.4 g of germanium (Ge) catalyst was added as a catalyst, and 5.1 g of phosphoric acid was added as a stabilizer.

[0129] Subsequently, the esterification reaction was performed at 2.0 kgf / cm² relative to atmospheric pressure. 2 A polyester resin (copolymer) was prepared through the same process as in Example 1, except that the process was carried out at 260 ℃ under a high pressure condition, the polycondensation reaction was carried out at 280 ℃ until the intrinsic viscosity (IV) was 0.65 dl / g or higher, and the solid phase polymerization reaction was carried out at 220 ℃ until the solid phase occupancy viscosity (IV) reached 1.34 dl / g.

[0131] <Comparative Example 6>

[0132] 2952.9 g of terephthalic acid (TPA), 1469.3 g of ethylene glycol (EG), and 26.1 g of 1,4-cyclohexanedimethanol (CHDM) were mixed and added. Subsequently, 11.2 g of germanium (Ge) catalyst was added as a catalyst, and 2.5 g of phosphoric acid was added as a stabilizer.

[0133] Subsequently, the esterification reaction was performed at 1.5 kgf / cm² relative to atmospheric pressure. 2A polyester resin (copolymer) was prepared through the same process as in Example 1, except that the process was carried out at 260 ℃ under high pressure, the polycondensation reaction was carried out at 275 ℃ until the intrinsic viscosity (IV) was 0.57 dl / g or higher, and the solid phase polymerization reaction was carried out at 220 ℃ until the solid phase occupancy viscosity (IV) reached 0.92 dl / g.

[0135] Polyester resin test example

[0136] 1) Young's Shear Viscosity (ZSV)

[0137] The zero shear viscosity of the polyester resins prepared in Examples 1 to 6 and Comparative Examples 1 to 6, respectively, was measured. Specifically, the polyester resin samples of Examples 1 to 6 and Comparative Examples 1 to 6 were placed in an oven at 150°C and dried for 6 hours under conditions of supplying and exhausting nitrogen to remove moisture, and then sealed and stored to prevent moisture penetration. Subsequently, a plate with an upper diameter of 25 mm and a lower diameter of 40 mm was mounted on a rheometer (HR 20, TA Instruments) and calibration was performed. Nitrogen was supplied at 10 L / min, and the temperature of the measurement section was raised to 250°C. After the temperature of the rheometer's measurement section stabilized, the sample was placed on the lower plate. Afterward, the sample was melted for 6 minutes, and the position of the upper plate was adjusted so that the upper and lower plates were positioned parallel to each other at a distance of 1 mm. Then, the excess resin was trimmed by opening the measuring section. After trimming was completed, the temperature of the measuring section was restored to 250 ℃ and stabilized. Then, the complex viscosity of the polyester resin was measured under a nitrogen atmosphere while varying the angular frequency from 0.5 rad / s to 500 rad / s, and the complex viscosity measured at each frequency of 0.5 rad / s was defined as the zero-shear viscosity.

[0139] 2) Melting temperature (Tm)

[0140] Using a differential scanning calorimeter (Mettler Toledo), the polyester resin was melted and quenched to completely remove the thermal history, and then heated at a rate of 10 °C / min for measurement. The maximum point of the endothermic peak caused by the melting of the resin was set as the melting point (Tm).

[0142] 3) Intrinsic viscosity (IV, @35 ℃)

[0143] The polyester resins of Examples 1 to 6 and Comparative Examples 1 to 6 were each dissolved in orthochlorophenol (OCP) at 150°C at a concentration of 0.12%, and then the intrinsic viscosity (IV, dl / g) was measured using a Ubelrod type viscometer in a constant temperature bath at 35°C.

[0145] <Preparation Examples 1 to 8 and Comparative Preparation Examples 1 to 8>

[0146] Extrusion blow molded articles were manufactured using the polyester resins of Examples 1 to 6 and Comparative Examples 1 to 6.

[0147] Polyester resin was injected into the hopper (H) of the extrusion blow molding machine, the temperature (°C) of the barrel (100), the temperature (°C) of the die (200), and the melt pressure (bar) were set as shown in the table below, and a parison (P) was blown into the mold (300) to manufacture an extrusion blow molded product.

[0149] Subsequently, the value was calculated according to the following Equation 1.

