KR20250025248A - Thermoplastic polyester elastomer resin and method of manufacturing the same - Google Patents

Abstract

The present invention relates to a thermoplastic polyester elastomer resin, a method for producing the same, and an article comprising the same. The thermoplastic polyester elastomer resin may have high mechanical strength, elongation, etc., and excellent elasticity and compression-elastic recovery force. Accordingly, the thermoplastic polyester elastomer resin may be utilized in the production of various articles (e.g., fibers, foams, shoe parts, etc.).

Description

Thermoplastic polyester elastomer resin and method of manufacturing the same {THERMOPLASTIC POLYESTER ELASTOMER RESIN AND METHOD OF MANUFACTURING THE SAME}

The present invention relates to a thermoplastic polyester elastomer resin having excellent physical properties such as mechanical strength, elasticity, and compression-elastic recovery force, and a method for producing the same, while comprising a hard block having thermoplastic properties and a soft block having elastomeric properties (introducing PTMG and EO-PPG).

Thermoplastic elastomer (TPE) resins include hard segments derived from thermoplastic polymers and having thermoplastic properties, and soft segments derived from elastomers, which are rubber-like substances, and having elastomeric properties. Compared to conventional thermosetting rubber, the hard blocks physically bonded by crystals are similar to chemical cross-linking called "vulcanization," and the soft blocks are similar to non-crystalline rubber-like properties.

Among the above TPE resins, thermoplastic polyester elastomer (TPEE) resins have high mechanical strength and excellent impact resistance, heat resistance, flexibility, and moldability, and are used in the manufacture of automobile parts, electrical and electronic parts, fibers, films, etc.

The above TPEE resin mainly includes a tetramethylene ester crystalline hard block and a polyether polyol ester amorphous soft block. As raw materials for manufacturing the soft block of the above TPEE resin, polyethylene ether glycol (PEG), poly(1,2-propylene) glycol (PPG), polytetramethylene ether glycol (PTMG), etc. have been used.

However, the TPEE resin manufactured using the above PEG as a raw material has a disadvantage of high moisture content characteristics, and the PPG has poor polymerization reactivity, so they are not often used as a raw material for manufacturing TPEE resin. On the other hand, the TPEE resin manufactured using the above PTMG as a raw material has good physical properties such as mechanical strength and elongation, but there is a limit to increasing physical properties such as elasticity and compressive elasticity recovery force to a target level or higher.

Therefore, there is a need to develop a new TPEE resin that has excellent properties such as mechanical strength and elongation, as well as high elasticity and compressive elasticity recovery, so that it can be used in the manufacture of various products.

Republic of Korea Publication Patent No. 2021-0080090

In order to solve the above-mentioned conventional problems, the inventors of the present invention have conducted various studies, and as a result, it has been confirmed that a thermoplastic polyester elastomer (TPEE) resin having excellent mechanical strength and improved elasticity and compression-elastic recovery is obtained by blending two or more kinds of polyester elastomer resins in which the crystallinity and crystallization speed of the soft block are controlled to be low while preventing phase separation between the hard block and the soft block.

Accordingly, the task of the present invention is to provide a thermoplastic polyester elastomer resin having excellent mechanical strength, elasticity and compression-elastic recovery force, and a method for producing the same.

In addition, another object of the present invention is to provide a composition or article comprising the thermoplastic polyester elastomer resin.

In order to solve the above problem, the present invention provides a thermoplastic polyester elastomer resin comprising a first polyester elastomer resin including a repeating unit (a) represented by the following chemical formula 1 and a repeating unit (b) represented by the following chemical formula 2; and a second polyester elastomer resin including a repeating unit (a) represented by the following chemical formula 1 and a repeating unit (c) represented by the following chemical formula 3:

[Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

In the above chemical formulas 1 to 3,

R ¹ to R ³ are each independently a C ₁ to C ₁₂ straight-chain, branched, or cyclic divalent aliphatic hydrocarbon group; or a C ₆ to C ₁₂ divalent aromatic hydrocarbon group,

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.

In addition, the present invention provides a method for producing a thermoplastic polyester elastomer resin, comprising: (1-1) a step of reacting a first glycol component, a first dicarboxylic acid component, and a first high molecular weight glycol component to obtain a first polyester elastomer resin; (1-2) a step of reacting a second glycol component, a second dicarboxylic acid component, and a second high molecular weight glycol component to obtain a second polyester elastomer resin; and (1-3) a step of melt-blending the first polyester elastomer resin and the second polyester elastomer resin, wherein the first polyester elastomer resin includes a repeating unit (a) represented by the chemical formula 1 and a repeating unit (b) represented by the chemical formula 2, and the second polyester elastomer resin includes a repeating unit (a) represented by the chemical formula 1 and a repeating unit (c) represented by the chemical formula 3.

In addition, the present invention provides a composition comprising the thermoplastic polyester elastomer resin.

In addition, the present invention provides an article comprising the thermoplastic polyester elastomer resin.

The thermoplastic polyester elastomer resin according to the present invention can exhibit excellent mechanical strength because it includes a first polyester elastomer resin to which polytetramethylene ether glycol (PTMG) is applied for the formation of a soft block. In addition, the thermoplastic polyester elastomer resin according to the present invention can exhibit excellent elasticity and compressive elasticity recovery force because it includes a second polyester elastomer resin to which ethylene oxide-added polypropylene glycol (EO-PPG) is applied, which has a methylene side branch attached to the polyol chain main chain for the formation of a soft block to restrict the movement of polymer chains of the soft block and generate sufficient free volume between polymer chains to lower crystallinity and crystallization speed and increase incompatibility with the hard block to promote phase separation from the hard block.

As such, the thermoplastic polyester elastomer resin according to the present invention exhibits excellent mechanical strength, elasticity and compressive elastic recovery while exhibiting a desired level of hardness, and thus can be utilized in the manufacture of various articles such as automobile parts, electrical and electronic parts, fibers, films, matrices, cushioning materials, foams, and shoe parts.

Hereinafter, the present invention will be described in detail. Herein, the present invention is not limited to the contents described below, and may be modified in various forms as long as the gist of the invention is not changed.

The word “comprising” or “including” as used herein is intended to specify particular features, regions, steps, processes, elements and/or components, and does not exclude the presence or addition of other features, regions, steps, processes, elements and/or components, unless specifically stated otherwise.

In this specification, the terms first, second, etc. are used to describe various components, and the components are not limited to the terms. The terms are used for the purpose of distinguishing one component from another.

All numbers and expressions indicating the amounts of ingredients, reaction conditions, etc. described in this specification can be understood to be modified by the term "about" in all cases unless otherwise specified.

Thermoplastic polyester elastomer (TPEE) resin forms an elastomer matrix by phase separation due to the incompatibility of crystalline hard blocks and amorphous soft blocks, thereby exhibiting elastic properties like rubber. In order to improve the elastic properties of such thermoplastic polyester elastomer resin, it is required to clearly control the boundary distinction between the hard blocks and the soft blocks. Specifically, by increasing the difference in crystallinity/amorphism of the hard blocks and the soft blocks to improve the incompatibility while increasing the free volume of the polymer chains, the phase separation can be made to occur more clearly. That is, the hard block needs to crystallize as quickly as possible, and the soft block needs to crystallize as late as possible, whereby a thermoplastic polyester elastomer resin having high mechanical strength and excellent elastic properties can be obtained.

Based on these points, the thermoplastic polyester elastomer resin according to the present invention has the characteristics of a mixture of a first polyester elastomer resin in which the crystallinity and crystallization speed of the soft block are controlled to be low by applying polytetramethylene ether glycol (PTMG) when forming the soft block, and a second polyester elastomer resin in which the incompatibility of the soft block and the hard block is increased by applying ethylene oxide-added polypropylene glycol (EO-PPG) when forming the soft block, thereby controlling phase separation to be distinct, which will be specifically described as follows.

Thermoplastic polyester elastomer resin

A thermoplastic polyester elastomer resin according to the present invention comprises a first polyester elastomer resin comprising a repeating unit (a) represented by the following chemical formula 1 and a repeating unit (b) represented by the following chemical formula 2; and a second polyester elastomer resin comprising a repeating unit (a) represented by the following chemical formula 1 and a repeating unit (c) represented by the following chemical formula 3.

[Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

In the above chemical formulas 1 to 3,

R ¹ to R ³ are the same or different from each other, and each independently represents a C ₁ to C ₁₂ straight-chain, branched, or cyclic divalent aliphatic hydrocarbon group; or a C ₆ to C ₁₂ divalent aromatic hydrocarbon group,

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.

