Thermoplastic polyester elastomer resin and preparation method thereof

Abstract

The invention relates to thermoplastic polyester elastomer resin, a preparation method thereof and a product containing the resin. The thermoplastic polyester elastomer resin has good elasticity and compression resilience and high mechanical strength, elongation and other properties. Thus, the thermoplastic polyester elastomer resin can be used to produce various products (such as fibers, foams, footwear components).

Description

Technical Field

[0001] This invention relates to a thermoplastic polyester elastomer resin comprising a hard segment having thermoplastic properties and a soft segment having elastomeric properties (introducing PO3G and EO-PPG), and having excellent physical properties such as mechanical strength, elasticity and compression resilience, as well as a method for preparing the resin. Background Technology

[0002] Thermoplastic elastomer (TPE) resins comprise hard segments derived from thermoplastic polymers with thermoplastic properties and soft segments derived from rubber-like materials with elastomeric properties. Compared to traditional thermosetting rubbers, the hard segments, which are physically bonded through crystals, resemble a chemical crosslinking process called "vulcanization," while the soft segments exhibit properties similar to amorphous rubber.

[0003] Thermoplastic polyester elastomer (TPEE) resins in TPE resins have high mechanical strength and excellent impact resistance, heat resistance, flexibility and moldability; therefore, they are used to prepare automotive parts, electrical and electronic components, fibers and films.

[0004] TPEE resin mainly consists of crystalline hard segments of tetramethylene ester and amorphous soft segments of polyether polyol ester. Polyethylene glycol ether (PEG), poly(1,2-propanediol) glycol (PPG), ethylene oxide-added polypropylene glycol (EO-PPG), and polytetramethylene ether glycol (PTMG) have been used as raw materials for preparing the soft segments of TPEE resin. However, TPEE resin prepared using PEG as a raw material has the disadvantage of high moisture content, and PPG has low polymerization reactivity; therefore, they are not commonly used as raw materials for preparing TPEE resin. Therefore, PTMG, EO-PPG, or combinations thereof are mainly used to prepare the soft segments of TPEE resin.

[0005] TPEE resins prepared using PTMG as a raw material exhibit good physical properties, such as mechanical strength and elongation; however, there are limitations in increasing physical properties, such as elasticity and compression resilience, at desired or higher levels. Furthermore, TPEE resins prepared using EO-PPG as a raw material have high crystallinity, resulting in excellent moldability; however, their physical properties, such as mechanical strength and elongation, are poor.

[0006] Therefore, there is a need to develop a new type of TPEE resin with excellent physical properties, such as mechanical strength and elongation, as well as high elasticity and compression resilience, so that it can be used to prepare a variety of products. Summary of the Invention

[0007] Technical issues

[0008] To address the aforementioned traditional problems, the inventors conducted various studies. The results showed that by blending two or more polyester elastomer resins, thermoplastic polyester elastomer (TPEE) resins with excellent mechanical properties and enhanced elasticity and compression resilience were obtained, wherein the crystallinity and crystallization rate of the soft segments were controlled at low levels, while phase separation between the hard and soft segments was prevented.

[0009] Therefore, one object of the present invention is to provide a thermoplastic polyester elastomer resin with excellent mechanical strength, as well as excellent elasticity and compression resilience, and a method for preparing the same.

[0010] Furthermore, another object of the present invention is to provide a composition or article comprising the thermoplastic polyester elastomer resin.

[0011] Solution to the problem

[0012] To achieve the above objectives, the present invention provides a thermoplastic polyester elastomer resin comprising a first polyester elastomer resin comprising repeating units (a) represented by Formula 1 and repeating units (b) represented by Formula 2; and a second polyester elastomer resin comprising repeating units (a) represented by Formula 1 and repeating units (c) represented by Formula 3. [Formula 1]

[0013] [Equation 2]

[0014] [Formula 3]

[0015] In equations 1 to 3, R 1 To R 3 Each independently is C1 to C 12 Straight-chain, branched, or cyclic divalent aliphatic hydrocarbon groups, or C6 to C6 groups. 12 The divalent aromatic hydrocarbon group, where m is an integer from 2 to 6, n is an integer from 2 to 3, p is an integer from 10 to 30, t is an integer from 1 to 30, and s is an integer from 1 to 40.

[0016] Furthermore, the present invention provides a method for preparing a thermoplastic polyester elastomer resin, the method comprising: (1-1) reacting a first diol component, a first dicarboxylic acid component, and a first high molecular weight diol component to obtain a first polyester elastomer resin; (1-2) reacting a second diol component, a second dicarboxylic acid component, and a second high molecular weight diol component to obtain a second polyester elastomer resin; and (1-3) melt-blending the first polyester elastomer resin and the second polyester elastomer resin; wherein the first polyester elastomer resin comprises a repeating unit (a) represented by Formula 1 above and a repeating unit (b) represented by Formula 2 above; and the second polyester elastomer resin comprises a repeating unit (a) represented by Formula 1 above and a repeating unit (c) represented by Formula 3 above.

[0017] Furthermore, the present invention provides a composition comprising the aforementioned thermoplastic polyester elastomer resin.

[0018] Furthermore, the present invention provides an article comprising the aforementioned thermoplastic polyester elastomer resin.

[0019] Beneficial effects of the invention

[0020] In the thermoplastic polyester elastomer resin of the present invention, since a first polyester elastomer resin comprising polytrimethylene ether glycol (PO3G) is used in the formation of its soft segments, it exhibits excellent mechanical strength. Furthermore, in the thermoplastic polyester elastomer resin of the present invention, since a second polyester elastomer resin comprising ethylene oxide-added polypropylene glycol (EO-PPG) is used in the formation of its soft segments, wherein the methylene side chain is attached to the polyol backbone, restricting the movement of the polymer chains in the soft segments, generating sufficient free volume between the polymer chains, reducing crystallinity and crystallization rate, and increasing incompatibility with hard segments, thereby accelerating phase separation from the hard segments; therefore, it can exhibit excellent elasticity and compression resilience.

[0021] As described above, the thermoplastic polyester elastomer resin of the present invention has excellent mechanical strength, elasticity and compression resilience, while exhibiting the desired level of hardness; therefore, it can be used to produce a variety of products, such as automotive parts, electrical and electronic components, fibers, films, matrices, cushioning materials, foams, footwear components, etc.

[0022] Best Implementation of the Invention

[0023] The present invention will be described in detail below. The present invention is not limited to the contents disclosed below; it can be modified in various forms as long as the spirit of the invention remains unchanged.

[0024] In this specification, the term "comprising" is intended to specify a particular feature, region, step, method, element, and / or component. Unless otherwise expressly stated, the presence or addition of any other feature, region, step, method, element, and / or component is not excluded.

[0025] In this specification, the terms first, second, etc., are used to describe various components. However, these components should not be limited by these terms. These terms are only used to distinguish one element from another.

[0026] Unless otherwise stated, all numbers and expressions relating to the quantities of components, reaction conditions, etc., used herein should be understood to be modified by the term “about”.

[0027] In thermoplastic polyester elastomer (TPEE) resins, phase separation occurs due to the incompatibility between crystalline hard segments and amorphous soft segments, forming an elastomer matrix that exhibits rubber-like elasticity. To increase the elasticity of TPEE resins, it is necessary to control the clear boundary between hard and soft segments. Specifically, phase separation can be achieved more clearly when the difference in crystallinity and amorphity between hard and soft segments increases to enhance incompatibility and simultaneously increase the free volume of the polymer chains. In other words, hard segments need to crystallize as quickly as possible, while soft segments need to be induced to crystallize as late as possible. Therefore, TPEE resins with high mechanical strength and excellent elastic properties can be obtained.

[0028] In summary, the thermoplastic polyester elastomer resin of the present invention is a mixture of a first polyester elastomer resin and a second polyester elastomer resin. When forming soft segments, the first polyester elastomer resin containing polytrimethylene ether glycol (PO3G) is used to control the crystallinity and crystallization rate of the soft segments at a low level. Furthermore, when forming soft segments, the second polyester elastomer resin containing ethylene oxide-added polypropylene glycol (EO-PPG) is used to increase the incompatibility between the soft and hard segments, thereby achieving clear phase separation. A detailed explanation follows.

[0029] Thermoplastic polyester elastomer resin

[0030] The thermoplastic polyester elastomer resin of the present invention comprises a first polyester elastomer resin containing repeating units (a) represented by Formula 1 and repeating units (b) represented by Formula 2; and a second polyester elastomer resin containing repeating units (a) represented by Formula 1 and repeating units (c) represented by Formula 3. [Formula 1]

[0031] [Equation 2]

[0032] [Formula 3]

[0033] In equations 1 to 3, R 1 To R 3 They are the same or different from each other, and are independently classified as C1 to C. 12 Straight-chain, branched, or cyclic divalent aliphatic hydrocarbon groups, or C6 to C6... 12 The divalent aromatic hydrocarbon group, where m is an integer from 2 to 6, n is an integer from 2 to 3, p is an integer from 10 to 30, t is an integer from 1 to 30, and s is an integer from 1 to 40.

[0034] First polyester elastomer resin

[0035] The first polyester elastomer resin of the present invention is used to increase the mechanical strength of thermoplastic polyester elastomer resin.

[0036] The repeating unit (a) represented by Formula 1 contained in the first polyester elastomer resin can be a repeating unit constituting the hard segment of the first polyester elastomer resin. In Formula 1, R 1 Specifically, it could be C5 to C 12 Cyclic divalent aliphatic hydrocarbon groups or C6 to C6 12 The divalent aromatic hydrocarbon group, m can be an integer from 3 to 5. For example, R 1 It can be cyclohexylene or phenylene, and m can be 4.

