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 excellent elasticity and compression elasticity recovery, and also has high mechanical strength, elongation and the like. Therefore, the thermoplastic polyester elastomer resin can be used for manufacturing various articles (such as fibers, foams, shoe parts and the like).

Description

Technical Field

[0001] This invention relates to a thermoplastic polyester elastomer resin comprising a thermoplastic hard segment and an elastic soft segment (introduced with PTMG and EO-PPG), and exhibiting excellent physical properties such as mechanical strength, elasticity, and compression elastic recovery, as well as a method for preparing the resin. Background Technology

[0002] Thermoplastic elastomer (TPE) resins consist of hard segments derived from thermoplastic polymers with thermoplasticity and soft segments derived from elastomers with elasticity, resembling rubber. Compared to traditional thermosetting rubbers, the hard segments are physically bonded through crystals, similar to chemical cross-linking, a process known as "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 manufacture automotive parts, electrical and electronic components, fibers and films.

[0004] TPEE resin is mainly composed of crystalline hard segments of tetramethylene ester and amorphous soft segments of polyether polyol ester. Polyether glycol (PEG), poly(1,2-propanediol) (PPG), and polytetramethylene ether glycol (PTMG) have been used as raw materials for preparing the soft segments of TPEE resin.

[0005] However, TPEE resins prepared from PEG have the disadvantage of high moisture content, while PPG has low polymerization reactivity; therefore, they are not commonly used as raw materials for preparing TPEE resins. Meanwhile, TPEE resins prepared from PTMG have good physical properties, such as mechanical strength and elongation, but their elasticity and compressive elastic recovery are difficult to improve to ideal levels or higher.

[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 elasticity recovery, which can be used to prepare various 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 increasing the incompatibility between hard and soft segments and controlling the crystallinity and crystallization rate of the soft segments at low levels, thermoplastic polyester elastomer (TPEE) resins with excellent mechanical strength and enhanced elasticity and compressive elasticity recovery can be obtained.

[0009] Therefore, one object of the present invention is to provide a thermoplastic polyester elastomer resin having excellent mechanical strength, excellent elasticity and compression elastic recovery, and a method for preparing the resin.

[0010] 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 repeating units (a) represented by Formula 1; repeating units (b) represented by Formula 2; and repeating units (c) represented by Formula 3, and satisfying the following relation 1:

[0013] [Formula 1]

[0014]

[0015] [Equation 2]

[0016]

[0017] [Formula 3]

[0018]

[0019] [Relation 1]

[0020] 0.3 ≤ y / z ≤ 35

[0021] In equations 1 to 3, R 1 To R 3 Each independently is C1 to C 12 Linear, 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 4 to 6, 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.

[0022] In Equation 1, y is the weight of the repeating unit (b) represented by Equation 2 in the thermoplastic polyester elastomer resin, and z is the weight of the repeating unit (c) represented by Equation 3 in the thermoplastic polyester elastomer resin.

[0023] Furthermore, the present invention provides a method for preparing a thermoplastic polyester elastomer resin, the method comprising: (1-1) reacting a diol component; a dicarboxylic acid component; and a high molecular weight diol component to obtain a reactant; and (1-2) subjecting the reactant to a polycondensation reaction, wherein the thermoplastic polyester elastomer resin comprises a repeating unit (a) represented by Formula 1 above, a repeating unit (b) represented by Formula 2 above, and a repeating unit (c) represented by Formula 3 above, and satisfies the above relation 1.

[0024] Furthermore, the present invention provides a composition comprising the aforementioned thermoplastic polyester elastomer resin.

[0025] Furthermore, the present invention provides an article comprising the aforementioned thermoplastic polyester elastomer resin.

[0026] Beneficial effects of the invention

[0027] The thermoplastic polyester elastomer resin of the present invention exhibits excellent mechanical strength due to the use of polytetramethylene ether glycol (PTMG) in the preparation of its soft segments. Furthermore, in the thermoplastic polyester elastomer resin of the present invention, ethylene oxide-added polypropylene glycol (EO-PPG) is used in the preparation of its soft segments, wherein the methylene side chains are attached to the polyol backbone, restricting the movement of the soft segment polymer chains, generating sufficient free volume between the polymer chains, reducing crystallinity and crystallization rate, and increasing incompatibility with hard segments, thereby accelerating phase separation from hard segments; therefore, it can possess excellent elasticity and compressive elastic recovery.

[0028] As described above, the thermoplastic polyester elastomer resin of the present invention has excellent mechanical strength, elasticity and compressive elastic recovery, while exhibiting the desired hardness; therefore, it can be used to produce a variety of products, such as automotive parts, electrical and electronic parts, fibers, films, matrices, cushioning materials, foams and shoe components, etc.

[0029] Best Implementation of the Invention

[0030] 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 essential points of the invention are not altered.

[0031] 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.

[0032] Throughout 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 used to distinguish one element from another.

[0033] 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”.

[0034] 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 elastic properties. To improve the elastic properties 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.

[0035] In summary, in this invention, when forming the soft segments of the thermoplastic polyester elastomer resin, polytetramethylene ether glycol (PTMG) is used to reduce the crystallinity and crystallization rate of the soft segments; simultaneously, ethylene oxide-added polypropylene glycol (EO-PPG) is used to increase incompatibility with the hard segments, thereby achieving clear phase separation. The specific explanation is as follows.

[0036] Thermoplastic polyester elastomer resin

[0037] The thermoplastic polyester elastomer of the present invention comprises repeating units (a) represented by the following formula 1; repeating units (b) represented by the following formula 2; and repeating units (c) represented by the following formula 3.

[0038] [Formula 1]

[0039]

[0040] [Equation 2]

[0041]

[0042] [Formula 3]

[0043]

[0044] 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 Linear, 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 4 to 6, 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.