First polyester elastomer resin

The first polyester elastomer resin according to the present invention serves to increase the mechanical strength of the thermoplastic polyester elastomer resin.

The repeating unit (a) represented by the chemical formula 1 included in the first polyester elastomer resin may be a repeating unit constituting a hard block of the first polyester elastomer resin. In the chemical formula 1, R ¹ is specifically a C ₅ to C ₁₂ cyclic divalent aliphatic hydrocarbon group, or a C ₆ to C ₁₂ divalent aromatic hydrocarbon group, and m may be an integer of 3 to 5. For example, R ¹ may be a cyclohexylene group or a phenylene group, and m may be an integer of 4.

The repeating unit (b) represented by the chemical formula 2 included in the first polyester elastomer resin may be a repeating unit constituting a soft block of the first polyester elastomer resin. In the chemical formula 2, R ² may specifically be a C ₅ to C ₁₂ cyclic divalent aliphatic hydrocarbon group, or a C ₆ to C ₁₂ divalent aromatic hydrocarbon group. In addition, n may be an integer of 4 or 5, and p may be an integer of 15 to 25. For example, R ² may be a cyclohexylene group or a phenylene group, n may be an integer of 4, and p may be an integer of 18 to 22.

The repeating unit (a) represented by the above chemical formula 1 can be derived from the reaction of a glycol component including 1,4-butanediol and a dicarboxylic acid component, and the repeating unit (b) represented by the above chemical formula 2 can be derived from the reaction of a dicarboxylic acid component and a high molecular weight glycol component including polytetramethylene ether glycol.

Specifically, the first polyester elastomer resin may be a resin obtained by using a dicarboxylic acid component (first dicarboxylic acid component), a glycol component (first glycol component), and a high molecular weight glycol component (first high molecular weight glycol component) as reaction raw materials.

The above dicarboxylic acid component (e.g., a dicarboxylic acid, an ester thereof, a chloride thereof, or an anhydride thereof) may be an aliphatic dicarboxylic acid component, an aromatic dicarboxylic acid component, or a combination thereof.

The aliphatic dicarboxylic acid component may be a linear, branched, or cyclic aliphatic dicarboxylic acid component. The aliphatic dicarboxylic acid component may have 4 or more, 5 or more, 6 or more, or 7 or more carbon atoms, and may have 20 or less, 15 or less, 13 or less, 12 or less, or 10 or less. Specifically, the aliphatic dicarboxylic acid component may have 4 to 20, 5 to 15, or 6 to 10 carbon atoms.

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, isodecylsuccinic acid, maleic acid, fumaric acid, glutaric acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid.

The number of carbon atoms of the aromatic dicarboxylic acid component may be 6 or more, 7 or more, 8 or more, or 10 or more, and 25 or less, 20 or less, or 15 or less. Specifically, the number of carbon atoms of the aromatic dicarboxylic acid component may be 6 to 25, 6 to 15, or 6 to 10.

For example, the aromatic dicarboxylic acid component may include, but is not limited to, at least one selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 4,4'-stilbenedicarboxylic acid, 2,5-furandicarboxylic acid, 2,5-thiophenedicarboxylic acid, and dimethyl terephthalate.

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

The glycol component may be a component that forms a tetramethyl ester hard block (e.g., repeating unit (a) of chemical formula 1) through an esterification reaction or an ester exchange reaction with the dicarboxylic acid component. The glycol component may have 2 or more, 3 or more, or 4 or more carbon atoms, and may be 15 or less, 12 or less, 10 or less, or 8 or less. Specifically, the glycol component may have 2 to 15, 3 to 10, 4 to 8, or 4 to 6 carbon atoms.

For example, the glycol component may be ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 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, polytetramethylene glycol, polyhexamethylene glycol, a copolymer of ethylene oxide and tetrahydrofuran, polycarbonate diol, It may include at least one selected from the group consisting of polyneopentyl glycol, poly-3-methylpentanediol, and poly-1,5-pentanediol, but is not limited thereto. Specifically, the glycol component may include at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol.

Preferably, the glycol component may include 1,4-butanediol. The amount of the 1,4-butanediol used (the amount introduced 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 mol% of the glycol component (first glycol component). Specifically, the amount of 1,4-butanediol used may be 75 to 100 mol%, 80 to 100 mol%, 83 to 100 mol%, 85 to 100 mol%, 90 to 100 mol%, or 90 to 95 mol%.

The number average molecular weight of these glycol components is not particularly limited, but may be less than 400 g/mol, less than 350 g/mol, less than 300 g/mol, or less than 250 g/mol.

The high molecular weight glycol component may be a component that forms a poly(alkylene oxide) ester soft block (e.g., repeating unit (b) of Chemical Formula 2) through an esterification reaction or an ester exchange reaction with the dicarboxylic acid component. The high molecular weight glycol component may include polytetramethylene ether glycol (PTMG). Since the high molecular weight glycol component includes the polytetramethylene ether glycol (PTMG), the mechanical strength of a thermoplastic polyester elastomer resin including a first polyester elastomer resin obtained therefrom can be significantly increased.

Preferably, the high molecular weight glycol component can be composed of polytetramethylene ether glycol (PTMG). The amount of polytetramethylene ether glycol (PTMG) used (amount introduced during reaction) is not particularly limited, but 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 mol% of the high molecular weight glycol component (first high molecular weight glycol component). Specifically, the amount of polytetramethylene ether glycol (PTMG) used may be 50 to 100 mol%, 50 to 99.5 mol%, 60 to 99 mol%, 65 to 95 mol%, 70 to 90 mol%, 75 to 90 mol%, or 75 to 85 mol%.

The number average molecular weight of the high molecular weight glycol component including the polytetramethylene ether glycol (PTMG) is not particularly limited, but may 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 may 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, in order to ensure good phase separation with the hard block, the number average molecular weight of the high molecular weight glycol component including the polytetramethylene ether glycol (PTMG) may be 400 to 5,000 g/mol, 800 to 3,500 g/mol, or 1,000 to 3,000 g/mol.

For example, the number average molecular weight of the polytetramethylene ether glycol (PTMG) 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.

According to the present invention, the first polyester elastomer resin may include a structure (repeating unit or structural unit) represented by the following chemical formula 4 in which the repeating unit (a) represented by the chemical formula 1 and the repeating unit (b) represented by the chemical formula 2 are bonded to each other.

[Chemical Formula 4]

In the chemical formula 4 above, m, n and p are the same as described above, and a and b are weight ratios.

These first polyester elastomer resins can satisfy the following equation 1:

[Formula 1]

0.5 ≤ a / b ≤ 3.0

In the above equation 1,

a is the weight occupied by the repeating unit (a) represented by the chemical formula 1 in the first polyester elastomer resin (total weight of the first polyester elastomer resin),

b is the weight occupied by the repeating unit (b) represented by the chemical formula 2 in the first polyester elastomer resin (total weight of the first polyester elastomer resin).

Specifically, the ratio of a / b in the above formula 1 may 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 ratio of a / b is within the above range, the mechanical strength of the thermoplastic polyester elastomer resin can be achieved at a desired level.

According to the present invention, the first polyester elastomer resin may have an intrinsic viscosity (IV) of 1.0 ㎗/g or more, and specifically, 1.1 ㎗/g or more, 1.2 ㎗/g or more, 1.3 ㎗/g or more, 1.4 ㎗/g or more, or 1.5 ㎗/g or more (e.g., 1.0 to 1.9 ㎗/g, 1.25 to 1.88 ㎗/g, or 1.32 to 1.86 ㎗/g).

In addition, the first polyester elastomer resin may have a tensile strength of 190 kgf/cm ² or greater as measured according to ASTM D638, and specifically, 200 kgf/cm ² or greater, 210 kgf/cm ² or greater, 220 kgf/cm ² or greater, 230 kgf/cm ² or greater, 250 kgf/cm ² or greater, 300 kgf/cm ² or greater, or 350 kgf/cm ² or greater (e.g., 190 to 345 kgf/cm ² , 205 to 340 kgf/cm ² , or 260 to 320 kgf/cm ² ).

Second polyester elastomer resin

The second polyester elastomer resin according to the present invention serves to increase the elasticity and compression-elastic recovery force of the thermoplastic polyester elastomer resin.

The repeating unit (a) represented by the chemical formula 1 included in the second polyester elastomer resin may be a repeating unit constituting a hard block of the second polyester elastomer resin. In the chemical formula 1, R ¹ is specifically a C ₅ to C ₁₂ cyclic divalent aliphatic hydrocarbon group, or a C ₆ to C ₁₂ divalent aromatic hydrocarbon group, and m may be an integer of 3 to 5. For example, R ¹ may be a cyclohexylene group or a phenylene group, and m may be an integer of 4.