[0037] The repeating unit (b) represented by Formula 2 contained in the first polyester elastomer resin can be a repeating unit constituting the soft segment of the first polyester elastomer resin. In Formula 2, R 2 Specifically, it could be C5 to C 12 Cyclic divalent aliphatic hydrocarbon groups or C6 to C6 12 The divalent aromatic hydrocarbon group. Furthermore, n can be 2 or 3, and p can be an integer from 15 to 25. For example, R 2 It can be cyclohexylene or phenylene, n can be 3, and p can be an integer from 18 to 22.

[0038] The repeating unit (a) represented by Formula 1 can be derived from the reaction of a diol component containing 1,4-butanediol and a dicarboxylic acid component. The repeating unit (b) represented by Formula 2 can be derived from the reaction of a dicarboxylic acid component and a high molecular weight diol component containing polytrimethylene ether glycol.

[0039] Specifically, the first polyester elastomer resin can be a resin obtained by using a dicarboxylic acid component (first dicarboxylic acid component), a diol component (first diol component), and a high molecular weight diol component (first high molecular weight diol component) as reaction raw materials.

[0040] The dicarboxylic acid component (e.g., dicarboxylic acid, its ester, chloride, or anhydride) can be an aliphatic dicarboxylic acid component, an aromatic dicarboxylic acid component, or a combination thereof.

[0041] The aliphatic dicarboxylic acid component can be a straight-chain, branched, or cyclic aliphatic dicarboxylic acid component. The number of carbon atoms in the aliphatic dicarboxylic acid component can be 4 or more, 5 or more, 6 or more, or 7 or more, and can be 20 or less, 15 or less, 13 or less, 12 or less, or 10 or less. Specifically, the number of carbon atoms in the aliphatic dicarboxylic acid component can be 4 to 20, 5 to 15, or 6 to 10.

[0042] For example, the aliphatic dicarboxylic acid component may include, but is not limited to, at least one selected from the group consisting of adipic acid, sebacic acid, succinic acid, isodecanic acid, maleic acid, fumaric acid, glutaric acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid.

[0043] The aromatic dicarboxylic acid component may have 6 or more, 7 or more, 8 or more, or 10 or more carbon atoms, and may have 25 or fewer, 20 or fewer, or 15 or fewer carbon atoms. Specifically, the aromatic dicarboxylic acid component may have 6 to 25, 6 to 15, or 6 to 10 carbon atoms.

[0044] For example, the aromatic dicarboxylic acid component may include at least one selected from the group consisting of terephthalic acid, isophthalic acid, naphthalic acid, biphenyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 2,5-furan dicarboxylic acid, 2,5-thiophene dicarboxylic acid and dimethyl terephthalate, but is not limited thereto.

[0045] Preferably, the dicarboxylic acid component may include at least one selected from the group consisting of terephthalic acid and dimethyl terephthalate. The amount (at least one component) of at least one of terephthalic acid and dimethyl terephthalate used (the amount added in the reaction) is not particularly limited, but may be 50 mol% or more, 65 mol% or more, 70 mol% or more, 85 mol% or more, 90 mol% or more, or 95 mol% or more based on the total molar percentage of the dicarboxylic acid component (the first dicarboxylic acid component). Specifically, the amount of terephthalic acid, dimethyl terephthalate, or combinations thereof may be 50 mol% to 100 mol%, 55 mol% to 100 mol%, 60 mol% to 100 mol%, 70 mol% to 100 mol%, 85 mol% to 100 mol%, or 90 mol% to 95 mol%.

[0046] The diol component can undergo esterification or transesterification with the dicarboxylic acid component to form a tetramethyl ester hard segment (e.g., repeating unit (a) of Formula 1). The number of carbon atoms in the diol component can be 2 or more, 3 or more, or 4 or more, and can be 15 or less, 12 or less, 10 or less, or 8 or less. Specifically, the number of carbon atoms in the diol component can be 2 to 15, 3 to 10, 4 to 8, or 4 to 6.

[0047] For example, the diol component may comprise at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanediol, 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, 2,3-butanediol, 3-methyl-1,5-pentanediol, 3-methyl-2,4-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylenediol, polyhexamethylenediol, copolymers of ethylene oxide and tetrahydrofuran, polycarbonate diol, polyneoprene glycol, poly-3-methylpentanediol, and poly-1,5-pentanediol. Specifically, the diol component may include at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,4-cyclohexanediethanol, but is not limited thereto.

[0048] Preferably, the diol component may comprise 1,4-butanediol. The amount of 1,4-butanediol used (the amount added in the reaction) is not particularly limited, but it can be 75 mol% or more, 80 mol% or more, 83 mol% or more, 85 mol% or more, 90 mol% or more, or 95 mol% or more based on the total molar percentage of the diol component (the first diol component). Specifically, the amount of 1,4-butanediol used can be 75 mol% to 100 mol%, 80 mol% to 100 mol%, 83 mol% to 100 mol%, 85 mol% to 100 mol%, 90 mol% to 100 mol%, or 90 mol% to 95 mol%.

[0049] There are no particular restrictions on the number-average molecular weight of the diol component, but it can be less than 400 g / mol, less than 350 g / mol, less than 300 g / mol, or less than 250 g / mol.

[0050] The high molecular weight diol component can undergo esterification or transesterification with the dicarboxylic acid component to form soft segments of the poly(epoxyalkyl) ester (e.g., repeating unit (b) of Formula 2). The high molecular weight diol component may include polytrimethylene ether diol (PO3G). Because the high molecular weight diol component contains polytrimethylene ether diol (PO3G), the mechanical strength of the thermoplastic polyester elastomer resin comprising the first polyester elastomer resin obtained therefrom can be significantly improved.

[0051] Preferably, the high molecular weight diol component may consist of polytrimethylene ether glycol (PO3G). The amount of polytrimethylene ether glycol (PO3G) used (the amount added in the reaction) is not particularly limited, but it can be 50 mol% or more, 60 mol% or more, 75 mol% or more, 85 mol% or more, 95 mol% or more, or 97 mol% or more, based on the total molar percentage of the high molecular weight diol component (the first high molecular weight diol component). Specifically, the amount of polytrimethylene ether glycol (PO3G) can be 50 mol% to 100 mol%, 50 mol% to 99.5 mol%, 60 mol% to 99 mol%, 65 mol% to 95 mol%, 70 mol% to 90 mol%, 75 mol% to 90 mol%, or 75 mol% to 85 mol%.

[0052] There are no particular limitations on the number-average molecular weight of the high molecular weight diol component containing polytrimethylene ether glycol (PO3G), but it can be 400 g / mol or greater, 500 g / mol or greater, 600 g / mol or greater, 700 g / mol or greater, or 800 g / mol or greater, and can be 6000 g / mol or less, 5000 g / mol or less, 4000 g / mol or less, or 3000 g / mol or less. Specifically, to ensure good phase separation from the hard segment, the number-average molecular weight of the high molecular weight diol component containing polytrimethylene ether glycol (PO3G) can be 400 to 5000 g / mol, 800 to 3500 g / mol, or 1000 to 3000 g / mol.

[0053] For example, the number average molecular weight of polytrimethylene ether glycol (PO3G) can be 500 to 4,000 g / mol, 600 to 4,000 g / mol, 800 to 3,500 g / mol, or 1,000 to 3,000 g / mol.

[0054] The first polyester elastomer resin of the present invention may include a structure (repeating unit or structural unit) represented by Formula 4 below, which is a combination of a repeating unit (a) represented by Formula 1 above and a repeating unit (b) represented by Formula 2 above.

[0055] [Formula 4]

[0056] In Equation 4, m, n, and p are the same as described above, and a and b are weight ratios.

[0057] Furthermore, the first polyester elastomer resin can satisfy the following relationship 1.

[0058] [Relation 1]

[0059] 0.5 ≤ a / b ≤ 3.0

[0060] In Equation 1, a is the weight of the repeating unit (a) represented by Equation 1 in the first polyester elastomer resin (total weight of the first polyester elastomer resin), and b is the weight of the repeating unit (b) represented by Equation 2 in the first polyester elastomer resin (total weight of the first polyester elastomer resin).

[0061] Specifically, the a / b ratio in Equation 1 above can be 0.6 to 2.9, 0.7 to 2.8, 0.8 to 2.7, 0.9 to 2.6, or 1.0 to 2.5. When the a / b ratio is within the above range, the mechanical strength of the thermoplastic polyester elastomer resin can be controlled to the desired level.

[0062] The intrinsic viscosity (IV) of the first polyester elastomer resin of the present invention may be 1.0 dl / g or higher, specifically, 1.15 dl / g or higher, 1.3 dl / g or higher, 1.5 dl / g or higher, 1.7 dl / g or higher, or 1.8 dl / g or higher (e.g., 1.0 to 1.9 dl / g, 1.25 to 1.85 dl / g, or 1.3 to 1.8 dl / g).

[0063] Furthermore, the first polyester elastomer resin of the present invention, when measured according to ASTM D638 standard, has a tensile strength of 190 kgf / cm². 2 Or higher, specifically, 210 kgf / cm³ 2 Or higher, 220 kgf / cm 2 Or higher, 240 kgf / cm 2 Or higher, 260 kgf / cm 2 Or higher, 280 kgf / cm 2 Or higher, 320 kgf / cm 2 Or higher, or 360 kgf / cm 2 Or higher (e.g., 190 to 390 kgf / cm³) 2 220 to 380 kgf / cm 2 Or 250 to 350 kgf / cm 2 ).

[0064] Second polyester elastomer resin

[0065] The second polyester elastomer resin of the present invention is used to increase the elasticity and compression resilience of thermoplastic polyester elastomer resins.