[0045] The repeating unit (a) represented by Equation 1 can be a repeating unit constituting the hard segment of thermoplastic polyester elastomer resin. In Equation 1, R 1 Specifically, it can be C5 to C 12 Cyclic divalent aliphatic hydrocarbon groups or C6 to C6 12 A divalent aromatic hydrocarbon group, where m can be an integer from 3 to 5. For example, R 1 It can be cyclohexenyl or phenylene, and m can be an integer of 4.

[0046] The repeating unit (b) represented by Equation 2 and the repeating unit (c) represented by Equation 3 can each be a repeating unit constituting a soft segment of thermoplastic polyester elastomer resin. In Equation 2, R 2 Specifically, it can be C5 to C 12 Cyclic divalent aliphatic hydrocarbon groups or C6 to C6 12 The divalent aromatic hydrocarbon group is an integer. Furthermore, n can be an integer of 4 or 5, and p can be an integer from 15 to 25. For example, R 2 It can be cyclohexenyl or phenylene, n can be an integer of 4, and p can be an integer from 18 to 22. In formula 3, R 3 Specifically, it can be C5 to C 12 Cyclic divalent aliphatic hydrocarbon groups or C6 to C6 12 The divalent aromatic hydrocarbon group is an integer. 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 cyclohexenyl or phenylene, t can be an integer from 10 to 20, and s can be an integer from 10 to 30.

[0047] For example, the thermoplastic polyester elastomer resin according to the present invention may include repeating units represented by Formula 4 and / or repeating units represented by Formula 5, such as repeating units (a) represented by Formula 1, repeating units (b) represented by Formula 2 and repeating units (c) represented by Formula 3 above, combined with each other.

[0048] [Formula 4]

[0049]

[0050] [Formula 5]

[0051]

[0052] In equations 4 and 5, R 1 R 2 R 3 m, n, p, t, and s are the same as described above, while x, y, and z are weight ratios.

[0053] According to the present invention, the repeating unit (a) represented by Formula 1 can be 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 can be derived from the reaction of a dicarboxylic acid component and a high molecular weight diol component comprising polytetramethylene ether diol (first high molecular weight diol 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 comprising polypropylene glycol (second high molecular weight diol component) with ethylene oxide addition.

[0054] Specifically, the thermoplastic polyester elastomer resin according to the present invention can be a resin obtained by using a dicarboxylic acid component, a diol component, and a high molecular weight diol component (a first high molecular weight diol component and a second high molecular weight diol component) as reaction raw materials.

[0055] 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.

[0056] The aliphatic dicarboxylic acid component can be branched, branched, or cyclic. The aliphatic dicarboxylic acid component can have 4 or more, 5 or more, 6 or more, or 7 or more carbon atoms, and can have 20 or fewer, 15 or fewer, 13 or fewer, 12 or fewer, or 10 or fewer carbon atoms. Specifically, the aliphatic dicarboxylic acid component can have 4 to 20, 5 to 15, or 6 to 10 carbon atoms.

[0057] For example, the aliphatic dicarboxylic acid component may include at least one selected from the group consisting of adipic acid, sebacic acid, succinic acid, isodecylsuccinic acid, maleic acid, fumaric acid, glutaric acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid, but is not limited thereto.

[0058] 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.

[0059] 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-furandicarboxylic acid, 2,5-thiophene dicarboxylic acid and dimethyl terephthalate, but is not limited thereto.

[0060] Preferably, the dicarboxylic acid component may include at least one selected from the group consisting of terephthalic acid and dimethyl terephthalate. The amount (amount added during the reaction) of at least one component selected from the group consisting of 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. 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%.

[0061] The diol component can undergo esterification or transesterification with the dicarboxylic acid component to form a hard segment of the tetramethylene ester (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, or 4 to 8.

[0062] 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.

[0063] Preferably, the diol component may include 1,4-butanediol. The amount of 1,4-butanediol (the amount added during the reaction) is not particularly limited, but 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. 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%.

[0064] There are no particular restrictions on the number-average molecular weight of the diol component, but it may be less than 400 g / mol, less than 350 g / mol, less than 300 g / mol, or less than 250 g / mol.

[0065] 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 units (b) of Formula 2 and (c) of Formula 3). The high molecular weight diol component may contain polytetramethylene ether glycol (PTMG) and ethylene oxide-added polypropylene glycol (EO-PPG). Because the high molecular weight diol component contains polytetramethylene ether glycol (PTMG), the mechanical strength of the thermoplastic polyester elastomer resin can be significantly improved. Furthermore, because the high molecular weight diol component contains ethylene oxide-added polypropylene glycol (EO-PPG), the elasticity and compressive elastic recovery of the thermoplastic polyester elastomer resin can be significantly improved.

[0066] Preferably, the high molecular weight diol component may consist of polytetramethylene ether glycol (PTMG) and polypropylene glycol (EO-PPG) formed by the addition of ethylene oxide. The amount of PTMG (added during the reaction) is not particularly limited, but 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 total composition of the first and second high molecular weight diol components). Specifically, the amount of PTMG can be 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%. Furthermore, there are no particular limitations on the amount of ethylene oxide-added polypropylene glycol (EO-PPG) used (the amount added during the reaction), but it can be based on the total molar percentage of the high molecular weight glycol components (the total composition of the first and second high molecular weight glycol components) of 50 mol% or less, 40 mol% or less, 25 mol% or less, 15 mol% or less, 5 mol% or less, or 3 mol% or less. Specifically, the amount of ethylene oxide-added polypropylene glycol (EO-PPG) used can be from 0.5 mol% to 50 mol%, 1 mol% to 40 mol%, 5 mol% to 35 mol%, 10 mol% to 30 mol%, 15 mol% to 30 mol%, or 15 mol% to 25 mol%.