[0150] [Equation 1]

[0151]

[0153] Extrusion blow molding test example

[0154] 1) EBM moldability of bottles

[0155] The moldability of the containers obtained through the manufacturing processes of Manufacturing Examples 1 to 8 and Comparative Manufacturing Examples 1 to 8 was evaluated according to the following evaluation criteria by weighing the containers obtained through an 800 ml handle-ware bottle mold using an extrusion blow molding machine (Bekum EBM machine, Bekum Co.), and the results are shown in the table below.

[0156] ◎: When the container weighs 160 g or more

[0157] ○: When the weight of the container is 140 g or more and less than 160 g

[0158] △: When the weight of the container is 120 g or more and less than 140 g

[0159] ×: Container cannot be molded, non-uniform molded product

[0161] 1) Yellowness of the molded product

[0162] The yellowness of the molded articles obtained through the manufacturing processes of Manufacturing Examples 1 to 8 and Comparative Manufacturing Examples 1 to 8 was evaluated. The yellowness of the molded articles was evaluated visually according to the following evaluation criteria for the containers obtained from the mold for an 800 ml handle-ware bottle using an extrusion blow molding machine (Bekum EBM machine, Bekum Co.), and the results are shown in the table below.

[0163] If colorless: ×

[0164] If there is a yellow color: ○

[0165] Cases where plastic surgery is not possible: -

[0167] division Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Preparation Example 7 Preparation Example 8 profit Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Barrel temperature (°C) 260 245 250 250 250 245 250 265 Die temperature (°C) 230 220 220 200 215 210 225 225 melt-pressure(bar) 117 127 113 124 138 130 100 150 Zero shear viscosity (Poise) 125,000 125,000 100,000 70,000 112,500 97,500 97,500 140,000 Tm (℃) 231 231 236 215 245 229 229 233 Intrinsic viscosity (@35 ℃) (dl / g) 1.02 1.02 0.98 0.94 1.25 1.09 1.09 1.14 T barrel - T die 30 25 30 50 35 35 25 40 Exponential according to Equation 1 16 14 13 17 16 15 11 23 Extrusion blow molding properties ○ ◎ ○ ◎ ◎ ◎ ◎ ◎ Yellowness of molded products × × × × × × × ×

[0169] division Comparative Manufacturing Example 1 Comparative Manufacturing Example 2 Comparative Manufacturing Example 3 Comparative Manufacturing Example 4 Comparative Manufacturing Example 5 Comparative Manufacturing Example 6 Comparative Manufacturing Example 7 Comparative Manufacturing Example 8 profit Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Barrel temperature (°C) 220 240 250 205 275 290 300 250 Die temperature (°C) 200 180 220 205 260 245 240 235 melt-pressure(bar) 160 150 35 70 18 23 160 95 Zero shear viscosity (Poise) 30,000 15,000 12,000 12,000 25,000 25,000 145,000 67,000 Tm (℃) - - 240 240 260 260 257 250 Intrinsic viscosity (@35 ℃)(dl / g) 0.80 0.75 0.75 0.75 0.85 0.85 1.34 0.92 T bd 20 60 30 0 15 45 60 20 Exponential according to Equation 1 - - 2 0 1.4 4 35 4 Extrusion blow molding properties △ △ × × × × ○ × Yellowness of molded products × × - - - - ○ -

[0171] As a result, the polyester resin according to the embodiment of the present invention has a Young's shear viscosity of 70,000 Poise to 140,000 Poise, whereas the polyester resin according to the comparative example of the present invention did not satisfy this Young's shear viscosity.

[0172] In addition, the polyester resin according to the embodiment of the present invention had a melting point of 215 ℃ to 245 ℃, and the polyester resin according to the comparative example of the present invention had a melting point that was not measured or was 240 ℃ to 260 ℃.

[0173] In addition, it was confirmed that the containers of Manufacturing Examples 1 to 8, made from the polyester resin according to the above examples, possess excellent quality by exhibiting excellent extrusion blow moldability and simultaneously showing colorless color in the yellowness evaluation. On the other hand, it was confirmed that the containers of Comparative Manufacturing Examples 1 to 8, made from the polyester resin according to the above comparative examples, exhibited relatively low extrusion blow moldability or had high yellowness, resulting in a decrease in quality compared to Manufacturing Examples 1 to 8. Explanation of the symbols

[0175] 100: Barrel 110: The 1st Euro 120: Screw 130: Heater 200: Die 210: The 2nd Euro 220: Induction member 230: Blower 231: Blower pipe 300: Mold H: Hopper C: Controller P: Parish