[0066] The repeating unit (a) represented by Formula 1 contained in the second polyester elastomer resin can be a repeating unit constituting the hard segment of the second polyester elastomer resin. In Formula 1, R 1 Specifically, it could be C5 to C 12 Cyclic divalent aliphatic hydrocarbon groups or C6 to C6 12 The divalent aromatic hydrocarbon group, m can be an integer from 3 to 5. For example, R 1 It can be cyclohexylene or phenylene, and m can be 4.

[0067] The repeating unit (c) represented by Formula 3 contained in the second polyester elastomer resin can be a repeating unit constituting the soft segment of the second polyester elastomer resin. In Formula 3, R 3 Specifically, it could be C5 to C 12 Cyclic divalent aliphatic hydrocarbon groups or C6 to C6 12 The divalent aromatic hydrocarbon group. Furthermore, t can be an integer from 5 to 25, and s can be an integer from 5 to 35. For example, R 3 It can be cyclohexylene or phenylene, t can be an integer from 10 to 20, and s can be an integer from 10 to 30.

[0068] The repeating unit (a) represented by Formula 1 can be derived from the reaction of a diol component containing 1,4-butanediol and a dicarboxylic acid component. The repeating unit (c) represented by Formula 3 can be derived from the reaction of a dicarboxylic acid component and a high molecular weight diol component containing polypropylene glycol undergoing ethylene oxide addition.

[0069] Specifically, the second polyester elastomer resin can be a resin obtained by using a dicarboxylic acid component (second dicarboxylic acid component), a diol component (second diol component), and a high molecular weight diol component (second high molecular weight diol component) as reaction raw materials.

[0070] The dicarboxylic acid component (e.g., dicarboxylic acid, its ester, chloride, or anhydride) can be an aliphatic dicarboxylic acid component, an aromatic dicarboxylic acid component, or a combination thereof.

[0071] The aliphatic dicarboxylic acid component can be a straight-chain, branched, or cyclic aliphatic dicarboxylic acid component. The number of carbon atoms in the aliphatic dicarboxylic acid component can be 4 or more, 5 or more, 6 or more, or 7 or more, and can be 20 or less, 15 or less, 13 or less, 12 or less, or 10 or less. Specifically, the number of carbon atoms in the aliphatic dicarboxylic acid component can be 4 to 20, 5 to 15, or 6 to 10.

[0072] For example, the aliphatic dicarboxylic acid component may include, but is not limited to, at least one selected from the group consisting of adipic acid, sebacic acid, succinic acid, isodecanic acid, maleic acid, fumaric acid, glutaric acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid.

[0073] The aromatic dicarboxylic acid component may have 6 or more, 7 or more, 8 or more, or 10 or more, and may have 25 or fewer, 20 or fewer, or 15 or fewer. Specifically, the aromatic dicarboxylic acid component may have 6 to 25, 6 to 15, or 6 to 10 carbon atoms.

[0074] For example, the aromatic dicarboxylic acid component may include at least one selected from the group consisting of terephthalic acid, isophthalic acid, naphthalic acid, biphenyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 2,5-furan dicarboxylic acid, 2,5-thiophene dicarboxylic acid and dimethyl terephthalate, but is not limited thereto.

[0075] Preferably, the dicarboxylic acid component may include at least one selected from the group consisting of terephthalic acid and dimethyl terephthalate. The amount (the amount added in the reaction) of at least one component selected from terephthalic acid and dimethyl terephthalate is not particularly limited, but may be 50 mol% or more, 65 mol% or more, 70 mol% or more, 85 mol% or more, 90 mol% or more, or 95 mol% or more based on the total molar percentage of the dicarboxylic acid component (second dicarboxylic acid component). Specifically, the amount of terephthalic acid, dimethyl terephthalate, or combinations thereof may be 50 mol% to 100 mol%, 55 mol% to 100 mol%, 60 mol% to 100 mol%, 70 mol% to 100 mol%, 85 mol% to 100 mol%, or 90 mol% to 95 mol%.

[0076] The diol component can undergo esterification or transesterification with the dicarboxylic acid component to form a tetramethyl ester hard segment (e.g., repeating unit (a) of Formula 1). The number of carbon atoms in the diol component can be 2 or more, 3 or more, or 4 or more, and can be 15 or less, 12 or less, 10 or less, or 8 or less. Specifically, the number of carbon atoms in the diol component can be 2 to 15, 3 to 10, 4 to 8, or 4 to 6.

[0077] For example, the diol component may comprise at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanediol, 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, 2,3-butanediol, 3-methyl-1,5-pentanediol, 3-methyl-2,4-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylenediol, polyhexamethylenediol, copolymers of ethylene oxide and tetrahydrofuran, polycarbonate diol, polyneoprene glycol, poly-3-methylpentanediol, and poly-1,5-pentanediol. Specifically, the diol component may include at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,4-cyclohexanediethanol.

[0078] Preferably, the diol component may comprise 1,4-butanediol. The amount of 1,4-butanediol used (the amount added in the reaction) is not particularly limited, but it may be 75 mol% or more, 80 mol% or more, 83 mol% or more, 85 mol% or more, 90 mol% or more, or 95 mol% or more, based on the total molar percentage of the diol component (second diol component). Specifically, the amount of 1,4-butanediol may be 75 mol% to 100 mol%, 80 mol% to 100 mol%, 83 mol% to 100 mol%, 85 mol% to 100 mol%, 90 mol% to 100 mol%, or 90 mol% to 95 mol%.

[0079] There are no particular restrictions on the number-average molecular weight of the diol component, but it can be less than 400 g / mol, less than 350 g / mol, less than 300 g / mol, or less than 250 g / mol.

[0080] The high molecular weight diol component can undergo esterification or transesterification with the dicarboxylic acid component to form soft segments of poly(epoxyalkyl) esters (e.g., repeating unit (c) of Formula 3). The high molecular weight diol component may include ethylene oxide-added polypropylene glycol (EO-PPG). Because the high molecular weight diol component contains ethylene oxide-added polypropylene glycol (EO-PPG), the elasticity and compression resilience of the thermoplastic polyester elastomer resin can be significantly improved.

[0081] Preferably, the high molecular weight glycol component may consist of ethylene oxide-added polypropylene glycol (EO-PPG). The amount of ethylene oxide-added polypropylene glycol (EO-PPG) used (the amount added in the reaction) is not particularly limited, but it may be 50 mol% or more, 60 mol% or more, 75 mol% or more, 85 mol% or more, 95 mol% or more, or 97 mol% or more, based on the total molar percentage of the high molecular weight glycol component (the second high molecular weight glycol component). Specifically, the amount of ethylene oxide-added polypropylene glycol (EO-PPG) used may be 50 mol% to 100 mol%, 50 mol% to 99.5 mol%, 60 mol% to 99 mol%, 65 mol% to 95 mol%, 70 mol% to 90 mol%, 75 mol% to 90 mol%, or 75 mol% to 85 mol%.

[0082] There are no particular limitations on the number-average molecular weight of the high molecular weight diol component comprising ethylene oxide-added polypropylene glycol (EO-PPG), but it can be 400 g / mol or more, 500 g / mol or more, 600 g / mol or more, 700 g / mol or more, or 800 g / mol or more, and can be 6,000 g / mol or less, 5,000 g / mol or less, 4,000 g / mol or less, or 3,000 g / mol or less. Specifically, for good phase separation from the hard segment, the number-average molecular weight of the high molecular weight diol component can be 400 to 5,000 g / mol, 800 to 3,500 g / mol, or 1,000 to 3,000 g / mol.

[0083] For example, the number average molecular weight of ethylene oxide-added polypropylene glycol (EO-PPG) can be 1,000 to 4,000 g / mol, 1,500 to 3,500 g / mol, 2,000 to 3,500 g / mol, or 2,000 to 3,000 g / mol.

[0084] The second polyester elastomer resin of the present invention may include a structure (repeating unit or structural unit) represented by Formula 5 below, which is formed by combining the repeating unit (a) represented by Formula 1 above and the repeating unit (c) represented by Formula 3 above.

[0085] [Formula 5]

[0086] In Equation 5, m, t, and s are the same as described above, and a and c are weight ratios.

[0087] Furthermore, the second polyester elastomer resin can satisfy the following relationship 2.

[0088] [Relation 2]

[0089] 0.5 ≤ a / c ≤ 2.5

[0090] In Equation 2, a is the weight of the repeating unit (a) represented by Equation 1 in the second polyester elastomer resin (total weight of the second polyester elastomer resin), and c is the weight of the repeating unit (c) represented by Equation 3 in the second polyester elastomer resin (total weight of the second polyester elastomer resin).

[0091] Specifically, the a / c ratio in Equation 2 above can be 0.6 to 2.4, 0.7 to 2.3, 0.8 to 2.2, 0.9 to 2.1, or 1.0 to 2.0. When the a / c ratio is within the above range, the elasticity and compression resilience of the thermoplastic polyester elastomer resin can be controlled to the desired level.

[0092] Two or more types of second polyester elastomer resins can be used. That is, when considering the properties of thermoplastic polyester elastomer resins, second-1 polyester elastomer resin and second-2 polyester elastomer resin can be used as the second polyester elastomer resin.

[0093] The intrinsic viscosity (IV) of the second polyester elastomer resin of the present invention can be 1.0 dl / g or higher, specifically 1.03 dl / g or higher, 1.05 dl / g or higher, 1.07 dl / g or higher, 1.1 dl / g or higher, or 1.3 dl / g or higher (e.g., 1.0 to 1.5 dl / g, 1.05 to 1.45 dl / g, or 1.25 to 1.4 dl / g).