The repeating unit (c) represented by the chemical formula 3 included in the second polyester elastomer resin may be a repeating unit constituting a soft block of the second polyester elastomer resin. In the chemical formula 3, R ³ may specifically be a C ₅ to C ₁₂ cyclic divalent aliphatic hydrocarbon group, or a C ₆ to C ₁₂ divalent aromatic hydrocarbon group. In addition, t may be an integer of 5 to 25, and s may be an integer of 5 to 35. For example, R ³ may be a cyclohexylene group or a phenylene group, t may be an integer of 10 to 20, and s may be an integer of 10 to 30.

The repeating unit (a) represented by the above chemical formula 1 can be derived from the reaction of a glycol component including 1,4-butanediol and a dicarboxylic acid component, and the repeating unit (c) represented by the above chemical formula 3 can be derived from the reaction of a dicarboxylic acid component and a high molecular weight glycol component including ethylene oxide-added polypropylene glycol.

Specifically, the second polyester elastomer resin may be a resin obtained by using a dicarboxylic acid component (second dicarboxylic acid component), a glycol component (second glycol component), and a high molecular weight glycol component (second high molecular weight glycol component) as reaction raw materials.

The above dicarboxylic acid component (e.g., a dicarboxylic acid, an ester thereof, a chloride thereof, or an anhydride thereof) may be an aliphatic dicarboxylic acid component, an aromatic dicarboxylic acid component, or a combination thereof.

The aliphatic dicarboxylic acid component may be a linear, branched, or cyclic aliphatic dicarboxylic acid component. The aliphatic dicarboxylic acid component may have 4 or more, 5 or more, 6 or more, or 7 or more carbon atoms, and may have 20 or less, 15 or less, 13 or less, 12 or less, or 10 or less. Specifically, the aliphatic dicarboxylic acid component may have 4 to 20, 5 to 15, or 6 to 10 carbon atoms.

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, isodecylsuccinic acid, maleic acid, fumaric acid, glutaric acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid.

The number of carbon atoms of the aromatic dicarboxylic acid component may be 6 or more, 7 or more, 8 or more, or 10 or more, and 25 or less, 20 or less, or 15 or less. Specifically, the number of carbon atoms of the aromatic dicarboxylic acid component may be 6 to 25, 6 to 15, or 6 to 10.

For example, the aromatic dicarboxylic acid component may include, but is not limited to, at least one selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 4,4'-stilbenedicarboxylic acid, 2,5-furandicarboxylic acid, 2,5-thiophenedicarboxylic acid, and dimethyl terephthalate.

Preferably, the dicarboxylic acid component may include at least one selected from the group consisting of terephthalic acid and dimethyl terephthalate. The amount used (amount introduced during reaction) of at least one (at least one component) selected from the group consisting of terephthalic acid and dimethyl terephthalate is not particularly limited, but may be at least 50 mol%, at least 65 mol%, at least 70 mol%, at least 85 mol%, at least 90 mol%, or at least 95 mol% based on the total mol% of the dicarboxylic acid component (second dicarboxylic acid component). Specifically, the amount of the terephthalic acid, the dimethyl terephthalate, or a combination thereof may be 50 to 100 mol %, 55 to 100 mol %, 60 to 100 mol %, 70 to 100 mol %, 85 to 100 mol %, or 90 to 95 mol %.

The glycol component may be a component that forms a tetramethyl ester hard block (e.g., repeating unit (a) of chemical formula 1) through an esterification reaction or an ester exchange reaction with the dicarboxylic acid component. The glycol component may have 2 or more, 3 or more, or 4 or more carbon atoms, and may be 15 or less, 12 or less, 10 or less, or 8 or less. Specifically, the glycol component may have 2 to 15, 3 to 10, 4 to 8, or 4 to 6 carbon atoms.

For example, the glycol component may be ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 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, polytetramethylene glycol, polyhexamethylene glycol, a copolymer of ethylene oxide and tetrahydrofuran, polycarbonate diol, It may include at least one selected from the group consisting of polyneopentyl glycol, poly-3-methylpentanediol, and poly-1,5-pentanediol, but is not limited thereto. Specifically, the glycol component may include at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol.

Preferably, the glycol component may include 1,4-butanediol. The amount of the 1,4-butanediol used (the amount introduced 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 mol% of the glycol component (second glycol component). Specifically, the amount of 1,4-butanediol used may be 75 to 100 mol%, 80 to 100 mol%, 83 to 100 mol%, 85 to 100 mol%, 90 to 100 mol%, or 90 to 95 mol%.

The number average molecular weight of these glycol components is not particularly limited, but may be less than 400 g/mol, less than 350 g/mol, less than 300 g/mol, or less than 250 g/mol.

The high molecular weight glycol component may be a component that forms a poly(alkylene oxide) ester soft block (e.g., repeating unit (c) of chemical formula 3) through an esterification reaction or an ester exchange reaction with the dicarboxylic acid component. The high molecular weight glycol component may include ethylene oxide addition polypropylene glycol (EO-PPG). Since the high molecular weight glycol component includes the ethylene oxide addition polypropylene glycol (EO-PPG), the elasticity and compression-elastic recovery force of the thermoplastic polyester elastomer resin can be significantly increased.

Preferably, the high molecular weight glycol component can be composed of ethylene oxide added polypropylene glycol (EO-PPG). The amount of the ethylene oxide added polypropylene glycol (EO-PPG) used (amount added during reaction) is not particularly limited, but 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 mol% of the high molecular weight glycol component (second high molecular weight glycol component). Specifically, the amount of the ethylene oxide added polypropylene glycol (EO-PPG) used may be 50 to 100 mol%, 50 to 99.5 mol%, 60 to 99 mol%, 65 to 95 mol%, 70 to 90 mol%, 75 to 90 mol%, or 75 to 85 mol%.

The number average molecular weight of the high molecular weight glycol component including the above ethylene oxide-added polypropylene glycol (EO-PPG) is not particularly limited, but may 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 may 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, in order to ensure good phase separation with the hard block, the number average molecular weight of the high molecular weight glycol component may be 400 to 5,000 g/mol, 800 to 3,500 g/mol, or 1,000 to 3,000 g/mol.

For example, the number average molecular weight of the 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.

According to the present invention, the second polyester elastomer resin may include a structure (repeating unit or structural unit) represented by the following chemical formula 5, in which the repeating unit (a) represented by the chemical formula 1 and the repeating unit (c) represented by the chemical formula 3 are bonded to each other.

[Chemical Formula 5]

In the chemical formula 5 above, m, t and s are the same as described above, and a and c are weight ratios.

These second polyester elastomer resins can satisfy the following equation 2:

[Formula 2]

0.5 ≤ a / c ≤ 2.5

In the above equation 2,

a is the weight occupied by the repeating unit (a) represented by the chemical formula 1 in the second polyester elastomer resin (total weight of the second polyester elastomer resin),

c is the weight occupied by the repeating unit (c) represented by the chemical formula 3 in the second polyester elastomer resin (total weight of the second polyester elastomer resin).

Specifically, the ratio of a / c in the above formula 2 may 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 ratio of a / c is within the above range, the elasticity and compression-elastic recovery force of the thermoplastic polyester elastomer resin can be optimized to a desired level.

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

According to the present invention, the second polyester elastomer resin may have an intrinsic viscosity (IV) of 1.0 ㎗/g or more, specifically, 1.03 ㎗/g or more, 1.05 ㎗/g or more, 1.08 ㎗/g or more, 1.1 ㎗/g or more, or 1.3 ㎗/g or more (e.g., 1.0 to 1.45 ㎗/g, 1.04 to 1.38 ㎗/g, or 1.2 to 1.25 ㎗/g).

In addition, the second polyester elastomer resin may have a tensile strength of 100 kgf/cm ² or greater as measured according to ASTM D638, and specifically, 105 kgf/cm ² or greater, 115 kgf/cm ² or greater, 125 kgf/cm ² or greater, 140 kgf/cm ² or greater, 160 kgf/cm ² or greater, 170 kgf/cm ² or greater, or 180 kgf/cm ² or greater (e.g., 100 to 200 kgf/cm ² , 110 to 190 kgf/cm ² , or 150 to 180 kgf/cm ² ).