[0067] The number-average molecular weight of the high molecular weight diol component, composed of polytetramethylene ether glycol (PTMG) and ethylene oxide-modified polypropylene glycol (EO-PPG), is not particularly limited, but 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, or 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, to ensure good phase separation from the hard segments, the number-average molecular weight of the high molecular weight diol component can be from 400 g / mol to 5,000 g / mol or from 1,000 g / mol to 3,000 g / mol.

[0068] For example, the number average molecular weight of polytetramethylene ether glycol (PTMG) may be from 500 g / mol to 4,000 g / mol, 600 g / mol to 4,000 g / mol, 800 g / mol to 3,500 g / mol, or 1,000 g / mol to 3,000 g / mol. Similarly, the number average molecular weight of ethylene oxide-added polypropylene glycol (EO-PPG) may be from 1,000 g / mol to 4,000 g / mol, 1,500 g / mol to 3,500 g / mol, 2,000 g / mol to 3,500 g / mol, or 2,000 g / mol to 3,000 g / mol.

[0069] Furthermore, according to the present invention, the content (x) of the repeating unit (a) represented by Formula 1 is not particularly limited, but can be based on a total weight of 20% to 70% by weight, 22% to 68% by weight, 24% to 65% by weight, 26% to 63% by weight, or 27% to 60% by weight of the thermoplastic polyester elastomer resin. When the content (x) of the repeating unit (a) is within the above range, a thermoplastic polyester elastomer resin with the desired level of mechanical strength (e.g., tensile strength) and hardness can be provided.

[0070] Furthermore, the content (y) of the repeating unit (b) represented by Formula 2 is not particularly limited, but can be based on a total weight of 10% to 75% by weight, 11% to 70% by weight, 12% to 65% by weight, 13% to 62% by weight, or 14% to 60% by weight of the thermoplastic polyester elastomer resin. When the content (y) of the repeating unit (b) is within the above range, it provides a thermoplastic polyester elastomer resin that offers excellent mechanical strength and elongation, while maintaining the desired level of elasticity and compressive elasticity recovery.

[0071] Furthermore, the content (z) of the repeating unit (c) represented by Formula 3 is not particularly limited, but can be based on a total weight of the thermoplastic polyester elastomer resin of 0.5 wt% to 40 wt%, 0.8 wt% to 38 wt%, 1 wt% to 35 wt%, 1.2 wt% to 32 wt%, or 1.5 wt% to 30 wt%. When the content (z) of the repeating unit (c) is within the above range, a thermoplastic polyester elastomer resin with excellent elasticity and compression elasticity recovery, and mechanical strength and elongation at the desired level can be provided.

[0072] The thermoplastic polyester elastomer resin according to the present invention can be a resin comprising repeating units (a), repeating units (b) and repeating units (c), and the content ratio (weight ratio) between these repeating units is controlled within a specific range.

[0073] Specifically, the thermoplastic polyester elastomer resin according to the present invention can satisfy the following relationship 1. When the thermoplastic polyester elastomer resin satisfies the following relationship 1, it can have the desired high molecular weight and higher mechanical strength.

[0074] [Relation 1]

[0075] 0.3 ≤ y / z ≤ 35

[0076] In Equation 1, y is the 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 weight of the repeating unit (c) represented by Equation 3 in the thermoplastic polyester elastomer resin (total weight of the thermoplastic polyester elastomer resin).

[0077] Specifically, in relation 1, the ratio of y / z can be 0.35 to 33, 0.4 to 32.5, 0.5 to 28, 0.8 to 25, 1 to 20, 1.2 to 15, 2 to 13, or 3 to 7.

[0078] Furthermore, the thermoplastic polyester elastomer resin according to the present invention can satisfy the following relationship 2. When the thermoplastic polyester elastomer resin satisfies the following relationship 2, it can have superior elasticity and compressive elastic recovery.

[0079] [Relationship 2]

[0080] 0.5 ≤ (y + z) / x ≤ 3.0

[0081] In Equation 2, x is the weight of the repeating unit (a) represented by Equation 1 in the thermoplastic polyester elastomer resin (total weight of the thermoplastic polyester elastomer resin), y is the 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 weight of the repeating unit (c) represented by Equation 3 in the thermoplastic polyester elastomer resin (total weight of the thermoplastic polyester elastomer resin).

[0082] Specifically, in relation 2, the ratio of (y+z) / x can be 0.55 to 2.95, 0.6 to 2.90, 0.65 to 2.88, 0.7 to 2.85, 0.75 to 2.75, 0.8 to 2.65, 1 to 2.55, or 1.15 to 2.45.

[0083] Furthermore, the thermoplastic polyester elastomer resin according to the present invention may further comprise repeating units (d) derived from reactive compatibilizers. When the thermoplastic polyester elastomer resin further comprises repeating units (d), it may have enhanced elasticity and compressive elastic recovery, as well as mechanical strength and elongation.

[0084] A reactive compatibilizer is an additive that prevents phase separation between the components of a mixture of two or more raw materials (resin mixtures) 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 of the mixed raw material components and reacts with the functional groups of the other raw material component. When added to a raw material mixture for reactive extrusion processing, it may induce the formation of block copolymers or graft copolymers.

[0085] Reactive compatibilizers can be selected from isocyanate compounds, carbodiimide compounds (e.g., polycarbodiimide compounds containing two or more -N=C=N- structures), epoxy compounds, oxazoline compounds, compounds with glycidyl groups, and compounds with maleic anhydride structures. Isocyanate compounds are highly reactive with water; therefore, their reactivity and handling (storage) convenience may be difficult to control. Carbodiimide compounds are expensive; therefore, their economic feasibility may be low. Furthermore, epoxy compounds can exhibit significant differences in reactivity due to variations in epoxy equivalent 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 the feedstock components. Therefore, compounds with glycidyl groups or maleic anhydride structures are preferred as reactive compatibilizers.