[0094] Furthermore, the second polyester elastomer resin of the present invention has a tensile strength of 100 kgf / cm² as tested according to ASTM D638. 2 Or higher, specifically, 105 kgf / cm³ 2 Or higher, 110 kgf / cm 2 Or higher, 115 kgf / cm 2 Or higher, 120 kgf / cm 2 Or higher, 140 kgf / cm 2 Or higher, 160 kgf / cm 2 Or higher, or 180 kgf / cm 2 Or higher (e.g., 100 to 200 kgf / cm²) 2 120 to 190 kgf / cm 2 or 150 to 180 kgf / cm 2 ).

[0095] The blending ratio of the first and second polyester elastomer resins contained in the thermoplastic polyester elastomer resin of this invention can be 40:60 to 99:1, 45:55 to 99:1, 50:50 to 98:2, 55:45 to 98:2, 60:40 to 90:10, 65:35 to 90:10, 70:30 to 85:15, or 75:25 to 85:15 by weight. Since the blending ratio of the first and second polyester elastomer resins is within the above ranges, a thermoplastic polyester elastomer resin with excellent elasticity, compression resilience, and mechanical strength can be provided.

[0096] Thermoplastic polyester elastomer resins may include mixtures of a first polyester elastomer resin and a second polyester elastomer resin, crosslinked products of a first polyester elastomer resin and a second polyester elastomer resin, or combinations thereof. Specifically, the thermoplastic polyester elastomer resin may be a blended resin in which a first polyester elastomer resin and a second polyester elastomer resin are blended, a crosslinked resin in which the first polyester elastomer resin and the second polyester elastomer resin are physically or chemically bonded (copolymerized thermoplastic polyester elastomer resin), or a resin consisting of a blended resin and a crosslinked resin.

[0097] The thermoplastic polyester elastomer resin of the present invention includes a first polyester elastomer resin and a second polyester elastomer resin. That is, it can be a resin containing repeating units (a), repeating units (b), and repeating units (c), wherein the content ratio (weight ratio) between these repeating units is controlled within a specific range.

[0098] Specifically, the thermoplastic polyester elastomer resin of the present invention can satisfy the following relationship 3. Because the thermoplastic polyester elastomer resin satisfies the following relationship 3, it can have the desired molecular weight and high mechanical strength.

[0099] [Relationship 3]

[0100] 0.5 ≤ (y + z) / x ≤ 3.0

[0101] In Equation 3, x is the total weight of the thermoplastic polyester elastomer resin represented by the repeating unit (a) of Equation 1 (total weight of thermoplastic polyester elastomer resin), y is the total weight of the thermoplastic polyester elastomer resin represented by the repeating unit (b) of Equation 2 (total weight of thermoplastic polyester elastomer resin), and z is the total weight of the thermoplastic polyester elastomer resin represented by the repeating unit (c) of Equation 3 (total weight of thermoplastic polyester elastomer resin).

[0102] Specifically, in relation 3, the ratio of (y + z) / x can be 0.55 to 2.95, 0.65 to 2.90, 0.68 to 2.85, 0.7 to 2.8, 0.75 to 2.7, 0.8 to 2.6, 1 to 2.55, 1.05 to 2.45, 1.08 to 2.4, or 1.1 to 2.3.

[0103] Furthermore, the thermoplastic polyester elastomer resin of the present invention can satisfy the following relationship 4. Because the thermoplastic polyester elastomer resin satisfies the following relationship 4, it can exhibit superior elasticity and compression resilience.

[0104] [Relationship 4]

[0105] 0.3 ≤ y / z ≤ 37

[0106] In Equation 4, y is the total weight of the repeating unit (b) represented by Equation 2 in the thermoplastic polyester elastomer resin (total weight of the thermoplastic polyester elastomer resin), and z is the total weight of the repeating unit (c) represented by Equation 3 in the thermoplastic polyester elastomer resin (total weight of the thermoplastic polyester elastomer resin).

[0107] Specifically, in relation 4, the ratio of y / z can be 0.5 to 36.7, 0.55 to 36, 0.58 to 30, 0.6 to 25, 0.8 to 20, 1 to 15, 1.05 to 10, 1.1 to 8, 1.2 to 5, 1.3 to 4.5, or 1.5 to 4.

[0108] Furthermore, the thermoplastic polyester elastomer resin of the present invention may further include reactive compatibilizers, bonding structures derived from reactive compatibilizers, or combinations thereof, to further enhance elasticity and compression resilience, as well as mechanical strength, elongation, etc.

[0109] A reactive compatibilizer is an additive that prevents phase separation between resin components in a mixture of two or more resins and helps improve miscibility by forming a stable and long-lasting continuous phase. Specifically, a reactive compatibilizer is a reactive polymer that is compatible with one component of a resin mixture and reacts with the functional groups of another resin component. When added to a mixture of two resins (i.e., a first polyester elastomer resin and a second polyester elastomer resin) for a reactive extrusion process, it can induce the formation of block copolymers or graft copolymers.

[0110] Reactive compatibilizers can be selected from the group consisting of isocyanate compounds, carbodiimide compounds (e.g., polycarbodiimide compounds having two or more -N=C=N- structures in the molecule), epoxy compounds, oxazoline compounds, compounds with glycidyl groups, and compounds with maleic anhydride structures. Isocyanate compounds are too reactive with water; therefore, reactivity and handling (storage) convenience may be difficult to control. Carbodiimide compounds are expensive; therefore, economic feasibility may be low. Furthermore, epoxy compounds may exhibit large differences in reactivity due to epoxy equivalents and the number of functional groups, making reactivity difficult to control. Oxazoline compounds have lower reactivity than other compounds; therefore, it is difficult to expect them to enhance the miscibility between resin components. Therefore, compounds with glycidyl groups or compounds with maleic anhydride structures are preferred as reactive compatibilizers.

[0111] Compounds containing a glycidyl group can specifically be glycidyl-modified olefin-based rubber polymers, preferably polymers grafted with glycidyl (meth)acrylate onto polyolefin-based rubber copolymers (glycidyl (meth)acrylate-grafted polyolefin elastomers). Compounds containing a maleic anhydride structure can specifically be polymers grafted with maleic anhydride onto polyolefin-based rubber copolymers (maleic anhydride-grafted polyolefin elastomers).

[0112] For example, a reactive compatibilizer may be a poly(ethylene-co-methacrylate-co-glycidyl methacrylate) having a structure represented by Formula 6. Alternatively, a reactive compatibilizer may be a poly(ethylene-co-ethyl acrylate-co-maleic anhydride) having a structure represented by Formula 7.

[0113] [Formula 6]

[0114] [Formula 7]

[0115] In Equation 6, a is an integer from 116 to 268, b is an integer from 12 to 29, and c is an integer from 2 to 7. For example, in Equation 6, based on the total weight of poly(ethylene-co-methacrylate-co-glycidyl methacrylate), structure a can account for 65% to 75% by weight, structure b can account for 20% to 25% by weight, and structure c can account for 5% to 10% by weight.

[0116] Additionally, in Formula 7, d is an integer from 129 to 300, e is an integer from 8 to 25, and f is an integer from 1 to 3. For example, in Formula 7, based on the total weight of poly(ethylene-co-ethyl acrylate-co-maleic anhydride), structure d can account for 72% to 84% by weight, structure e can account for 15% to 25% by weight, and structure f can account for 1% to 3% by weight.

[0117] Examples of commercially available reactive compatibilizers include Rotarder AX8840, Rotarder AX8900, and Rotarder AX4720.

[0118] The amount of reactive compatibilizer used in this invention (the amount added in the reaction) is not particularly limited, but it can be 0.1% to 10% by weight, 0.3% to 9% by weight, 0.5% to 8% by weight, 0.8% to 7% by weight, 1% to 5% by weight, 1.5% to 4.5% by weight, or 2% to 4% by weight, based on the total weight of the thermoplastic polyester elastomer resin (the total weight of the first and second polyester elastomer resins). When the amount of reactive compatibilizer is within the above range, the thermoplastic polyester elastomer resin can have the desired level of melt viscosity, thereby improving moldability (processability).

[0119] When a reactive compatibilizer is used, the thermoplastic polyester elastomer resin of the present invention may comprise repeating units (a) represented by Formula 1 above, repeating units (b) represented by Formula 2 above, repeating units (c) represented by Formula 3 above, and bonding structures derived from the reactive compatibilizer (e.g., structures represented by Formula 6 or Formula 7 above). Specifically, the thermoplastic polyester elastomer resin may be a copolymerized thermoplastic polyester elastomer resin, wherein the structures represented by Formula 4 above and the structures represented by Formula 5 above are combined by the structures represented by Formula 6 above or the structures represented by Formula 7 above.

[0120] The thermoplastic polyester elastomer resin of the present invention selectively includes a reactive compatibilizer, as well as a first polyester elastomer resin and a second polyester elastomer resin, wherein the high molecular weight diol components (PO3G and EO-PPG) are each used to form the soft segments as described above, thereby enhancing the performance.

[0121] Specifically, the thermoplastic polyester elastomer resin of the present invention, when measured according to ASTM D638, has a tensile strength of 150 kgf / cm². 2 Or larger, 170 kgf / cm 2 Or larger, 190 kgf / cm 2 Or larger, 195 kgf / cm 2 Or larger, 200 kgf / cm 2 Or larger, 205 kgf / cm2 Or larger, 220 kgf / cm 2 Or larger, 230 kgf / cm 2 Or larger, 240 kgf / cm 2 Or larger or 250 kgf / cm 2 Or even greater. More specifically, the tensile strength can be from 190 to 350 kgf / cm². 2 195 to 335 kgf / cm 2 200 to 325 kgf / cm 2 Or 210 to 320 kgf / cm 2 .

[0122] The intrinsic viscosity (IV) of the thermoplastic polyester elastomer resin of the present invention can be 0.9 to 2.4 dl / g, 1.0 to 2.4 dl / g, 1.05 to 2.3 dl / g, 1.1 to 2.2 dl / g, 1.2 to 2 dl / g, 1.3 to 1.9 dl / g, 1.35 to 1.88 dl / g, or 1.4 to 1.85 dl / g.