According to the present invention, the mixing ratio of the first polyester elastomer resin and the second polyester elastomer resin included in the thermoplastic polyester elastomer resin may be a weight ratio of 40:60 to 99:1, a weight ratio of 45:55 to 99:1, a weight ratio of 50:50 to 98:2, a weight ratio of 55:45 to 98:2, a weight ratio of 60:40 to 90:10, a weight ratio of 65:35 to 90:10, a weight ratio of 70:30 to 85:15, or a weight ratio of 75:25 to 85:15. When the mixing ratio of the first and second polyester elastomer resins is within the above range, a thermoplastic polyester elastomer resin having excellent elasticity and compression-elastic recovery force in addition to mechanical strength can be provided.

The thermoplastic polyester elastomer resin may include a mixture in which the first polyester elastomer resin and the second polyester elastomer resin are mixed, a crosslinked product in which the first polyester elastomer resin and the second polyester elastomer resin are combined, or a combination thereof. Specifically, the thermoplastic polyester elastomer resin may be a mixed resin in which the first polyester elastomer resin and the second polyester elastomer resin are mixed, a crosslinked resin in which the first polyester elastomer resin and the second polyester elastomer resin are physically or chemically combined (copolymerized thermoplastic polyester elastomer resin), or a resin in which the mixed resin and the crosslinked resin are mixed.

According to the present invention, the thermoplastic polyester elastomer resin comprises the first polyester elastomer resin and the second polyester elastomer resin, thereby including the repeating unit (a), the repeating unit (b) and the repeating unit (c), wherein the content ratio (weight ratio) between these repeating units is controlled within a specific range.

Specifically, the thermoplastic polyester elastomer resin according to the present invention can satisfy the following Equation 3. As the thermoplastic polyester elastomer resin satisfies the following Equation 3, it can have a desired high molecular weight and higher mechanical strength.

[Formula 3]

0.5 ≤ (y + z) / x ≤ 3.0

In the above equation 3,

x is the total weight occupied by the repeating unit (a) represented by the chemical formula 1 in the thermoplastic polyester elastomer resin (total weight of the thermoplastic polyester elastomer resin),

y is the total weight occupied by the repeating unit (b) represented by the chemical formula 2 in the thermoplastic polyester elastomer resin (total weight of the thermoplastic polyester elastomer resin),

z is the total weight occupied by the repeating unit (c) represented by the chemical formula 3 in the thermoplastic polyester elastomer resin (total weight of the thermoplastic polyester elastomer resin).

Specifically, in the above formula 3, 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, 1.15 to 2.45, 1.16 to 2.10, or 1.17 to 2.00.

In addition, the thermoplastic polyester elastomer resin according to the present invention can satisfy the following Equation 4. As the thermoplastic polyester elastomer resin satisfies the following Equation 4, the elasticity and compression-elastic recovery force can be more excellent.

[Formula 4]

0.3 ≤ y / z ≤ 37

In the above equation 4,

y is the total weight occupied by the repeating unit (b) represented by the chemical formula 2 in the thermoplastic polyester elastomer resin (total weight of the thermoplastic polyester elastomer resin),

z is the total weight occupied by the repeating unit (c) represented by the chemical formula 3 in the thermoplastic polyester elastomer resin (total weight of the thermoplastic polyester elastomer resin).

Specifically, the ratio of y/z in the above formula 3 can be 0.35 to 36.5, 0.38 to 35, 0.4 to 32, 0.4 to 30.5, 0.5 to 20, 0.8 to 15, 1 to 10, 1.1 to 8, 1.2 to 5, 1.3 to 3.5, or 1.5 to 4.5.

Meanwhile, the thermoplastic polyester elastomer resin according to the present invention may further include a reactive compatibilizer, a bonding structure derived from the reactive compatibilizer, or a combination thereof, in order to further enhance elasticity and compressive-elastic recovery force, as well as mechanical strength, elongation, etc.

The above reactive compatibilizer is an additive that helps improve miscibility by preventing phase separation between each resin component in a mixture of two or more resins and enabling the formation of a stable and long-term continuous phase. Specifically, the reactive compatibilizer is a reactive polymer that is compatibilizable with one resin when two resins are mixed and reacts with a functional group of the other resin, and when this is added to a mixture of two resins (i.e., the first polyester elastomer resin and the second polyester elastomer resin) and a reactive extrusion process is performed, it can induce the formation of a block copolymer or a graft copolymer.

These reactive compatibilizers can be selected from the group consisting of isocyanate compounds, carbodiimide compounds (for example, polycarbodiimide compounds having two or more -N=C=N- structures in the molecule), epoxy compounds, oxazoline compounds, compounds having a glycidyl group, and compounds having a maleic anhydride structure. Here, the isocyanate compound has too high a reactivity with moisture, so that reactivity control and handling (storage) may be difficult, and the carbodiimide compound is expensive, so that economic feasibility may be low. In addition, the epoxy compound has a large difference in the degree of reactivity depending on the epoxy equivalent and the number of functional groups, so that reactivity control may be difficult, and the oxazoline compound has low reactivity compared to other compounds, so that it may be difficult to expect an effect of improving miscibility between resin components. Therefore, it may be preferable to use a compound having a glycidyl group or a compound having a maleic anhydride structure as the reactive compatibilizer.

The compound having the glycidyl group may specifically be a glycidyl group-modified olefin rubber polymer, and preferably may be a polymer in which glycidyl (meth)acrylate is grafted onto a polyolefin rubber copolymer (Glycidyl methacrylate grafted polyolefin elastomers). The compound having the maleic anhydride structure may specifically be a polymer in which maleic anhydride is grafted onto a polyolefin rubber copolymer (Maleic anhydride grafted polyolefin elastomers).

For example, the reactive compatibilizer may be poly(ethylene-co-methylacrylate-co-glycidyl methacrylate) comprising a structure represented by the following chemical formula 6. In addition, the reactive compatibilizer may be poly(ethylene-co-ethylacrylate-co-maleic anhydride) comprising a structure represented by the following chemical formula 7.

[Chemical formula 6]

[Chemical formula 7]

In the chemical 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. For example, in the chemical formula 6, based on the total weight of poly(ethylene-co-methylacrylate-co-glycidyl methacrylate), structure a may be 65 to 75 wt%, structure b may be 20 to 25 wt%, and structure c may be 5 to 10 wt%.

In addition, in the chemical 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 the chemical formula 7, based on the total weight of poly(ethylene-co-ethylacrylate-co-maleic anhydride), structure d may be 72 to 84 wt%, structure e may be 15 to 25 wt%, and structure f may be 1 to 3 wt%.

As such reactive commercialization agents, commercially available products include Rotader AX8840, Rotader AX8900, and Rotader AX4720.

According to the present invention, the amount of the reactive compatibilizer used (amount introduced during reaction) is not particularly limited, but may be 0.1 to 10 wt%, 0.3 to 9 wt%, 0.5 to 8 wt%, 0.8 to 7 wt%, 1 to 5 wt%, 1.5 to 4.5 wt%, or 2 to 4 wt%, 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 the reactive compatibilizer used is within the above range, the thermoplastic polyester elastomer resin has a melt viscosity at a desired level, thereby improving the moldability (processability) of the thermoplastic polyester elastomer resin.

By introducing such a reactive compatibilizer, the thermoplastic polyester elastomer resin according to the present invention may include a repeating unit (a) represented by the chemical formula 1, a repeating unit (b) represented by the chemical formula 2, a repeating unit (c) represented by the chemical formula 3, and a bonding structure derived from the reactive compatibilizer (for example, a structure represented by the chemical formula 6 or the chemical formula 7). For example, the thermoplastic polyester elastomer resin may be a copolymerized thermoplastic polyester elastomer resin in which a structure represented by the chemical formula 4 and a structure represented by the chemical formula 5 are bonded by a structure represented by the chemical formula 6 or a structure represented by the chemical formula 7.

The thermoplastic polyester elastomer resin according to the present invention can exhibit improved physical properties by selectively including the reactive compatibilizer together with the first polyester elastomer resin and the second polyester elastomer resin to which the high molecular weight glycol component (PTMG, EO-PPG) is respectively applied for forming a soft block as described above.

Specifically, the thermoplastic polyester elastomer resin according to the present invention may have a tensile strength measured according to ASTM D638 of 150 kgf/cm ² or more, 170 kgf/cm ² or more, 190 kgf/cm 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 may be 190 to 350 kgf/cm ² , 195 to 335 kgf/cm ² , 200 to 325 kgf/cm ² , or 210 to 320 kgf/cm ² .

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

The thermoplastic polyester elastomer resin according to the present invention may have a Shore D hardness of 20 to 60, 25 to 55, 28 to 53, 28 to 50, 30 to 48, or 30 to 45.