[0086] Compounds having glycidyl groups can specifically be olefin-based rubber polymers modified with glycidyl groups, preferably polymers grafted with glycidyl (meth)acrylate onto polyolefin-based rubber copolymers (glycidyl (meth)acrylate grafted polyolefin elastomers). Compounds having maleic anhydride structures can specifically be polymers grafted with maleic anhydride onto polyolefin-based rubber copolymers (maleic anhydride grafted polyolefin elastomers).

[0087] For example, the reactive compatibilizer can be poly(ethylene-co-methacrylate-co-glycidyl methacrylate). Therefore, the repeating unit (d) may have the structure shown in Formula 6 below. Furthermore, the reactive compatibilizer can be poly(ethylene-co-ethyl acrylate-co-maleic anhydride). Therefore, the repeating unit (d) may be as shown in Formula 7 below.

[0088] [Formula 6]

[0089]

[0090] [Formula 7]

[0091]

[0092] For poly(ethylene-co-methacrylate-co-glycidyl methacrylate), in Formula 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.

[0093] Furthermore, for poly(ethylene-co-ethyl acrylate-co-maleic anhydride), 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.

[0094] Examples of commercially available reactive compatibilizers include Rotarder AX8840, Rotarder AX8900, and Rotarder AX4720.

[0095] According to the present invention, the content of the repeating unit (d) derived from the reactive compatibilizer is not particularly limited, but can be 0.1% to 10% by weight, 0.5% to 10% by weight, 1% to 5% by weight, or 2% to 4% by weight based on the total weight of the thermoplastic polyester elastomer resin. When the content of the repeating unit (d) is within the above range, the required melt viscosity level can be ensured, thereby improving the moldability (processability) of the thermoplastic polyester elastomer resin.

[0096] As described above, the physical properties of the thermoplastic polyester elastomer resin according to the present invention can be enhanced by using high molecular weight diol components (PTMG and EO-PPG) to form soft segments while controlling the amount of the corresponding reaction raw materials.

[0097] Specifically, the thermoplastic polyester elastomer resin according to the present invention, when measured according to ASTM D638 standard, has a tensile strength of up to 190 kgf / cm². 2 or more, 195 kgf / cm 2 or more, 200 kgf / cm 2 or more, 205 kgf / cm 2 or more, 220 kgf / cm 2 or more, 230 kgf / cm 2 or more, 240 kgf / cm 2 or more, or 250 kgf / cm 2 Or more. More specifically, the tensile strength might be 190 kgf / cm². 2 Up to 350 kgf / cm 2 195 kgf / cm 2 Up to 335 kgf / cm 2 200 kgf / cm 2 Up to 325 kgf / cm 2 or 210 kgf / cm 2Up to 320 kgf / cm 2 .

[0098] The intrinsic viscosity (IV) of the thermoplastic polyester elastomer resin according to the present invention can be from 1.0 dl / g to 2.4 dl / g, specifically, from 1.05 dl / g to 2.3 dl / g, from 1.1 dl / g to 2.2 dl / g, from 1.2 dl / g to 2 dl / g, from 1.3 dl / g to 1.9 dl / g, from 1.35 dl / g to 1.88 dl / g, or from 1.4 dl / g to 1.85 dl / g.

[0099] The Shore D hardness of the thermoplastic polyester elastomer resin according to the present invention can be 20 to 60, specifically, it can be 25 to 55, 28 to 53, 28 to 50, 30 to 48 or 30 to 45.

[0100] The compression set (compression elastic recovery) of the thermoplastic polyester elastomer resin according to the present invention is 30% to 60%, 30% to 59%, 31% to 58%, 31% to 57%, 32% to 56%, 32% to 55%, 33% to 53%, 33% to 50%, 34% to 49%, or 34% to 48%.

[0101] The restoring force (elasticity) of the thermoplastic polyester elastomer resin according to the present invention is 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%.

[0102] The thermoplastic polyester elastomer resin according to the present invention satisfies the following relation 3 and / or relation 4, thereby exhibiting excellent mechanical strength, elasticity, and compressive elastic recovery.

[0103] [Relationship 3]

[0104] H / R ≤ 0.75

[0105] [Relationship 4]

[0106] 0.8 ≤ H / CS

[0107] In equations 3 and 4, 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.

[0108] Specifically, the H / R ratio can be 0.3 to 0.75, 0.32 to 0.73, 0.34 to 0.7, 0.35 to 0.68, 0.38 to 0.65, 0.4 to 0.63, or 0.4 to 0.6.

[0109] In addition, the H / CS ratio can be 0.8 to 0.95, 0.8 to 0.93, 0.81 to 0.92, 0.82 to 0.91, 0.83 to 0.9, 0.84 to 0.89, or 0.85 to 0.88.

[0110] The thermoplastic polyester elastomer resin described in this invention possesses excellent basic physical properties (e.g., heat resistance, impact resistance, and moldability) and exhibits superior performance in mechanical strength, elasticity, and compressive strength recovery. Therefore, it can be used to produce a wide variety of products. Specifically, the thermoplastic polyester elastomer resin can be used to produce fibers, films, foams (foam-type molded articles), and shoe components (e.g., cushioning materials for shoe midsoles, outsoles, and insoles).

[0111] Preparation method of thermoplastic polyester elastomer

[0112] The thermoplastic polyester elastomer resin according to the present invention can be prepared by esterification or transesterification followed by polycondensation. Specifically, the method for preparing the thermoplastic polyester elastomer resin according to the present invention includes: (1-1) reacting a diol component, a dicarboxylic acid component, and a high molecular weight diol component to obtain a reactant; and (1-2) subjecting the reactant to a polycondensation reaction, which will be described in detail below.