[0123] The Shore D hardness of the thermoplastic polyester elastomer resin of the present invention can be 20 to 60, 25 to 55, 28 to 53, 28 to 50, 30 to 48 or 30 to 45.

[0124] The compression set (compression resilience) of the thermoplastic polyester elastomer resin of the present invention can be 30% to 60%, 31% to 58%, 33% to 57%, 35% to 56%, 37% to 55%, 39% to 54%, 40% to 53%, or 42% to 52%.

[0125] The resilience (elasticity) of the thermoplastic polyester elastomer resin of the present invention can be 50% to 80%, 51% to 79%, 52% to 78%, 54% to 76%, 55% to 75%, 56% to 74%, 58% to 73%, or 60% to 70%.

[0126] The thermoplastic polyester elastomer resin of the present invention satisfies the following relation 5 and / or relation 6, thereby exhibiting excellent mechanical strength, elasticity, and compression resilience.

[0127] [Relation 5]

[0128] H / R ≤ 0.97

[0129] [Relationship 6]

[0130] 0.6 ≤ H / CS

[0131] In equations 5 and 6, H is the Shore D hardness of the thermoplastic polyester elastomer resin as measured according to ASTM D2240, R is the resilience of the thermoplastic polyester elastomer resin as measured according to ASTM D2632, and CS is the compression set of the thermoplastic polyester elastomer resin as measured according to ISO 816 Method b.

[0132] Specifically, the H / R ratio can be 0.75 or less, 0.73 or less, 0.70 or less, or 0.68 or less, and 0.3 or more, 0.32 or more, 0.34 or more, 0.38 or more, 0.4 or more, 0.42 or more, or 0.48 or more (e.g., 3 to 0.75, 0.32 to 0.75, 0.34 to 0.73, 0.38 to 0.73, 0.4 to 0.70, 0.42 to 0.70, or 0.48 to 0.68).

[0133] In addition, the H / CS ratio can be 0.7 or greater, 0.8 or greater, 0.81 or greater, or 0.82 or greater, and 0.95 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.89 or less, or 0.88 or less (e.g., 0.7 to 0.95, 0.8 to 0.93, 0.8 to 0.92, 0.81 to 0.91, 0.81 to 0.9, 0.82 to 0.89, or 0.82 to 0.88).

[0134] The thermoplastic polyester elastomer resin of the present invention possesses basic physical properties (e.g., heat resistance, impact resistance, moldability, etc.) and excellent mechanical strength, elasticity, and compression resilience. Therefore, it can be used to produce a variety of products. Specifically, the thermoplastic polyester elastomer resin can be used to produce fibers, films, foams (foam-type molded articles), and footwear components (e.g., cushioning materials for shoe midsoles, outsoles, and insoles).

[0135] Method for preparing thermoplastic polyester elastomer resin

[0136] The thermoplastic polyester elastomer resin of the present invention can be prepared by the following steps: obtaining a first thermoplastic polyester elastomer resin and a second thermoplastic polyester elastomer resin respectively through esterification or transesterification reactions of various reactants, followed by polycondensation reaction, and melt blending of these resins. Specifically, the method for preparing the thermoplastic polyester elastomer resin of the present invention includes (1-1) reacting a first diol component, a first dicarboxylic acid component, and a first high molecular weight diol component to obtain a first polyester elastomer resin; (1-2) reacting a second diol component, a second dicarboxylic acid component, and a second high molecular weight diol component to obtain a second polyester elastomer resin; and (1-3) melt blending the first polyester elastomer resin and the second polyester elastomer resin, the reactions of which will be described in detail below.

[0137] Step (1-1): Preparation of the first polyester elastomer resin

[0138] In this invention, step (1-1) involves adding a first diol component, a first dicarboxylic acid component, and a first high molecular weight diol component as reaction raw materials to a reactor (esterification reactor or transesterification reactor) and carrying out an esterification reaction or transesterification reaction to obtain a reactant, followed by a polycondensation reaction to obtain a first polyester elastomer resin. Preferably, the first diol component comprises 1,4-butanediol, and the first high molecular weight diol component comprises polytrimethylene ether diol (PO3G). The descriptions of these components are the same as described above and are therefore omitted. Furthermore, the description of the first dicarboxylic acid component is the same as described above and is therefore omitted.

[0139] For esterification reactors or transesterification reactions, the first diol component, the first dicarboxylic acid component, and the first high molecular weight diol component are added to the reactor all at once. Alternatively, the first diol component and the first dicarboxylic acid component are added first, and the temperature is increased. When the reactor temperature reaches a certain level, the first high molecular weight diol component can be added. For example, the first high molecular weight diol component can be added under a nitrogen atmosphere at a temperature of 180°C to 280°C, while simultaneously removing water or methanol as a byproduct.

[0140] Esterification or transesterification can be carried out in the presence of a catalyst. There are no particular limitations on the catalyst, as long as it is a known catalyst. Specifically, at least one catalyst selected from the group consisting of titanium-based catalysts, germanium-based catalysts, antimony-based catalysts, aluminum-based catalysts, and tin-based catalysts can be used.

[0141] For example, titanium-based catalysts may include at least one selected from the group consisting of tetraethyl titanate, tripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, 2-ethylhexyl titanate, octyl glycol titanate, triethanolamine titanate, acetylacetone titanate, ethyl acetoacetate titanate, isostearate titanate, and titanium dioxide. Germanium-based catalysts may include at least one selected from the group consisting of germanium dioxide, germanium tetrachloride, germanium glycol oxide, and germanium acetate.

[0142] The amount of catalyst (the amount added to the reaction) can be adjusted appropriately according to the reaction conditions and the type of catalyst. For example, a catalyst can be added such that the weight of the metal component (e.g., Ti, Ge, Sb, Al, Sn, etc.) contained in the catalyst is 0.0001 to 0.005 parts by weight of the total weight of the first diol component, the first dicarboxylic acid component, and the first high molecular weight diol component added to the reactor.

[0143] Meanwhile, during esterification or transesterification, one or more additives selected from the group consisting of crystallizing agents, antioxidants, and polymerization branching agents can be added.

[0144] Crystallizing agents such as crystal nucleating agents, ultraviolet absorbers, polyolefin resins, and polyamide resins can be used.

[0145] At least one of the group consisting of hindered phenolic compounds, phosphites, and thioethers can be used as an antioxidant.

[0146] Polyols having 3 to 6 hydroxyl groups; polycarboxylic acids or their anhydrides having 3 to 4 carboxyl groups; or hydroxy acids having a total of 3 to 6 hydroxyl and carboxyl groups can be used as branching agents for the polymerization reaction. Specifically, the polyol may include at least one selected from the group consisting of glycerol, sorbitol, pentaerythritol, 1,1,4,4-tetra(hydroxymethyl)cyclohexane, trimethylolpropane, and 1,2,6-hexanetriol. Furthermore, the polycarboxylic acid may include hexabenzoic acid, trimellitic acid, triphenyltetracarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2-ethanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, and 1,2,3,4-cyclopentanetetracarboxylic acid. For example, trimellitic acid, trimellitic anhydride, trimethylolpropane, or combinations thereof may be used as branching agents for the polymerization reaction to control the melt index (MI) of the thermoplastic polyester elastomer resin to the desired level.

[0147] There is no particular limitation on the amount of the branching agent in the polymerization reaction (the amount added in the reaction), but its concentration can be from 0.00015 equivalents to 0.005 equivalents per 100 grams of the first thermoplastic polyester elastomer resin.

[0148] Esterification or transesterification reactions are usually carried out without the addition of solvents, but inert solvents such as water and glycols can be added to accelerate the removal of volatile components.

[0149] The conditions for esterification or transesterification reactions can be adjusted appropriately based on the reaction environment and the molecular weight of the desired reactants. Specifically, the pressure for esterification or transesterification reactions can be 0.01 kg / cm². 2 Or larger, 0.05 kg / cm 2 Or larger, or 0.1 kg / cm 2 Or larger, and could be 1.5 kg / cm². 2 or smaller, 1 kg / cm 2 or smaller, 0.5 kg / cm 2 Or smaller, or 0.3 kg / cm 2Or lower. The temperature for esterification or transesterification can be 140°C or higher, 160°C or higher, 180°C or higher, or 200°C or higher, and can be 300°C or lower, 280°C or lower, 270°C or lower, 250°C or lower, or 220°C or lower. Esterification or transesterification can be carried out under a nitrogen atmosphere. For example, esterification or transesterification can be carried out under a nitrogen atmosphere and a concentration of 0.05 to 1.5 kg / cm³. 2 And it is carried out under conditions of 180 to 280°C.

[0150] Esterification or transesterification can be carried out in a batch or continuous manner.

[0151] The termination point of an esterification or transesterification reaction can be determined by taking into account the theoretical amount of water or methanol as a byproduct formed from the first dicarboxylic acid component, or by when no more byproducts are discharged.

[0152] The reactants obtained through the esterification or transesterification reaction can undergo polycondensation. In this case, there are no particular restrictions on the conditions for carrying out the polycondensation reaction.

[0153] Specifically, the polycondensation reaction can be carried out under a vacuum atmosphere. Furthermore, the pressure of the polycondensation reaction can be 0.01 to 600 mmHg, 0.05 to 200 mmHg, 0.1 to 100 mmHg, 0.5 to 50 mmHg, or 1 to 10 mmHg. Additionally, the temperature of the polycondensation reaction can be 150 to 300°C, 200 to 290°C, 220 to 280°C, or 230 to 260°C. For example, the polycondensation reaction can be carried out under reduced pressure of 0.1 to 10 mmHg and at 200 to 260°C for 1 to 24 hours. When the polycondensation reaction is carried out under the above conditions, a first polyester elastomer resin with the desired molecular weight and intrinsic viscosity (IV) can be produced, while byproducts are sufficiently removed.