The thermoplastic polyester elastomer resin according to the present invention may have a compression set (compression-elastic recovery) of 30 to 60 %, 33 to 59 %, 35 to 58 %, 37 to 57 %, 40 to 56 %, 42 to 55 %, 43 to 54 %, or 44 to 54 %.

The thermoplastic polyester elastomer resin according to the present invention may have a resilience of 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 %.

The thermoplastic polyester elastomer resin according to the present invention can have excellent mechanical strength, elasticity, and compression-elastic recovery by satisfying the following formula 5 and/or formula 6.

[Formula 5]

H/R ≤ 0.95

[Formula 6]

0.6 ≤ H / CS

In the above 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,

CS is the compression set of thermoplastic polyester elastomer resins measured according to ISO 816 Method B.

Specifically, the H/R ratio can be 0.3 to 0.75, 0.32 to 0.75, 0.34 to 0.73, 0.38 to 0.73, 0.4 to 0.70, 0.45 to 0.70, or 0.5 to 0.68.

Additionally, the H/CS ratio can be 0.8 to 0.95, 0.8 to 0.93, 0.81 to 0.92, 0.81 to 0.91, 0.81 to 0.9, 0.82 to 0.89, or 0.82 to 0.88.

The thermoplastic polyester elastomer resin according to the present invention can be utilized in the manufacture of various products because it has excellent mechanical strength, elasticity, and compressive elastic recovery while securing basic physical properties (e.g., heat resistance, impact resistance, moldability, etc.). Specifically, the thermoplastic polyester elastomer resin can be useful in the manufacture of fibers, films, foams (molded products in the form of foam), shoe parts (e.g., cushioning materials for shoe midsoles, shoe outsoles, and shoe insoles), etc.

Method for producing thermoplastic polyester elastomer resin

The thermoplastic polyester elastomer resin according to the present invention can be manufactured by subjecting each reactant raw material to an esterification reaction or an ester exchange reaction and then a polycondensation reaction to manufacture first and second polyester elastomer resins, respectively, and then melt-blending these resins. Specifically, the method for manufacturing the thermoplastic polyester elastomer resin according to the present invention includes: (1-1) a step of reacting a first glycol component, a first dicarboxylic acid component, and a first high molecular weight glycol component to obtain a first polyester elastomer resin; (1-2) a step of reacting a second glycol component, a second dicarboxylic acid component, and a second high molecular weight glycol component to obtain a second polyester elastomer resin; and (1-3) a step of melt-blending the first polyester elastomer resin and the second polyester elastomer resin, which will be specifically described as follows.

Step (1-1): Preparation of first polyester elastomer resin

According to the present invention, step (1-1) is a step of introducing a first glycol component, a first dicarboxylic acid component, and a first high molecular weight glycol component, which are reaction raw materials, into a reactor (esterification reactor or ester exchange reactor), performing an esterification reaction or an ester exchange reaction to obtain a reactant, and subjecting the reactant to a condensation polymerization reaction to obtain a first polyester elastomer resin. Here, preferably, the first glycol component includes 1,4-butanediol, and the first high molecular weight glycol component includes polytetramethylene ether glycol (PTMG). Since the description of each of these components is the same as described above, it will be omitted. In addition, since the description of the first dicarboxylic acid component is the same as described above, it will be omitted.

For the esterification reaction or ester exchange reaction, the first glycol component, the first dicarboxylic acid component, and the first high molecular weight glycol component may be simultaneously introduced into the reactor, or the first glycol component and the first dicarboxylic acid component may be introduced and the temperature of the reactor may be increased so that the temperature of the reactor reaches a certain level, and then the first high molecular weight glycol component may be introduced. For example, the introduction of the first high molecular weight glycol component may be performed at a temperature of 180 to 280° C. under a nitrogen atmosphere while removing by-products such as water or methanol.

The above esterification reaction or ester exchange reaction can be carried out in the presence of a catalyst. The catalyst is not particularly limited as long as it is a commonly known catalyst, and specifically, at least one selected from the group consisting of a titanium-based catalyst, a germanium-based catalyst, an antimony-based catalyst, an aluminum-based catalyst, and a tin-based catalyst can be used.

For example, the titanium-based catalyst may specifically include at least one selected from the group consisting of tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, triethanolamine titanate, acetylacetonate titanate, ethylacetoacetic ester titanate, isostearyl titanate, and titanium dioxide. The germanium-based catalyst may specifically include at least one selected from the group consisting of germanium dioxide, germanium tetrachloride, germanium ethyleneglycoxide, and germanium acetate.

The amount of the catalyst used (the amount introduced during the reaction) can be appropriately controlled depending on the reaction conditions and the type of catalyst. For example, the catalyst can be introduced so 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 weight part based on the total weight of the first glycol component, the first dicarboxylic acid component, and the first high molecular weight glycol component introduced into the reactor.

Meanwhile, in the esterification reaction or ester exchange reaction, one or more additives selected from the group consisting of a crystallizer, an antioxidant, and a polymerization reaction branching agent may be further added.

As the above crystallizing agent, a crystal nucleating agent, an ultraviolet absorber, a polyolefin resin, or a polyamide resin can be used.

As the above antioxidant, at least one selected from the group consisting of hindered phenol compounds, phosphite compounds, and thioether compounds can be used.

As the above polymerization reaction branching agent, a polyol having 3 to 6 hydroxyl groups; a polycarboxylic acid having 3 to 4 carboxyl groups, or an anhydride thereof; or a hydroxy acid having a total of 3 to 6 hydroxyl groups and carboxyl groups can be used. Specifically, the polyol can include at least one selected from the group consisting of glycerol, sorbitol, pentaerythritol, 1,1,4,4-tetrakis(hydroxymethyl)cyclohexane, trimethylol propane, and 1,2,6-hexane triol. In addition, the polycarboxylic acid may include at least one selected from the group consisting of hemimellitic acid, trimellitic acid, trimesspiromellitic 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, trimethylol propane, or a combination thereof may be used as the polymerization reaction branching agent to control the melt index (MI) of the thermoplastic polyester elastomer resin to a desired level.

The amount of this polymerization reaction branching agent to be used (the amount added during the reaction) is not particularly limited, but a concentration of 0.00015 to 0.005 equivalents per 100 g of the first polyester elastomer resin can be applied.

The above esterification reaction, or ester exchange reaction, is usually carried out without the addition of a solvent, but an inert solvent such as water or a diol may be added to facilitate the removal of volatile components.

The conditions of the above esterification reaction or ester exchange reaction can be appropriately controlled according to the reaction environment and the molecular weight of the desired reactant. Specifically, the pressure applied to the above esterification reaction or ester exchange reaction may be 0.01 kg/cm2 or more, 0.05 kg/cm2 or more, or 0.1 kg/cm2 or more, and may be 1.5 kg/cm2 or less, 1 kg/cm2 or less, 0.5 kg/cm2 or less, or 0.3 kg/cm2 or less. In addition, the temperature applied to the above esterification reaction or ester exchange reaction may be 140°C or more, 160°C or more, 180°C or more, or 200°C or more, and may be 300°C or less, 280°C or less, 270°C or less, 250°C or less, or 220°C or less. The esterification reaction or ester exchange reaction can be performed under a nitrogen atmosphere. For example, the esterification reaction or ester exchange reaction can be performed under conditions of 0.05 to 1.5 kg/cm2 and 180 to 280°C under a nitrogen atmosphere.

The above esterification reaction or ester exchange reaction can be performed batchwise or continuously.

The end point of the above esterification reaction or ester exchange reaction can be determined by considering the theoretical amount of water or methanol, which are by-products generated from the first dicarboxylic acid component, or when the outflow of by-products no longer occurs.

The reactants obtained through such esterification reaction or ester exchange reaction may undergo a polycondensation reaction. At this time, the conditions under which the polycondensation reaction is performed may not be particularly limited.

Specifically, the polycondensation reaction can be performed under a vacuum atmosphere. In addition, the pressure applied to 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. In addition, the temperature applied to 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 performed under reduced pressure conditions of 0.1 to 10 mmHg and 200 to 260°C for 1 to 24 hours in a vacuum atmosphere. By performing a polycondensation reaction under the above conditions, a first polyester elastomer resin having a desired molecular weight and intrinsic viscosity (IV) can be manufactured while sufficiently removing by-products.

By going through this process, a first polyester elastomer resin including repeating units ((a), (b)) represented by the chemical formulas 1 and 2 described above can be manufactured in a high yield.