[0113] Step (1-1): Esterification or transesterification

[0114] According to the present invention, step (1-1) involves adding a diol component, a dicarboxylic acid component, and a high molecular weight diol component as reactants to a reactor (esterification reactor or transesterification reactor) and carrying out an esterification reaction or transesterification reaction to obtain reactants. In this case, the diol component comprises 1,4-butanediol, and the high molecular weight diol component comprises polytetramethylene ether glycol (PTMG) and ethylene oxide-added polypropylene glycol (EO-PPG). The descriptions of these components are the same as above and are therefore omitted. Furthermore, the description of the dicarboxylic acid component is the same as above and is therefore omitted.

[0115] The diol component, dicarboxylic acid component, and high molecular weight diol component are added to the reactor all at once. Alternatively, the diol component and dicarboxylic acid component are added first, and then the temperature is increased. When the reactor temperature reaches a certain level, the high molecular weight diol can be added. For example, the 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.

[0116] Esterification or transesterification reactions can be carried out in the presence of a catalyst. That is, a catalyst can be added simultaneously with the reactants to the reactor. 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.

[0117] 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 germanium dioxide, germanium tetrachloride, germanium glycol oxide, and germanium acetate.

[0118] The amount of catalyst used (the amount added during 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 components (such as 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 diol components, dicarboxylic acid components, and high molecular weight diol components added to the reactor.

[0119] In addition, during esterification or transesterification, one or more additives selected from the group consisting of crystallizing agents, antioxidants, and polymerization branching agents may be added.

[0120] Crystallizing agents such as nucleating agents, ultraviolet absorbers, polyolefin resins, and polyamide resins can be used.

[0121] At least one of the group consisting of hindered phenolic compounds, phosphites, and thioethers can be used as an antioxidant.

[0122] 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 can 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.

[0123] There are no particular restrictions on the amount of branching agent used in the polymerization reaction (the amount added during the reaction), but its concentration can be from 0.00015 equivalents to 0.005 equivalents per 100 grams of thermoplastic polyester elastomer resin.

[0124] 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.

[0125] The conditions for esterification or transesterification reactions can be adjusted appropriately according to 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 More or 0.05 kg / cm 2 or more, or 0.1 kg / cm 2 More, and can be 1.5 kg / cm² 2 or less, 1kg / cm 2 or less, 0.5 kg / cm 2 Or less, or 0.3 kg / cm 2 Or less. 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 at 0.05 kg / cm³. 2 Up to 1.5 kg / cm 2 And it is carried out under conditions of 180°C to 280°C.

[0126] Esterification or transesterification can be carried out in batch or continuous manner.

[0127] The termination point of an esterification or transesterification reaction can be determined by taking into account the theoretical amount of water or methanol as byproducts formed from the dicarboxylic acid component, or by when no more byproducts are discharged.

[0128] Step (1-2): Polycondensation reaction

[0129] According to the present invention, step (1-2) is a step of subjecting the reactants obtained in step (1-1) to a polycondensation reaction. The conditions for carrying out the polycondensation reaction may not be particularly limited.

[0130] Specifically, the polycondensation reaction can be carried out under a vacuum atmosphere. Furthermore, the pressure of the polycondensation reaction can be from 0.01 mmHg to 600 mmHg, 0.05 mmHg to 200 mmHg, 0.1 mmHg to 100 mmHg, 0.5 mmHg to 50 mmHg, or 1 mmHg to 10 mmHg. In addition, the temperature of the polycondensation reaction can be from 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 a vacuum atmosphere at a reduced pressure of 0.1 to 10 mmHg and a temperature of 200 to 260°C for 1 to 24 hours. When the polycondensation reaction is carried out under the above conditions, a thermoplastic polyester elastomer resin with the desired molecular weight and intrinsic viscosity (IV) can be produced, while byproducts are sufficiently removed.

[0131] Through steps (1-1) and (1-2), thermoplastic polyester elastomer resins composed of repeating units ((a), (b) and (c)) represented by the above formulas 1 to 3 can be prepared in high yield.

[0132] Meanwhile, the thermoplastic polyester elastomer resin according to the present invention can be prepared by obtaining a first thermoplastic polyester elastomer resin and a second thermoplastic polyester elastomer resin as reaction raw materials through esterification reaction or transesterification reaction and polycondensation reaction, respectively, and then melting and kneading them together. Specifically, the method for preparing thermoplastic polyester elastomer according to the present invention includes: (2-1) reacting a diol component containing 1,4-butanediol, a first dicarboxylic acid component, and a first high molecular weight diol component containing polytetramethylene ether diol to obtain a first reactant; (2-2) reacting a diol component containing 1,4-butanediol, a second dicarboxylic acid component, and a second high molecular weight diol component containing polypropylene glycol added with ethylene oxide to obtain a second reactant; and (2-3) melting and kneading the first reactant, the second reactant, and a reactive compatibilizer together, the specific steps of which will be described in detail below.

[0133] Step (2-1): First esterification reaction or first transesterification reaction

[0134] According to the present invention, step (2-1) involves adding the first diol component, the first dicarboxylic acid component, and the first high molecular weight diol component as reactants to a reactor (esterification reactor or transesterification reactor) and carrying out an esterification reaction or transesterification reaction to obtain a reactant (intermediate reactant); and carrying out a polycondensation reaction to obtain a first reactant (first thermoplastic polyester elastomer resin).

[0135] The descriptions of the first diol component and the first dicarboxylic acid component are the same as those of the diol component and the dicarboxylic acid component, and are therefore omitted. The first high molecular weight diol component may include polytetramethylene ether glycol (PTMG). Specifically, it may consist only of polytetramethylene ether glycol (PTMG).

[0136] Meanwhile, the descriptions of the esterification, transesterification, and polycondensation reactions for preparing the first reactant are the same as those described above, and therefore are omitted.

[0137] Step (2-2): Second esterification reaction or second transesterification reaction

[0138] According to the present invention, step (2-2) involves adding the second diol component, the second dicarboxylic acid component, and the second high molecular weight diol component as reactants to a reactor (esterification reactor or transesterification reactor) and carrying out an esterification reaction or transesterification reaction to obtain a reactant (intermediate reactant); and carrying out a polycondensation reaction to obtain a second reactant (second thermoplastic polyester elastomer resin).