[0154] Through the above process, a first polyester elastomer resin comprising repeating units ((a) and (b)) represented by the above general formulas 1 and 2 can be prepared in high yield.

[0155] Step (1-2): Preparation of the second polyester elastomer resin

[0156] Steps (1-2) of this invention involve adding a second diol component, a second dicarboxylic acid component, and a second high molecular weight diol component, as reactants, into a reactor (esterification reactor or transesterification reactor) and carrying out an esterification or transesterification reaction to obtain reactants, followed by a polycondensation reaction to obtain a second polyester elastomer resin. The second diol component includes 1,4-butanediol, and the second high molecular weight diol component includes ethylene oxide-added polypropylene glycol (EO-PPG). The descriptions of these components are the same as described above and are therefore omitted. Furthermore, the description of the second dicarboxylic acid component is the same as described above and is therefore omitted.

[0157] For esterification reactors or transesterification reactions, the second diol component, the second dicarboxylic acid component, and the second high molecular weight diol component are added to the reactor all at once. Alternatively, the second diol component and the second dicarboxylic acid component are added first, and the temperature is increased. When the reactor temperature reaches a certain level, the second high molecular weight diol component can be added. For example, the second high molecular weight diol can be added under a nitrogen atmosphere at a temperature of 180°C to 280°C, while simultaneously removing water or methanol as byproducts.

[0158] The description of the esterification or transesterification reaction is the same as that of the esterification or transesterification reaction for the preparation of the first polyester elastomer resin; therefore, it is omitted.

[0159] Reactants obtained through esterification or transesterification can undergo polycondensation. In this case, there are no particular restrictions on the conditions for polycondensation. Specifically, the description of the polycondensation reaction is the same as that of the polycondensation reaction for preparing the first polyester elastomer resin; therefore, it is omitted.

[0160] Through the above steps, a second polyester elastomer resin comprising repeating units ((a) and (c)) represented by the above formulas 1 and 3 can be prepared in high yield.

[0161] Steps (1-3): Melt mixing

[0162] Step (1-3) of the present invention is the process of obtaining the first polyester elastomer resin in the melt blending step (1-1) and the second polyester elastomer resin in the step (1-2).

[0163] Melt mixing can be carried out under heating and / or pressure using melt mixing reactors such as single-screw extruders, twin-screw extruders, mixing rolls, Banbury mixers, batch mixers, molding machines, etc.

[0164] For melt blending, a premixing step can be performed on the first and second polyester elastomer resins. Specifically, the premixing step can be achieved by adding the first and second polyester elastomer resins to various mixers, such as V-type mixers, belt mixers, Henschel mixers, oscillating mixers, vortex mixers, planetary mixers, Banbury mixers, mill mixers, mixing rollers, and drum mixers, for premixing in solid form. The mixing time for solid form can vary depending on the type of mixer, but the mixing time can be adjusted so that when samples are taken at five random locations after mixing, the standard deviation of the target mix ratio is within 1%, and at most does not exceed 2%.

[0165] In the premixing step, known additives (e.g., colorants, fillers, sunscreens, heat stabilizers, etc.) can be added as needed. Here, the first and second polyester elastomer resins can be directly added to the melt-blending reactor without a premixing step. Alternatively, thermoplastic polyester elastomer resins can be prepared by premixing some raw material components, then melt-blending them to obtain reactants for use as masterbatches, mixing the remaining raw material components with the masterbatch, and then melt-blending them again.

[0166] Melt compounding can preferably be carried out in a single-screw extruder or a twin-screw extruder. There are no particular limitations on the temperature (e.g., the barrel temperature) of the extruder during melt compounding, and it can be determined based on miscibility, ease of extrusion, and extrusion reaction efficiency. Specifically, melt compounding can be carried out at a temperature 20°C to 30°C higher than the melt temperature (Tm) of the desired thermoplastic polyester elastomer resin. For example, the temperature during melt compounding can be 170°C to 230°C, 180°C to 225°C, 190°C to 220°C, 195°C to 215°C, or 200°C to 210°C. Specifically, melt compounding can be performed at 150 to 230 rpm, 160 to 225 rpm, 170 to 220 rpm, 180 to 210 rpm, 190 to 205 rpm, or 195 to 200 rpm. When melt compounding is carried out under these conditions, sufficient melt compounding and reactive extrusion can be achieved, and an appropriate yield per unit time can be obtained. If the above conditions are not met, the thermoplastic polyester elastomer resin may thermally decompose, or its melting characteristics may be poor, resulting in insufficient melt mixing.

[0167] There are no particular restrictions on the blending ratio of the first polyester elastomer resin and the second polyester elastomer resin in the melt blending, but it can be a weight ratio of 40:60 to 99:1, 45:55 to 99:1, 50:50 to 98:2, 55:45 to 98:2, 60:40 to 90:10, 65:35 to 90:10, 70:30 to 85:15 or 75:25 to 85:15.

[0168] Meanwhile, the melt blending in steps (1-3) can be carried out in the presence of a reactive compatibilizer. Specifically, steps (1-3) can be carried out by premixing the first polyester elastomer resin and the second polyester elastomer resin with the reactive compatibilizer and then melt blending them, or by adding the first polyester elastomer resin, the second polyester elastomer resin and the reactive compatibilizer to a melt blending reactor without premixing and then melt blending them.

[0169] Because melt mixing is carried out in the presence of a reactive compatibilizer, the dispersibility of the first and second polyester elastomer resins can be maximized, and chemical crosslinking can be achieved. As a result, copolymer thermoplastic polyester elastomer resins with excellent mechanical strength, elasticity, and compression resilience can be prepared while ensuring basic physical properties.

[0170] Specifically, when a reactive compatibilizer is used, dispersion and bonding can be achieved between a second polyester elastomer resin and a first polyester elastomer resin without microphase separation. The second polyester elastomer resin has repeating units derived from ethylene oxide-added polypropylene glycol (EO-PPG) with an energy-repellent elastic effect (repeating unit (c) of Formula 3), and the first polyester elastomer resin has repeating units derived from polytrimethylene ether glycol (PO3G) that determines mechanical strength (repeating unit (b) of Formula 2). Therefore, thermoplastic polyester elastomer resins with excellent elasticity and compression resilience can be prepared.

[0171] Specifically, when melt compounding is performed using (added) reactive compatibilizers, the hydroxyl (-OH) or carboxyl (-COOH) groups present in the first polyester elastomer resin and the second polyester elastomer resin, respectively, can react with the glycidyl group or maleic anhydride structure in the reactive compatibilizer to form ether bonds or ester bonds.

[0172] The description of reactive compatibilizers is the same as above, and therefore omitted.

[0173] Compositions and Articles

[0174] The compositions of the present invention comprise the aforementioned thermoplastic polyester elastomer resin. Specifically, because the compositions of the present invention comprise a thermoplastic polyester elastomer resin having excellent mechanical strength, elasticity, and compression resilience, they can be used to produce a variety of products.

[0175] As needed, the compositions of the present invention may further comprise known solvents and additives.

[0176] Furthermore, the articles of the present invention comprise the aforementioned thermoplastic polyester elastomer resin. The articles of the present invention are not particularly limited, but may be fibers, foam (molded articles in foam form), or footwear components.

[0177] The fibers can be monocomponent fibers and / or multicomponent fibers (e.g., bicomponent fibers). The fibers can be made into woven fabrics, knitted fabrics, or nonwoven fabrics.

[0178] Foam (molded articles in foam form) can be manufactured by physical or chemical foaming processes of a composition comprising the aforementioned thermoplastic polyester elastomer resin in a mold or autoclave. There are no particular limitations on the density of the foam, but it can be from 0.15 to 0.45 g / cm³. 3 Because of the use of the aforementioned thermoplastic polyester elastomer resin, the foam exhibits high elasticity and energy rebound properties; therefore, it can be applied to straps, bogie gears, highly elastic shock-absorbing components, etc.

[0179] Footwear components are obtained by placing a composition comprising the aforementioned thermoplastic polyester elastomer resin into a mold and molding it. Specifically, it can be a cushioning material for a shoe midsole, outsole, or insole. Detailed Implementation

[0180] Invention Model

[0181] The present invention will now be described in more detail with reference to embodiments. However, these embodiments are provided for illustrative purposes only, and the present invention is not limited thereto.

[0182] [Polymerization Example 1]

[0183] Step (1-1): Preparation of reactants via transesterification

[0184] The volume is 1.2m³ 3 The transesterification reactor, equipped with a water-cooled tower and condenser, was charged with 18.1 kg of 1,4-butanediol (1,4-BD) as the diol component; 66.2 kg of polytrimethylene ether glycol (PO3G) as the high molecular weight diol component; 32.3 kg of dimethyl terephthalate (DMT) as the dicarboxylic acid component; 0.11 kg of trimellitic anhydride (TMA) as the polymerization branching agent; 0.25 kg of tetrabutyl titanate (TBT) as the reaction catalyst; 0.15 kg of I1098 and 0.15 kg of I1019 as the primary antioxidants; and 0.1 kg of I168 as the secondary antioxidant. Subsequently, the reactor was evacuated and nitrogen was introduced to restore the pressure in the reactor to 1 kg / cm². 2An inert atmosphere was created. The added raw materials were then stirred under a nitrogen atmosphere while the temperature was increased. When the temperature in the reactor reached approximately 200°C, the transesterification reaction proceeded for 3 hours, while the temperature was maintained at 200°C. During this process, the byproduct methanol was discharged through a column and condenser during the transesterification reaction, which continued until the methanol discharge ceased. After the transesterification reaction was completed, the nitrogen gas in the pressurized reactor was released to the outside, reducing the pressure inside the reactor to atmospheric pressure. The reactants (the resulting material) were then transferred to a 0.75 m³ / h reactor capable of reacting under vacuum. 3 condensation reactor.