Step (1-2): Preparation of second polyester elastomer resin

According to the present invention, step (1-2) is a step of introducing a second glycol component, a second dicarboxylic acid component, and a second high molecular weight glycol component, which are reaction raw materials, into a reactor (esterification reactor or ester exchange reactor), performing an esterification reaction or an ester exchange reaction to obtain a reactant, and subjecting the reactant to a condensation polymerization reaction to obtain a second polyester elastomer resin. Here, preferably, the second glycol component includes 1,4-butanediol, and the second high molecular weight glycol component includes ethylene oxide addition polypropylene glycol (EO-PPG). Since the description of each of these components is the same as described above, it will be omitted. In addition, since the description of the second dicarboxylic acid component is the same as described above, it will be omitted.

For the esterification reaction or ester exchange reaction, the second glycol component, the second dicarboxylic acid component, and the second high molecular weight glycol component may be simultaneously introduced into the reactor, or the second glycol component and the second dicarboxylic acid component may be introduced and the temperature of the reactor may be increased to a certain level, and then the second high molecular weight glycol component may be introduced. For example, the introduction of the second high molecular weight glycol component may be performed at a temperature of 180 to 280° C. under a nitrogen atmosphere while removing by-products such as water or methanol.

A description of this esterification reaction or ester exchange reaction is omitted because it is the same as the description of the esterification reaction or ester exchange reaction for producing the first polyester elastomer resin.

The reactant obtained through the above esterification reaction or ester exchange reaction may undergo a polycondensation reaction. At this time, the conditions under which the polycondensation reaction is performed may not be particularly limited. Specifically, the description of the polycondensation reaction is the same as the description of the polycondensation reaction for producing the first polyester elastomer resin, so it is omitted.

By going through this process, a second polyester elastomer resin including repeating units ((a), (c)) represented by the chemical formulas 1 and 3 described above can be manufactured in high yield.

Step (1-3): Melt mixing

According to the present invention, step (1-3) is a step of melt-mixing the first polyester elastomer resin obtained in step (1-1) and the second polyester elastomer resin obtained in step (1-2).

The above melt mixing can be performed under heating and/or pressurization conditions using a melt mixing reactor such as a single-screw extruder, a twin-screw extruder, a mixing roll, a Banbury mixer, a batch mixer, or a molding machine.

For the above melt mixing, the first polyester elastomer resin and the second polyester elastomer resin may go through a preliminary mixing process. Specifically, the preliminary mixing process may be performed by putting the first polyester elastomer resin and the second polyester elastomer resin into various mixers such as a V-type blender, a ribbon blender, a Henschel mixer, a rocking mixer, a tubular mixer, a planetary mixer, a Banbury mixer, a mill blender, a mixing roll, or a tumbler to pre-mix in a solid state. The mixing time in the solid state may vary depending on the type of mixer, but the mixing time may be adjusted so that the standard deviation is within 1% and at most 2% compared to the target mixing ratio when five locations are randomly sampled after mixing.

In this preliminary mixing process, commonly known additives (e.g., colorants, fillers, UV blockers, heat stabilizers, etc.) may be further added as needed. Here, the first polyester elastomer resin and the second polyester elastomer resin may be directly added to the melt mixing reactor without going through the preliminary mixing process. In addition, a thermoplastic polyester elastomer resin may be manufactured by mixing some of the raw material components in advance and then melt mixing the resulting reactant to form a masterbatch, mixing the remaining raw material components into the masterbatch, and then melt mixing again.

The above melt mixing can preferably be performed in the single-screw extruder or the twin-screw extruder. The temperature at which the melt mixing is performed through the extruder(s) (e.g., the barrel temperature of the extruder) is not particularly limited and can be determined in consideration of miscibility, ease of extrusion, extrusion reaction efficiency, etc. Specifically, the melt mixing can be performed at a temperature which is 20 to 30 ℃ higher than the melting temperature (T _m ) of the target thermoplastic polyester elastomer resin. For example, the temperature at which the melt mixing is performed can be 170 to 230 ℃, 180 to 225 ℃, 190 to 220 ℃, 195 to 215 ℃, or 200 to 210 ℃. Meanwhile, the extrusion speed (screw rotation speed) of the extruder(s) is not particularly limited, and specifically may be 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. Since melt mixing is performed under these conditions, sufficient melt mixing and reactive extrusion can be performed while having an appropriate throughput per unit time. If the above conditions are exceeded, the thermoplastic polyester elastomer resin may be thermally decomposed, or the melting characteristics may be poor, so that melt mixing may not be sufficiently performed.

The mixing ratio of the first polyester elastomer resin and the second polyester elastomer resin during the above melt mixing is not particularly limited, but considering the target properties of the thermoplastic polyester elastomer resin, the mixing ratio may be a weight ratio of 40:60 to 99:1, a weight ratio of 45:55 to 99:1, a weight ratio of 50:50 to 98:2, a weight ratio of 55:45 to 98:2, a weight ratio of 60:40 to 90:10, a weight ratio of 65:35 to 90:10, a weight ratio of 70:30 to 85:15, or a weight ratio of 75:25 to 85:15.

Meanwhile, the melt mixing of the step (1-3) may be performed in the presence of a reactive compatibilizer. Specifically, the step (1-3) may be performed by pre-mixing the first polyester elastomer resin and the second polyester elastomer resin with the reactive compatibilizer and melt mixing, or may be performed by introducing the first polyester elastomer resin, the second polyester elastomer resin, and the reactive compatibilizer into the melt mixing reactor and melt mixing without the pre-mixing.

Since the above melt mixing is performed in the presence of the reactive compatibilizer, the dispersibility of the first polyester elastomer resin and the second polyester elastomer resin is maximized and chemical cross-linking is achieved, thereby securing basic physical properties while producing a copolymer thermoplastic polyester elastomer resin having excellent mechanical strength, elasticity, and compression-elastic recovery force.

In particular, by introducing (adding) the above-mentioned reactive compatibilizer, a second polyester elastomer resin having a repeating unit (repeating unit (c) of chemical formula 3) derived from ethylene oxide-added polypropylene glycol (EO-PPG) having an energy repulsion elastic effect and a first polyester elastomer resin having a repeating unit (repeating unit (b) of chemical formula 2) derived from polytetramethylene ether glycol (PTMG) that determines mechanical strength are dispersed and combined without causing micro-phase separation, thereby producing a thermoplastic polyester elastomer resin having excellent elasticity and compression-elasticity recovery force.

Specifically, as the reactive compatibilizer is introduced (added) and melt-blended, the hydroxyl group (-OH) or carboxyl group (-COOH) present in each of the first polyester elastomer resin and the second polyester elastomer resin can react with the glycidyl group or maleic anhydride structure of the reactive compatibilizer to form an ether bond or an ester bond.

Descriptions of these reactive commercialization agents are the same as those described above and are therefore omitted.

Compositions and articles

The composition according to the present invention comprises the thermoplastic polyester elastomer resin described above. Specifically, the composition according to the present invention can be used for the production of various products because it comprises a thermoplastic polyester elastomer resin having excellent mechanical strength, elasticity, and compression-elastic recovery.

The composition according to the present invention may further contain conventionally known solvents and additives as needed.

Meanwhile, the article according to the present invention comprises the thermoplastic polyester elastomer resin described above. The article according to the present invention is not particularly limited, but may be a fiber, a foam (a molded article in the form of foam), or a shoe part.

The fibers may be monocomponent fibers and/or multicomponent fibers (e.g., bicomponent fibers). Such fibers may be used to produce woven, knitted, or nonwoven fabrics.

The above foam (a molded product in the form of foam) can be manufactured through a process of physically or chemically foaming the thermoplastic polyester elastomer resin described above in a mold or an autoclave. The density of the foam is not particularly limited, but may be 0.15 to 0.45 g/cm ³ . This foam has high elasticity and energy return properties due to the thermoplastic polyester elastomer resin described above, and can be applied to straps, reporting gears, high-elasticity buffer parts, etc.

The above shoe part is obtained by injecting the thermoplastic polyester elastomer resin described above into a mold and molding it, and can be specifically a shoe midsole, a shoe outersole, a cushioning material for a shoe insole, etc.

The present invention will be described in more detail through the following examples. However, the following examples are only intended to illustrate the present invention, and the scope of the present invention is not limited to these examples.