[0139] The descriptions of the second diol component and the second dicarboxylic acid component are the same as those of the diol component and the dicarboxylic acid component, and are therefore omitted. The second high molecular weight diol component may comprise ethylene oxide-added polypropylene glycol (EO-PPG). Specifically, it may consist solely of ethylene oxide-added polypropylene glycol (EO-PPG).

[0140] Meanwhile, the descriptions of the esterification, transesterification, and polycondensation reactions for preparing the second reactant are the same as those described above, and therefore are omitted.

[0141] Step (2-3): Melting and kneading

[0142] According to the present invention, step (2-3) is a step of melting and kneading together the first reactant obtained in step (2-1) and the second reactant obtained in step (2-2). During the melting and kneading process in step (2-3), a reactive compatibilizer is added, which enables chemical crosslinking while maximizing the dispersibility of the first and second reactants. Therefore, a thermoplastic polyester elastomer resin with excellent mechanical strength, elasticity, and compressive strength recovery can be prepared while maintaining basic physical properties. Specifically, when a reactive compatibilizer is used, the first and second reactants are dispersed and bonded in a microphase-separated state, with soft segments having repeating units derived from ethylene oxide addition polypropylene glycol (EO-PPG) (repeating unit (c) in Formula 3) exhibiting energy-repellent elasticity and soft segments having repeating units derived from polytetramethylene ether glycol (PTMG) (repeating unit (b) in Formula 2) that determine mechanical strength. Therefore, a thermoplastic polyester elastomer resin with excellent elasticity and compressive strength recovery can be prepared. The description of reactive compatibilizers is as described above and therefore omitted.

[0143] Meanwhile, melt kneading can be performed under heating and / or pressure using single-screw extruders, twin-screw extruders, mixing rollers, Banbury mixers, batch kneaders, molding machines, etc.

[0144] For melt kneading, the first and second reactants can be premixed. Specifically, the premixing process can be achieved by adding the first and second reactants to various mixers, such as V-type mixers, belt mixers, Henschel mixers, rocking mixers, vortex mixers, planetary mixers, Banbury mixers, mill mixers, mixing rollers, and drum mixers, to premix them in solid form. The mixing time for solid form may 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 mixture ratio is within 1%, and at most does not exceed 2%.

[0145] During the premixing process, known additives (such as colorants, fillers, sunscreens, heat stabilizers, etc.) can be added as needed. Here, the first and second reactants can be directly fed into a single-screw extruder, twin-screw extruder, mixing roller, Banbury mixer, batch kneader, molding machine, etc., for melt kneading without a premixing step. Furthermore, thermoplastic polyester elastomer resins can be prepared by premixing some raw material components, then melt-kneading them to obtain reactants for use as a masterbatch, mixing the remaining raw material components with the masterbatch, and then melt-kneading them again.

[0146] Meanwhile, there are no particular restrictions on the mixing ratio of the first reactant and the second reactant in the melt kneading process, but depending on the required physical properties of the thermoplastic polyester elastomer resin, the weight ratio 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 95:5, 60:40 to 90:10, 65:35 to 90:10, 70:30 to 85:15, or 75:25 to 85:15.

[0147] Specifically, melt kneading can be carried out in a single-screw extruder or a twin-screw extruder. There are no particular limitations on the temperature at which melt kneading occurs through the extruder (e.g., the barrel temperature of the extruder), and it can be determined based on factors such as miscibility, ease of extrusion, and extrusion reaction efficiency. Specifically, melt kneading can be performed at a temperature higher than the melting point (T0) of the desired thermoplastic polyester elastomer resin. mThe process should be carried out at a temperature 20°C to 30°C higher than normal. For example, the melt kneading temperature 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. Meanwhile, there are no particular limitations on the extrusion speed (screw speed) of the extruder. Specifically, it can be 150 rpm to 230 rpm, 160 rpm to 225 rpm, 170 rpm to 220 rpm, 180 rpm to 210 rpm, 190 rpm to 205 rpm, or 195 rpm to 200 rpm. When melt kneading is carried out under the above conditions, sufficient melt kneading 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 undergo thermal decomposition, or its melting characteristics may deteriorate, thereby reducing the melt kneading and reactive extrusion characteristics of the compatibilizer.

[0148] During melt kneading in a reactive compatibilizer, the hydroxyl (-OH) or carboxyl (-COOH) groups present in the first and second reactants react with the glycidyl group or maleic anhydride structure in the reactive compatibilizer to form ether bonds or ester bonds.

[0149] Specifically, through steps (2-1) and (2-3), a thermoplastic polyester elastomer resin composed of repeating units ((a), (b) and (c)) and repeating unit (d) represented by the above formulas 1 to 3 can be prepared in high yield.

[0150] Compositions and Articles

[0151] 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 compressive elastic recovery, they can be used to produce a variety of products.

[0152] The compositions according to the invention may also contain known solvents and additives as needed.

[0153] Furthermore, the articles of the present invention comprise the aforementioned thermoplastic polyester elastomer resin. There are no particular limitations on the articles of the present invention; they can be fibers, foam (molded articles in foam shape), or shoe parts.

[0154] The fiber can be a monocomponent fiber and / or a multicomponent fiber (e.g., a bicomponent fiber). This fiber can be made into woven fabrics, knitted fabrics, or nonwoven fabrics.

[0155] Foam (foam-like molded articles) can be manufactured by physical or chemical foaming processes of the aforementioned thermoplastic polyester elastomer resin in a mold or autoclave. There are no particular limitations on the density of the foam, but it may be around 0.15 g / cm³.3 Up to 0.45 g / cm 3 Between. Due to the use of the aforementioned thermoplastic polyester elastomer resin, this foam exhibits high elasticity and energy rebound properties; therefore, it can be applied to straps, bogie gears, highly elastic shock-absorbing components, etc.