[0185] Steps (1-2): Preparation of polyester elastomer resin via polycondensation reaction

[0186] Within 30 minutes, the pressure in the polycondensation reactor is reduced from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg). Simultaneously, the temperature of the polycondensation reactor is raised to 245°C within 1 hour, and the polycondensation reaction is carried out while maintaining the pressure in the reactor at 1 Torr (absolute pressure: 1 mmHg) or lower. In this case, the stirring speed can be set relatively high at the beginning of the polycondensation reaction. As the polycondensation reaction proceeds, the diol component produced as a byproduct is discharged through a column and condenser. The stirring speed is adjusted appropriately when the stirring power weakens due to increased reactant viscosity or when the reactant temperature rises above the set temperature. Subsequently, the polycondensation reaction continues until the intrinsic viscosity (IV) of the reactants (melt) in the reactor reaches 1.85 dl / g. When the intrinsic viscosity (IV) of the reactants in the reactor reaches the desired level, the reactants are discharged outside the reactor and formed into a filament. This filament is then solidified with a coolant and granulated so that the average weight of 100 granules is approximately 2.5 g to 4.0 g, thus obtaining the polyester elastomer resin.

[0187] [Composite Examples 2 and 3]

[0188] Except for the variation in the amount of polytrimethylene ether glycol (PO3G) added as a high molecular weight diol component in the transesterification reaction as shown in Table 1 below, the polyester elastomer resin was obtained by the same preparation method as in polymerization Example 1.

[0189] [Collaborative Examples 4 and 5]

[0190] Except that ethylene oxide-added polypropylene glycol (EO-PPG) was used instead of polytrimethylene ether glycol (PO3G) as the high molecular weight glycol component, and trimethylolpropane (TMP) was used instead of trimellitic anhydride (TMA) as the branching agent in the polymerization reaction and added to the transesterification reaction, with the amounts varying as shown in Table 1 below, polyester elastomer resin was obtained by the same preparation method as in polymerization Example 1.

[0191] [Table 1]

[0192] [Example 1]

[0193] 2.1 kg of the resin from Example 1 was used as the first polyester elastomer resin; 0.9 kg of the resin from Example 4 was used as the second polyester elastomer resin; and 60 g of Rotader ax 8900 was used as a reactive compatibilizer. The mixture was then solid-state mixed (the blending ratio of the first and second polyester elastomer resins was 70:30 by weight), and fed into a twin-screw extruder (Bautech, KZW20TW-30) set to a barrel temperature of 200°C (feed section temperature 150°C). Subsequently, it was melt-blended at a screw speed of 200 rpm and then granulated to obtain a thermoplastic polyester elastomer resin.

[0194] [Example 2]

[0195] The thermoplastic polyester elastomer resin was obtained by the same steps as in Example 1, except that 2.4 kg of the resin from Example 2 was polymerized as the first polyester elastomer resin; 0.6 kg of the resin from Example 4 was polymerized as the second polyester elastomer resin; and 60 g of Rotader Ax8840 was used as a reactive compatibilizer, and the mixture was solid-state mixed (the blending ratio of the first polyester elastomer resin and the second polyester elastomer resin was 80:20 by weight).

[0196] [Example 3]

[0197] The thermoplastic polyester elastomer resin was obtained by the same steps as in Example 1, except that 2.4 kg of the resin from Example 2 was used as the first polyester elastomer resin; 0.30 kg of the resin from Example 3 and 0.30 kg of the resin from Example 4 were used as the second polyester elastomer resin; and 60 g of Rotader Ax4720 was used as a reactive compatibilizer, and the mixture was solid-state mixed (the blending ratio of the first polyester elastomer resin and the second polyester elastomer resin was 80:20 by weight).

[0198] [Example 4]

[0199] The thermoplastic polyester elastomer resin was obtained by the same steps as in Example 1, except that 1.8 kg of the resin from Example 2 was polymerized as the first polyester elastomer resin; 1.2 kg of the resin from Example 5 was polymerized as the second polyester elastomer resin; and 60 g of Rotader AX8900 was used as a reactive compatibilizer, and the mixture was solid-state mixed (the blending ratio of the first polyester elastomer resin and the second polyester elastomer resin was 60:40 by weight).

[0200] [Example 5]

[0201] The thermoplastic polyester elastomer resin was obtained by the same steps as in Example 1, except that 2.925 kg of the resin from Example 2 was used as the first polyester elastomer resin; 0.075 kg of the resin from Example 4 was used as the second polyester elastomer resin; and 60 g of Rotader AX8900 was used as a reactive compatibilizer. Solid mixing was carried out (the blending ratio of the first polyester elastomer resin and the second polyester elastomer resin was 97.5:2.5 by weight), and the barrel temperature was set to 220°C (160°C in the feed section).

[0202] [Example 6]

[0203] The thermoplastic polyester elastomer resin was obtained by the same steps as in Example 1, except that 1.5 kg of the resin from Example 3 was polymerized as the first polyester elastomer resin; 1.5 kg of the resin from Example 5 was polymerized as the second polyester elastomer resin; and 60 g of Rotader AX4720 was used as a reactive compatibilizer. Solid mixing was carried out (the blending ratio of the first polyester elastomer resin and the second polyester elastomer resin was 50:50 by weight), and the barrel temperature was set to 220°C (160°C in the feed section).

[0204] [Example 7]

[0205] 0.6 kg of the resin from polymerization Example 3 was used as the first polyester elastomer resin, and 2.4 kg of the resin from polymerization Example 4 was used as the second polyester elastomer resin. The mixture was then solid-state blended (the blending ratio of the first and second polyester elastomer resins was 20:80 by weight), and fed into a twin-screw extruder (Bautech, KZW20TW-30) set to a barrel temperature of 200°C (feed section temperature of 150°C). Subsequently, it was melt-blended at a screw speed of 200 rpm and then granulated to obtain a thermoplastic polyester elastomer resin.

[0206] [Example 8]

[0207] 2.1 kg of the resin from Example 1 was used as the first polyester elastomer resin, and 0.9 kg of the resin from Example 4 was used as the second polyester elastomer resin. These were solid-state mixed (the blending ratio of the first and second polyester elastomer resins was 70:30 by weight), and then fed into a twin-screw extruder (Bautech, KZW20TW-30) set to a barrel temperature of 200°C (feed section temperature of 150°C). Subsequently, the mixture was melt-blended at a screw speed of 200 rpm and then granulated to obtain the thermoplastic polyester elastomer resin.

[0208] [Comparative Example 1]

[0209] The resin of polymerization Example 3 was used alone as a thermoplastic polyester elastomer resin.

[0210] [Comparative Example 2]

[0211] The resin of polymerization Example 4 was used alone as a thermoplastic polyester elastomer resin.

[0212] The composition and physical properties of the thermoplastic polyester elastomer resins obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were evaluated as follows. The results are shown in Tables 2 and 3 below.

[0213] [Test Example 1] Content of hard segments (Equation 1) and soft segments (Equations 2 and 3)

[0214] Each thermoplastic polyester elastomer resin was dissolved in CDCl3 solvent at a concentration of 3 mg / ml, and its 1H-NMR spectrum was obtained using nuclear magnetic resonance (JEOL, 600 MHz FT-NMR) at 25 °C. By analyzing the spectra, the contents (wt%) of BD, PTMG, and EO-PPG were calculated based on the total molar number of residues derived from the whole diol (BD, PTMG, EO-PPG, etc.) to confirm the content of hard and soft segments in the total weight of the thermoplastic polyester elastomer resin.

[0215] [Test Example 2] Shore D Hardness (H)

[0216] The hardness of each thermoplastic polyester elastomer resin was measured according to ASTM D2240 (type D hardness tester). Specifically, thermoplastic polyester elastomer resin granules were injection molded using an injection molding machine (ENGEL, Victory 80) to form specimens 100 mm wide, 100 mm long, and 2 mm thick. Three specimens were stacked to obtain a specimen with a thickness of 6 mm. Then, its hardness was measured.

[0217] [Test Example 3] Intrinsic Viscosity (IV)

[0218] Each thermoplastic polyester elastomer resin was dissolved in o-chlorophenol (OCP) at a concentration of 0.12% at 150°C to obtain a solution. The intrinsic viscosity of the thermoplastic polyester elastomer resin was determined using an Ubbelohde viscometer in a constant temperature bath at 35°C. Specifically, the temperature of the viscous tube was maintained at 35°C, and the time required for the solvent to pass through a specific internal cross section of the viscous tube (outflow time) and the time required for the solution to pass through were calculated to obtain the specific viscosity, which was used to calculate the intrinsic viscosity.

[0219] [Test Example 4] Melt Flow Index (MI)

[0220] According to ASTM D1238, each thermoplastic polyester elastomer resin is held at 220°C and a load of 2.16 kg for 4 minutes, and then the amount of material discharged per hour is averaged three times to calculate the melt index.

[0221] [Test Example 5] Melting Point (Tm)

[0222] Each thermoplastic polyester elastomer resin was dried under reduced pressure at 50°C for 15 hours, melted and quenched, and then scanned at 10°C / min using a differential scanning calorimeter (DSC, TA Instruments). The highest point of the endothermic peak caused by resin melting was then taken as the melting point (Tm).

[0223] [Test Example 6] Tensile Strength

[0224] The tensile strength of each thermoplastic polyester elastomer resin was measured according to ASTM D638. Specifically, thermoplastic polyester elastomer resin granules were injection molded using an injection molding machine (ENGEL, Victory 80) to form specimens 120 mm wide, 120 mm long, and 2 mm thick, which were then stamped to obtain ASTM Type I (dumbbell-shaped bar) tensile specimens. Next, the tensile strength of the specimens was measured using a tensile testing machine (Zwick Roell, Z010) at a speed of 50 mm / min.