Claims

Claim 1 A polyester resin comprising a dicarboxylic acid repeating unit derived from a dicarboxylic acid component and a diol repeating unit derived from a diol component, having a melting point (Tm) of 210 °C to 250 °C and a Zero Shear Viscosity (ZSV) of 70,000 Poise to 140,000 Poise. Claim 2 In claim 1, the polyester resin comprises a diol component including ethylene glycol as a first diol component. Claim 3 In claim 1, the polyester resin is a polyester resin in which the repeating unit derived from a diol component other than ethylene glycol is 2 mol% to 15 mol% based on the total molar amount of the diol repeating unit. Claim 4 A polyester resin according to claim 1, wherein the dicarboxylic acid component comprises a first dicarboxylic acid component selected from the group consisting of terephthalic acid and derivatives thereof. Claim 5 A polyester resin according to claim 1, wherein the dicarboxylic acid component comprises a second dicarboxylic acid component selected from the group consisting of isophthalic acid and derivatives thereof. Claim 6 A polyester resin according to claim 1, wherein the dicarboxylic acid component comprises one or more third dicarboxylic acid components selected from the group consisting of dimethyl isophthalate, phthalic acid, dimethyl phthalate, phthalic anhydride, 2,6-naphthalene dicarboxylic acid, dimethyl 2,6-naphthalene dicarboxylate, diphenyl dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, dimethyl 1,4-cyclohexane dicarboxylate, dimethyl 1,3-cyclohexane dicarboxylate, sebacic acid, succinic acid, isodecylic succinic acid, maleic acid, maleic anhydride, fumaric acid, adipic acid, glutaric acid, and azelaic acid. Claim 7 A polyester resin according to claim 1, wherein the diol component comprises one or more second diol components selected from the group consisting of diethylene glycol, isosorbide, cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Claim 8 In claim 1, the diol component is BHET, regenerated BHET, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-methylene-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-isopropyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, 3-methyl-2,4-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 4-(hydroxymethyl)cyclohexylmethyl 4-(hydroxymethyl)cyclohexanecarboxylate, A polyester resin comprising one or more third diol components selected from the group consisting of 4-(4-(hydroxymethyl)cyclohexylmethoxymethyl)cyclohexylmethanol and mixtures thereof. Claim 9 In claim 1, the polyester resin is a polyester resin having an intrinsic viscosity of 0.93 dl / g to 1.33 dl / g. Claim 10 An extrusion blow molded article comprising the polyester resin of claim 1. Claim 11 In claim 10, an extrusion blow molded article having an extrusion blow molding index according to the following Formula 1 of 5 to 30: [Formula 1] In the above Equation 1, the above T barrel is the temperature (°C) of the barrel conveying the polyester resin during molding processing, and the T die is the temperature (°C) of the die that discharges the polyester resin during molding processing, ZSV is the zero shear viscosity (Poise) of the polyester resin, and Tm is the melting point (°C) of the polyester resin. Claim 12 In claim 11, the above T barrel and T die The difference is 1 to 60, extruded blow molded product. Claim 13 In claim 10, the extrusion blow molded product is a packaging container, a food container, a beverage container, or a cosmetic container. Claim 14 A method for manufacturing an extrusion blown molded article, comprising: a step of melting and conveying the polyester resin of claim 1 through a barrel (100); and a step of discharging the molten polyester resin through a die (200) to manufacture an extrusion blown molded article. Claim 15 In claim 14, a method for manufacturing an extrusion blow molded article having an extrusion blow molding index according to the following Formula 1 of 5 to 30: [Formula 1] In the above Equation 1, the above T barrel is the temperature (°C) of the barrel conveying the polyester resin during molding processing, and the T die is the temperature (°C) of the die that discharges the polyester resin during molding processing, ZSV is the zero shear viscosity (Poise) of the polyester resin, and Tm is the melting point (°C) of the polyester resin. Claim 16 In claim 15, the above T barrel The temperature is 215 ℃ to 290 ℃, and the above T die A method for manufacturing an extrusion blow molded article, wherein the temperature is 180 ℃ to 280 ℃. Claim 17 In claim 15, the above T die Method for manufacturing an extrusion blow molded article in which Tm satisfies the following Equation 2: [Equation 2] 0 ℃ ≤ │T die - Tm│ ≤ 30 Claim 18 In claim 15, the above T barrel Method for manufacturing an extrusion blow molded article satisfying the following Equation 3: [Equation 3] Tm + 5 ≤ T barrel ≤ Tm + 40 Claim 19 In claim 15, the above T die A method for manufacturing an extrusion blow molded article satisfying the following Equation 4: [Equation 4] Tm - 30 ≤ T die ≤ Tm + 20

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