[0156] The shoe component is obtained by placing the aforementioned thermoplastic polyester elastomer resin into a mold and molding it. Specifically, it may be the midsole, outsole, or cushioning material of the insole. Detailed Implementation

[0157] Invention Model

[0158] 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.

[0159] [Example 1]

[0160] Step (1-1): Preparation of reactants via transesterification

[0161] The volume is 1.2 m³. 3 The transesterification reactor, equipped with a tower and a water-cooled condenser, was charged with 22.2 kg of 1,4-butanediol (BD) as the diol component; 46.3 kg of polytetramethylene ether glycol (PTMG) and 13.9 kg of ethylene oxide-added polypropylene glycol (EO-PPG) as the high molecular weight diol component; 37.4 kg of dimethyl terephthalate (DMT) as the dicarboxylic acid component; 0.06 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 inside the reactor to 1 kg / cm². 2 An inert atmosphere was created. The added raw materials were then stirred under a nitrogen atmosphere while the temperature was increased. When the temperature inside 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 the 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 reactor capable of reacting under vacuum. 3 condensation reactor.

[0162] Steps (1-2): Preparation of thermoplastic polyester elastomer resin via polycondensation reaction

[0163] The pressure in the polycondensation reactor is reduced from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) within 30 minutes. Simultaneously, the temperature of the polycondensation reactor is raised to 245°C within 1 hour, while maintaining the pressure in the reactor at 1 Torr (absolute pressure: 1 mmHg) or lower during the polycondensation reaction. In this case, a higher stirring speed can be set 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. The polycondensation reaction is then continued 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 a thermoplastic polyester elastomer resin.

[0164] [Examples 2 to 6]

[0165] Except for the variations in the content (unit: kg) of each raw material as shown in Table 1 below, each thermoplastic polyester elastomer resin was obtained by the same preparation method as in Example 1.

[0166] [Comparative Examples 1 to 7]

[0167] Except for the variations in the content (unit: kg) of each raw material as shown in Table 1 below, each thermoplastic polyester elastomer resin was obtained by the same preparation method as in Example 2.

[0168] [Table 1]

[0169]

[0170] [Table 2]

[0171]

[0172] The composition and physical properties of the thermoplastic polyester elastomer resins obtained in Examples 1 to 6 and Comparative Examples 1 to 7 were evaluated as follows. The results are shown in Tables 3 and 4 below.

[0173] [Test Example 1] Content of hard segments (Equation 1) and soft segments (Equations 2 and 3)

[0174] Each thermoplastic polyester elastomer resin was dissolved in CDCl3 solvent at a concentration of 3 mg / ml, and its composition was determined using nuclear magnetic resonance (FMRI) at 25°C. 1¹H-NMR spectra. By analyzing the spectra, the contents (wt%) of BD, PTMG, and EO-PPG are calculated based on the total molar number of residues derived from the whole diol (BD, PTMG, EO-PPG, etc.), thereby confirming the contents of hard and soft segments.

[0175] [Test Example 2] Shore D Hardness (H)

[0176] 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 then stacked to obtain a specimen with a thickness of 6 mm. The hardness was then measured.

[0177] [Test Example 3] Intrinsic Viscosity (IV)

[0178] 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.

[0179] [Test Example 4] Melt Viscosity (MI)

[0180] 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.

[0181] [Test Example 5] Melting Point (T) m )

[0182] Each thermoplastic polyester elastomer resin was dried under reduced pressure at 50°C for 15 hours, melted, and quenched. Then, it was scanned using a differential scanning calorimeter (DSC, TA Instruments) at a heating rate of 10°C / min. The highest point of the endothermic peak caused by resin melting was then taken as the melting point (T). m ).

[0183] [Test Example 6] Tensile Strength

[0184] The tensile strength of various thermoplastic polyester elastomer resins 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. These specimens 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.

[0185] [Test Example 7] Compression Permanent Deformation (CS)

[0186] The compression set of each thermoplastic polyester elastomer resin 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 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.

[0187] [Test Example 8] Resilience (R)

[0188] The restoring force of various thermoplastic polyester elastomer resins was measured according to ASTM D2632. Specifically, 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 restoring force.

[0189] [Table 3]

[0190]

[0191] [Table 4]

[0192]

[0193] According to Tables 3 and 4 above, the thermoplastic polyester elastomer resins of Examples 1 to 5, which consist of soft segments and hard segments (Formula 1) composed of repeating units (Formulas 2 and 3) derived from PTMG and EO-PPG, exhibit excellent performance in terms of mechanical strength, elasticity (restoring force) and compression set, i.e. elastic recovery after long-term deformation.

[0194] In contrast, the thermoplastic polyester elastomer resins using PTMG alone in Comparative Examples 1 to 3, while exhibiting good mechanical strength, showed poor elasticity or elastic recovery. The thermoplastic polyester elastomer resins using only EO-PPG in Comparative Examples 4 and 5 showed significantly poor mechanical strength. Furthermore, in Comparative Examples 6 and 7, thermoplastic polyester elastomer resins containing soft segments and hard segments (Formula 1) of repeating units derived from PTMG and EO-PPG (Formulas 2 and 3) were used, but the weight ratio of the soft segments and the weight ratio of the soft segments to the hard segments were not controlled within the range of this invention. Therefore, their elasticity (restoring force) and compression set (elastic recovery after long-term deformation) were poor.