[0225] [Test Example 7] Compression Permanent Deformation (CS)

[0226] The compression set of various thermoplastic polyester elastomer resins was measured according to ISO 816 Method B. Specifically, thermoplastic polyester elastomer resin granules were injection molded using a compression molding machine (WithLab, WL1700) to form specimens with a diameter of 29 mm and a thickness of 12.5 mm, and then compressed at 70°C with a compression ratio of 25% of the thickness for 22 hours. Subsequently, when the compressive force was removed, the residual strain was obtained, and the compression set was calculated based on this strain.

[0227] [Test Example 8] Elasticity (R)

[0228] The resilience of each thermoplastic polyester elastomer resin was measured according to ASTM D2632. Thermoplastic polyester elastomer resin granules were injection molded using a compression molding machine (WithLab, WL1700) to produce specimens with a diameter of 29 mm and a thickness of 12.5 mm. Next, a 28 g object was dropped onto the specimen, and the rebound height was measured and used to calculate the elasticity.

[0229] [Table 2]

[0230] [Table 3]

[0231] According to Tables 2 and 3 above, the thermoplastic polyester elastomer resins of Examples 1 to 8 of the present invention each comprise a soft segment and a hard segment (Formula 1). The soft segment comprises repeating units derived from PO3G and EO-PPG respectively (Formulas 2 and 3), which exhibit excellent mechanical strength, elasticity (resilience), and compression set (resilience after long-term deformation). In particular, the thermoplastic polyester elastomer resins of Examples 1-6, wherein a reactive compatibilizer is used, have excellent mechanical strength and high molecular weight, and possess the desired intrinsic viscosity.

[0232] In contrast, the thermoplastic polyester elastomer resin of Comparative Example 1, which uses PO3G alone, has good mechanical strength but poor elasticity and resilience, while the thermoplastic polyester elastomer resin of Comparative Example 2, which uses EO-PPG alone, has significantly poor mechanical strength.

Claims

1. A thermoplastic polyester elastomer resin comprising a first polyester elastomer resin, the first polyester elastomer resin comprising repeating units (a) represented by Formula 1 and repeating units (b) represented by Formula 2; and a second polyester elastomer resin, the second polyester elastomer resin comprising repeating units (a) represented by Formula 1 and repeating units (c) represented by Formula 3: [Equation 1]: ； [Equation 2]: ； [Equation 3]: ； In equations 1 to 3, R 1 To R 3 Each independently is C1 to C 12 Straight-chain, branched, or cyclic divalent aliphatic hydrocarbon groups, or C6 to C6 groups. 12 The divalent aromatic hydrocarbon group, where m is an integer from 2 to 6, n is an integer from 2 to 3, p is an integer from 10 to 30, t is an integer from 1 to 30, and s is an integer from 1 to 40.

2. The thermoplastic polyester elastomer resin according to claim 1, wherein the thermoplastic polyester elastomer further comprises a reactive compatibilizer, a bonding structure derived from the reactive compatibilizer, or a combination thereof.

3. The thermoplastic polyester elastomer resin according to claim 2, wherein the reactive compatibilizer is a compound having a glycidyl group or a compound having a maleic anhydride structure.

4. The thermoplastic polyester elastomer resin according to claim 2, wherein the reactive compatibilizer is poly(ethylene-co-methacrylate-co-glycidyl methacrylate) or poly(ethylene-co-ethyl acrylate-co-maleic anhydride).

5. The thermoplastic polyester elastomer resin according to claim 2, wherein the content of the reactive compatibilizer is from 0.1% to 10% by weight, based on the total weight of the thermoplastic polyester elastomer resin.

6. The thermoplastic polyester elastomer resin according to claim 1, wherein the blending ratio of the first polyester elastomer resin and the second polyester elastomer resin is from 40:60 to 99:1 by weight.

7. The thermoplastic polyester elastomer resin according to claim 1, comprising a mixture of the first polyester elastomer resin and the second polyester elastomer resin, a crosslinked product of the first polyester elastomer resin and the second polyester elastomer resin, or a combination thereof.

8. The thermoplastic polyester elastomer resin according to claim 1, wherein the first polyester elastomer resin satisfies the following relationship 1: [Relation 1]: 0.5 ≤ a / b ≤ 3.0; In Equation 1, a is the weight of the repeating unit (a) represented by Equation 1 in the first polyester elastomer resin, and b is the weight of the repeating unit (b) represented by Equation 2 in the first polyester elastomer resin.

9. The thermoplastic polyester elastomer resin according to claim 1, wherein the second polyester elastomer resin satisfies the following relationship 2: [Relation 2]: 0.5 ≤ a / c ≤ 2.5; In Equation 2, a is the weight of the repeating unit (a) represented by Equation 1 in the second polyester elastomer resin, and c is the weight of the repeating unit (c) represented by Equation 3 in the second polyester elastomer resin.

10. The thermoplastic polyester elastomer resin according to claim 1, wherein it satisfies the following relationship 3: [Relationship 3]: 0.5 ≤ (y + z) / x ≤ 3.0; In Equation 3, x is the total weight of the repeating unit (a) represented by Equation 1 in the thermoplastic polyester elastomer resin, y is the total weight of the repeating unit (b) represented by Equation 2 in the thermoplastic polyester elastomer resin, and z is the total weight of the repeating unit (c) represented by Equation 3 in the thermoplastic polyester elastomer resin.

11. The thermoplastic polyester elastomer resin according to claim 1, wherein it satisfies the following relationship 4: [Relation 4]: 0.3 ≤ y / z ≤ 37; In Equation 4, y is the total weight of the repeating unit (b) represented by Equation 2 in the thermoplastic polyester elastomer resin, and z is the total weight of the repeating unit (c) represented by Equation 3 in the thermoplastic polyester elastomer resin.

12. The thermoplastic polyester elastomer resin according to claim 1, wherein the tensile strength is 190 kgf / cm² when measured according to ASTM D638. 2 Or higher.

13. The thermoplastic polyester elastomer resin according to claim 1, wherein it satisfies the following relationship 5: [Relation 5]: H / R ≤ 0.97; In Equation 5, H is the Shore D hardness of the thermoplastic polyester elastomer resin as measured according to ASTM D2240, and R is the resilience of the thermoplastic polyester elastomer resin as measured according to ASTM D2632.

14. The thermoplastic polyester elastomer resin according to claim 1, wherein it satisfies the following relationship 6: [Relation 6]: 0.6 ≤ H / CS; In Equation 6, H is the Shore D hardness of the thermoplastic polyester elastomer resin as measured according to ASTM D2240, and CS is the compression set of the thermoplastic polyester elastomer resin as measured according to ISO 816 Method B.

15. The thermoplastic polyester elastomer resin according to claim 1, wherein the repeating unit (a) represented by formula 1 is derived from the reaction of a diol component comprising 1,4-butanediol and a dicarboxylic acid component; The repeating unit (b) represented by Formula 2 is derived from the reaction of the dicarboxylic acid component and the high molecular weight diol component containing polytrimethylene ether diol, and, The repeating unit (c) represented by Formula 3 is derived from the reaction of the dicarboxylic acid component and the high molecular weight diol component of polypropylene glycol containing ethylene oxide addition.

16. The thermoplastic polyester elastomer resin of claim 15, wherein the dicarboxylic acid component comprises at least one selected from the group consisting of terephthalic acid and dimethyl terephthalate.

17. The thermoplastic polyester elastomer resin of claim 15, wherein the number average molecular weight of the high molecular weight diol component comprising polytrimethylene ether diol and the number average molecular weight of the high molecular weight diol component comprising ethylene oxide-added polypropylene glycol are each independently 400 to 5,000 g / mol.

18. A method for preparing a thermoplastic polyester elastomer resin, comprising: (1-1) React the first diol component, the first dicarboxylic acid component and the first high molecular weight diol component to obtain the first polyester elastomer resin; (1-2) Reacting the second diol component, the second dicarboxylic acid component, and the second high molecular weight diol component to obtain a second polyester elastomer resin; and, (1-3) Melt-blending the first polyester elastomer resin and the second polyester elastomer resin; The first polyester elastomer resin comprises a repeating unit (a) represented by Formula 1 and a repeating unit (b) represented by Formula 2; and the second polyester elastomer resin comprises a repeating unit (a) represented by Formula 1 and a repeating unit (c) represented by Formula 3. [Equation 1]: ； [Equation 2]: ； [Equation 3]: ； In equations 1 to 3, R 1 To R 3 Each independently is C1 to C 12 Straight-chain, branched, or cyclic divalent aliphatic hydrocarbon groups, or C6 to C6 groups. 12 The divalent aromatic hydrocarbon group, where m is an integer from 2 to 6, n is an integer from 2 to 3, p is an integer from 10 to 30, t is an integer from 1 to 30, and s is an integer from 1 to 40.

19. The method for preparing thermoplastic polyester elastomer resin according to claim 18, wherein the melt mixing in steps (1-3) is carried out in the presence of a reactive compatibilizer.

20. The method for preparing a thermoplastic polyester elastomer resin according to claim 18, wherein the first diol component and the second diol component each independently comprise 1,4-butanediol. The first high molecular weight diol component includes polytrimethylene ether diol, and, The second high molecular weight diol component includes polypropylene glycol with ethylene oxide addition.

21. A composition comprising the thermoplastic polyester elastomer resin according to any one of claims 1 to 17.

22. An article comprising the thermoplastic polyester elastomer resin according to any one of claims 1 to 17.

23. The article of claim 22, wherein the article is a fiber, foam, or footwear component.

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