[Polymerization Example 1]

Step (1-1): Preparation of reactants through ester exchange reaction

In a 1.2 m2 volume ester exchange reactor connected to a water-coolable condenser and a column, 15.8 kg of 1,4-butanediol (1,4-BD) as a glycol component; 69.7 kg of polytetramethylene ether glycol (PTMG) as a high molecular weight glycol component; 29.4 kg of dimethyl terephthalate (DMT) as a dicarboxylic acid component; 0.05 kg of trimellitic anhydride (TMA) as a polymerization reaction branching agent; 0.25 kg of tetrabutyl titanate (TBT) as a reaction catalyst; 0.15 kg of I1098 and 0.15 kg of I1019 as primary antioxidants; and 0.1 kg of I168 as a secondary antioxidant were charged. Subsequently, the reactor was evacuated and nitrogen was flowed to reverse the pressure inside the reactor to 1 kg/cm2 to create an inert atmosphere. Thereafter, the input raw materials were stirred and heated under a nitrogen atmosphere, and when the temperature inside the reactor reached about 200°C, the ester exchange reaction was performed while maintaining the temperature at 200°C for 3 hours. At this time, methanol, a by-product, was discharged through the column and condenser during the ester exchange reaction, and the ester exchange reaction was continued until the outflow of methanol stopped. Thereafter, when the ester exchange reaction was completed, the nitrogen inside the pressurized reactor was discharged to the outside to lower the pressure of the reactor to normal pressure, and the reactant (result) inside the reactor was transferred to a 0.75 m2 polycondensation reactor capable of vacuum reaction.

Step (1-2): Preparation of polyester elastomer resin through polycondensation reaction

The pressure of the polycondensation reactor was lowered from normal pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the polycondensation reactor was raised to 245°C over 1 hour, and the polycondensation reaction was performed while maintaining the pressure of the polycondensation reactor at 1 Torr (absolute pressure: 1 mmHg) or less. At this time, the stirring speed was set fast in the early stage of the polycondensation reaction, and as the polycondensation reaction progressed, the glycol component, which is a by-product, was discharged through the column and condenser, and when the stirring force weakened due to the increase in the viscosity of the reactant or the temperature of the reactant rose above the set temperature, the stirring speed was appropriately adjusted. Thereafter, the polycondensation reaction was performed until the intrinsic viscosity (IV) of the reactant (melt) inside the reactor became 1.85 dl/g, and when the intrinsic viscosity (IV) of the reactant reached the desired level, the reactant was discharged outside the reactor to be stranded. Next, a polyester elastomer resin was obtained through a pelletizing process in which 100 cut pellets were solidified with a cooling liquid and then cut to have an average weight of about 2.5 to 4.0 g.

[Polymerization examples 2 and 3]

In the ester exchange reaction, a polyester elastomer resin was obtained through the same process as in Polymerization Example 1, except that the amount of polytetramethylene ether glycol (PTMG) introduced as a high molecular weight glycol component was applied as shown in Table 1 below.

[Polymerization examples 4 and 5]

In the ester exchange reaction, ethylene oxide-added polypropylene glycol (EO-PPG) was used instead of polytetramethylene ether glycol (PTMG) as a high molecular weight glycol component, and trimethylol propane (TMP) was used instead of trimellitic anhydride (TMA) as a polymerization reaction branching agent, and except that the amounts of these were applied as shown in Table 1 below, a polyester elastomer resin was obtained through the same process as in Polymerization Example 1.

Input raw materials Polymerization example 1 Polymerization example 2 Polymerization example 3 Polymerization example 4 Polymerization Example 5 DMT 29.4 37.6 59.6 35.8 53.1 1,4-BD 15.8 22.1 36.8 21.3 34.5 PTMG 69.7 60.0 35.5 - - PTMG Mn 2,000 2,000 1,000 - - EO-PPG - - - 61.7 41.3 EO-PPG Mn - - - 2,400 2,400 TMA 0.05 0.06 0.11 - - TMP - - - 0.16 0.14 I1098 0.15 0.15 0.15 0.15 0.15 I1019 0.15 0.15 0.15 0.15 0.15 I168 0.1 0.1 0.1 0.1 0.1 TBT 0.25 0.25 0.25 0.25 0.25 DMT: Dimethyl Terephthalate
1,4-BD: 1,4-butanediol
PTMG: Polytetramethylene ether glycol
EO-PPG: Ethylene oxide added polypropylene glycol
PTMG: Polytetramethylene ether glycol
TMA: Trimellitic anhydride
TMP: Trimethylol propane
TBT: Tetrabutyl Titanate

[Example 1]

As the first polyester elastomer resin, 2.1 kg of the resin of Polymerization Example 1; as the second polyester elastomer resin, 0.9 kg of the resin of Polymerization Example 4; and as the reactive compatibilizer, 60 g of Rotader AX8900 were mixed in a solid state (mixing ratio of the first polyester elastomer resin: the second polyester elastomer resin = weight ratio of 70:30), and then placed into a twin-screw extruder (Bautech, KZW20TW-30) set to a barrel temperature of 200°C (however, the feeder section is 150°C). Subsequently, melt kneading was performed at a screw rotation speed of 200 rpm, and then a pelletizing process was performed to obtain a thermoplastic polyester elastomer resin.

[Example 2]

A thermoplastic polyester elastomer resin was obtained through the same process as Example 1, except that 2.4 kg of the resin of Polymerization Example 2 as the first polyester elastomer resin; 0.6 kg of the resin of Polymerization Example 4 as the second polyester elastomer resin; and 60 g of Rotader AX8840 as the reactive compatibilizer were mixed in a solid phase (mixing ratio of the first polyester elastomer resin: the second polyester elastomer resin = weight ratio of 80:20).

[Example 3]

A thermoplastic polyester elastomer resin was obtained through the same process as Example 1, except that 2.4 kg of the resin of Polymerization Example 2 as the first polyester elastomer resin; 0.30 kg of the resin of Polymerization Example 4 and 0.30 kg of the resin of Polymerization Example 5 as the second polyester elastomer resins; and 60 g of Rotader AX4720 as the reactive compatibilizer were mixed in a solid phase (mixing ratio of the first polyester elastomer resin: the second polyester elastomer resin = weight ratio of 80:20).

[Example 4]

A thermoplastic polyester elastomer resin was obtained through the same process as Example 1, except that 1.8 kg of the resin of Polymerization Example 2 as the first polyester elastomer resin; 1.2 kg of the resin of Polymerization Example 5 as the second polyester elastomer resin; and 60 g of Rotader AX8900 as the reactive compatibilizer were mixed in a solid phase (mixing ratio of the first polyester elastomer resin: the second polyester elastomer resin = weight ratio of 60:40) and the barrel temperature was set to 220°C (however, 160°C in the feeder section).

[Example 5]

A thermoplastic polyester elastomer resin was obtained through the same process as Example 1, except that 2.925 kg of the resin of Polymerization Example 2 as the first polyester elastomer resin; 0.075 kg of the resin of Polymerization Example 4 as the second polyester elastomer resin; and 60 g of Rotader AX8900 as the reactive compatibilizer were mixed in a solid phase (mixing ratio of the first polyester elastomer resin: the second polyester elastomer resin = weight ratio of 97.5:2.5).

[Example 6]

A thermoplastic polyester elastomer resin was obtained through the same process as Example 1, except that 1.5 kg of the resin of Polymerization Example 3 as the first polyester elastomer resin; 1.5 kg of the resin of Polymerization Example 5 as the second polyester elastomer resin; and 60 g of Rotader AX4720 as the reactive compatibilizer were mixed in a solid phase (mixing ratio of the first polyester elastomer resin: the second polyester elastomer resin = weight ratio of 50:50) and the barrel temperature was set to 220°C (however, 160°C in the feeder section).

[Example 7]

0.6 kg of the resin of Polymerization Example 3 as the first polyester elastomer resin and 2.4 kg of the resin of Polymerization Example 5 as the second polyester elastomer resin were mixed in a solid phase (mixing ratio of the first polyester elastomer resin: the second polyester elastomer resin = weight ratio of 20:80), and then placed into a twin-screw extruder (Bautech, KZW20TW-30) having a barrel temperature set to 210°C (however, the feeder section is 150°C). Subsequently, melt kneading was performed at 200 rpm, and then a pelletizing process was performed to obtain a thermoplastic polyester elastomer resin.

[Example 8]

2.1 kg of the resin of Polymerization Example 1 as the first polyester elastomer resin and 0.9 kg of the resin of Polymerization Example 4 as the second polyester elastomer resin were mixed in a solid state (mixing ratio of the first polyester elastomer resin: the second polyester elastomer resin = weight ratio of 70:30), and then placed into a twin-screw extruder (Bautech, KZW20TW-30) having a barrel temperature set to 200°C (however, the feeder section is 150°C). Subsequently, melt kneading was performed at 200 rpm, and then a pelletizing process was performed to obtain a thermoplastic polyester elastomer resin.