Claims

1. A thermoplastic polyester elastomer resin comprising a repeating unit (a) represented by the following Formula 1; a repeating unit (b) represented by the following Formula 2; and a repeating unit (c) represented by the following Formula 3, and satisfying the following relation Formula 1: [Formula 1] [Formula 2] [Formula 3] [Relation Formula 1] In the relation Formula 1, y is a weight of the repeating unit (b) represented by the Formula 2 in the thermoplastic polyester elastomer resin, and z is a weight of the repeating unit (c) represented by the Formula 3 in the thermoplastic polyester elastomer resin. 2.The thermoplastic polyester elastomer resin according to claim 1, satisfying the following relation Formula 2: [Relation Formula 2] In the relation Formula 2, x is a weight of the repeating unit (a) represented by the Formula 1 in the thermoplastic polyester elastomer resin, y is a weight of the repeating unit (b) represented by the Formula 2 in the thermoplastic polyester elastomer resin, and z is a weight of the repeating unit (c) represented by the Formula 3 in the thermoplastic polyester elastomer resin. ； 4.The thermoplastic polyester elastomer resin according to claim 1, satisfying the following relation Formula 3: [Relation Formula 3] In the relation Formula 3, H is a Shore D hardness of the thermoplastic polyester elastomer resin measured according to ASTM D2240; and R is a resilience of the thermoplastic polyester elastomer resin measured according to ASTM D2632. ； 5.The thermoplastic polyester elastomer resin according to claim 1, satisfying the following relation Formula 4: [Relation Formula 4] In the relation Formula 4, H is a Shore D hardness of the thermoplastic polyester elastomer resin measured according to ASTM D2240; and CS is a compression set of the thermoplastic polyester elastomer resin measured according to ISO 816 Method B. ； 6.The thermoplastic polyester elastomer resin according to claim 1, having an intrinsic viscosity of 1.0 dl / g to 2.4 dl / g. ； In formulae 1 to 3, R 1 to R 3 each independently a linear, branched or cyclic divalent aliphatic group having from 1 to 6 carbon atoms; or a divalent aromatic group having from 6 to 10 carbon atoms, m is an integer from 2 to 6, n is an integer from 4 to 6, 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, and 12 12 each independently a linear, branched or cyclic divalent aliphatic group having from 1 to 6 carbon atoms; or a divalent aromatic group having from 6 to 10 carbon atoms, m is an integer from 2 to 6, n is an integer from 4 to 6, 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, and​ 7.The thermoplastic polyester elastomer resin according to claim 1, wherein the repeating unit (a) represented by the Formula 1 is derived from a reaction of a diol component comprising 1,4-butanediol; and a dicarboxylic acid component; the repeating unit (b) represented by the Formula 2 is derived from a reaction of the dicarboxylic acid component and a high molecular weight diol component comprising polytetramethylene ether glycol; and the repeating unit (c) represented by the Formula 3 is derived from a reaction of the dicarboxylic acid component and a high molecular weight diol component comprising polypropylene glycol added with ethylene oxide. The amount of the 1,4-butanediol is 75 mol% or more based on the total mole percentage of the diol component, and The amount of the polytetramethylene ether glycol is 50 mol% or more based on the total mole percentage of the high molecular weight diol component. ； 9.The thermoplastic polyester elastomer resin according to claim 7, wherein the dicarboxylic acid component comprises at least one selected from the group consisting of terephthalic acid and dimethyl terephthalate, and 3. The thermoplastic polyester elastomer resin according to claim 1, having a tensile strength of 190 kgf / cm2 or more when measured according to the ASTM D638 standard. 2 or more. The amount of the at least one selected from the group consisting of terephthalic acid and dimethyl terephthalate is 50 mol% or more based on the total mole percentage of the dicarboxylic acid component. ​ ； ​ ​ ​ ； ​ ​ ​ ​ ​ 8. The thermoplastic polyester elastomer resin according to claim 7, wherein, ​ ​ ​ ​ 10. The thermoplastic polyester elastomer resin according to claim 7, wherein the number average molecular weight of the high molecular weight diol component comprising polytetramethylene ether glycol and the number average molecular weight of the high molecular weight diol component comprising polypropylene glycol with ethylene oxide addition are each 400 g / mol to 5,000 g / mol.

11. The thermoplastic polyester elastomer resin according to claim 7, wherein the number average molecular weight of the high molecular weight diol component comprising polytetramethylene ether glycol and the number average molecular weight of the high molecular weight diol component comprising polypropylene glycol with ethylene oxide addition are each 1,000 g / mol to 3,000 g / mol.

12. A method for producing a thermoplastic polyester elastomer resin, comprising: (1-1) reacting a diol component, a dicarboxylic acid component, and a high molecular weight diol component to obtain a reactant; and (1-2) subjecting the reactant to a polycondensation reaction, wherein the thermoplastic polyester elastomer resin comprises a repeating unit (a) represented by the following Formula 1; a repeating unit (b) represented by the following Formula 2; and a repeating unit (c) represented by the following Formula 3, and satisfies the following relationship Formula 1: [Formula 1]: [Formula 2]: ； [Formula 3]: ； [Relationship Formula 1]: ； In the relationship Formula 1, y is the weight of the repeating unit (b) represented by Formula 2 in the thermoplastic polyester elastomer resin, and z is the weight of the repeating unit (c) represented by Formula 3 in the thermoplastic polyester elastomer resin. ； In formulae 1 to 3, R 1 to R 3 each independently a linear, branched or cyclic divalent aliphatic group having from 1 to 6 carbon atoms; or a divalent aromatic group having from 6 to 10 carbon atoms, m is an integer from 2 to 6, n is an integer from 4 to 6, 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, and 12 to R 12 each independently a linear, branched or cyclic divalent aliphatic group having from 1 to 6 carbon atoms; or a divalent aromatic group having from 6 to 10 carbon atoms, m is an integer from 2 to 6, n is an integer from 4 to 6, 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, and 13. A composition comprising the thermoplastic polyester elastomer resin according to any one of claims 1 to 11.

14. An article comprising the thermoplastic polyester elastomer resin according to any one of claims 1 to 11.

15. The article according to claim 14, wherein the article is a fiber, a foam, or a shoe component. ​

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