[Comparative Example 1]

The resin of polymerization example 3 was applied solely as a thermoplastic polyester elastomer resin.

[Comparative Example 2]

The resin of polymerization example 4 was applied solely as a thermoplastic polyester elastomer resin.

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

[Test Example 1] Contents of hard block (chemical formula 1) and soft block (chemical formula 2 and 3)

Thermoplastic polyester elastomer resin was dissolved in CDCl ₃ solvent at a concentration of 3 mg/mL, and then ¹ H-NMR spectrum was obtained at 25 ℃ using a nuclear magnetic resonance device (JEOL, 600 MHz FT-NMR). By analyzing the spectrum, the content (parts by weight) of BD, PTMG, and EO-PPG based on the total mole number of residues derived from all glycols (BD, PTMG, EO-PPG, etc.) was calculated, and this was used to confirm the contents of hard blocks and soft blocks included in the total weight of thermoplastic polyester elastomer resin.

[Test Example 2] Shore D hardness (H)

The hardness of thermoplastic polyester elastomer resin was measured according to ASTM D2240 (Durometer Type D). Specifically, thermoplastic polyester elastomer resin pellets were injection-molded using an injection molding machine (ENGEL, Victory 80) to produce test pieces measuring 100 mm in width, 100 mm in length, and 2 mm in thickness, and the hardness was measured by applying a test piece of 6 mm in thickness, which was made by overlapping three of these.

[Test Example 3] Intrinsic Viscosity (IV)

A thermoplastic polyester elastomer resin was dissolved in orthochlorophenol (OCP) at a concentration of 0.12% at 150°C to obtain a solution, and the intrinsic viscosity of the thermoplastic polyester elastomer resin was measured using a Ubbelrod-type viscometer in a constant temperature bath at 35°C. Specifically, the temperature of the viscosity tube was maintained at 35°C, and the time taken for the solvent to pass through a specific internal section of the viscosity tube (efflux time) and the time taken for the solution to pass through were measured to obtain the specific viscosity, which was then used to calculate the intrinsic viscosity.

[Test Example 4] Melting Index (MI)

According to ASTM D1238, the melt index was calculated by averaging the amount of discharged material per hour for three times after allowing the thermoplastic polyester elastomer resin to remain at 220°C and a 2.16 kg load for 4 minutes.

[Experimental Example 5] Melting Point (Tm)

Thermoplastic polyester elastomer resin was dried under reduced pressure at 50°C for 15 hours, rapidly melted and then scanned at a temperature of 10°C/min using a differential scanning calorimeter (DSC, TA Instruments). The highest point of the endothermic peak due to resin melting was then defined as the melting point (Tm).

[Test Example 6] Tensile strength

The tensile strength of thermoplastic polyester elastomer resin was measured according to ASTM D638. Specifically, thermoplastic polyester elastomer resin pellets were injection-molded using an injection molding machine (ENGEL, Victory 80) to produce test specimens measuring 120 mm in width, 120 mm in length, and 2 mm in thickness, and these were punched to prepare tensile test specimens of ASTM Type I (dumbbell-shaped bar). Next, the tensile strength of the tensile test specimens was measured at a speed of 50 mm/min using a tensile tester (Zwick Roell, Z010).

[Experimental Example 7] Compression Set (CS)

The compression set of thermoplastic polyester elastomer resin was measured according to ISO 816 Method B. Specifically, thermoplastic polyester elastomer resin pellets were injection-molded with a compression mold (WithLab, WL1700) to produce test pieces having a diameter of 29 mm and a thickness of 12.5 mm, which were then compressed at 70°C with a compression ratio of 25% for 22 hours. After the compressive force was removed, the residual strain was obtained, which was then used to calculate the compression set.

[Example 8] Resilience (R)

The resilience of thermoplastic polyester elastomer resin was measured according to ASTM D2632. Specifically, thermoplastic polyester elastomer resin pellets were injection-molded with a compression mold (WithLab, WL1700) to produce test pieces having a diameter of 29 mm and a thickness of 12.5 mm. Next, a 28 g weight was dropped on the test piece, and the rebound height was obtained, which was used to calculate the resilience.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Chemical formula 2
Repeat unit (b) Weight part (y) 52.0 51.2 48.6 36.5 59.3 30.4 12.2 52.0 Repeating unit (c) of chemical formula 3, weight part (z) 19.5 13.0 11.0 17.4 1.6 21.8 52.0 19.5 Repeating unit (a) of chemical formula 1 (weight part) (x) 28.4 35.7 40.3 46.0 39.1 47.7 35.6 28.4 y/z
(Weight ratio of soft block) 2.67 3.94 4.41 2.10 36.46 1.40 0.23 2.67 (y+z) / x
(Weight ratio of soft block/hard block) 2.52 1.80 1.48 1.17 1.56 1.09 1.80 2.52 H (shore D) 30 35 40 44 41 49 50 30 IV (㎗/g) 1.58 1.51 1.70 1.41 1.57 1.14 0.97 1.35 MI
(g/10min, 220℃) 26 21 21 20 21 20 38 35 Tm (℃) 197 195 198 216 193 213 208 213 tensile strength
(kgf/cm ² ) 212 217 241 289 242 303 155 174 Permanent compression set ratio
(CS, %) 37 43 49 54 50 58 54 43 Resilience
(R, %) 71 63 63 68 55 65 53 51 H/CS 0.82 0.81 0.82 0.81 0.82 0.84 0.93 0.70 H/R 0.42 0.56 0.63 0.65 0.75 0.75 0.95 0.59

division Comparative Example 1 Comparative Example 2 Repeating unit (b) of chemical formula 2, weight part (y) 40.1 - Repeating unit (c) of chemical formula 3, weight part (z) - 65.0 Repeating unit (a) of chemical formula 1 (weight part) (x) 59.9 34.6 y/z (weight ratio of soft block) - - (y+z) / x (weight ratio of soft block/hard block) 0.67 1.88 H (shore D) 55 28 IV (㎗/g) 1.33 1.38 MI (g/10min, 220℃) 12 24 Tm (℃) 202 194 Tensile strength (kgf/cm ² ) 340 120 Compression loss ratio (CS, %) 60 53 Resilience (R, %) 52 55 H/CS 0.92 0.53 H/R 1.06 0.51

Referring to Tables 2 and 3 above, it can be confirmed that the thermoplastic polyester elastomer resins of Examples 1 to 8 according to the present invention have excellent mechanical strength, elasticity, and compression set, which is elastic recovery after long-term deformation, because they include soft blocks containing PTMG and EO-PPG derived repeating units (chemical formulae 2 and 3) and hard blocks (chemical formulae 1). In particular, it can be seen that the thermoplastic polyester elastomer resins of Examples 1 to 6 into which a reactive compatibilizer is introduced have excellent mechanical strength and a high molecular weight, thereby exhibiting the desired intrinsic viscosity.

On the other hand, it can be confirmed that the thermoplastic polyester elastomer resin of Comparative Example 1, in which PTMG alone was used, has good mechanical strength, but poor elasticity and elastic recovery force, and the thermoplastic polyester elastomer resin of Comparative Example 2, in which EO-PPG alone was used, has significantly poor mechanical strength.

Claims (23)

A first polyester elastomer resin comprising a repeating unit (a) represented by the following chemical formula 1 and a repeating unit (b) represented by the following chemical formula 2; and
A thermoplastic polyester elastomer resin comprising a second polyester elastomer resin comprising a repeating unit (a) represented by the following chemical formula 1 and a repeating unit (c) represented by the following chemical formula 3:
[Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

In the above chemical formulas 1 to 3,
R ¹ to R ³ are each independently a C ₁ to C ₁₂ straight-chain, branched, or cyclic divalent aliphatic hydrocarbon group; or a C ₆ to C ₁₂ divalent aromatic hydrocarbon group,
m is an integer from 2 to 6,
n is an integer from 4 to 6,
p is an integer between 10 and 30,
t is an integer from 1 to 30,
s is an integer from 1 to 40. In paragraph 1,
A thermoplastic polyester elastomer resin, wherein the thermoplastic polyester elastomer resin further comprises a reactive compatibilizer, a bonding structure derived from the reactive compatibilizer, or a combination thereof. In the second paragraph,
A thermoplastic polyester elastomer resin, wherein the reactive compatibilizer is a compound having a glycidyl group or a compound having a maleic anhydride structure. In the second paragraph,
A thermoplastic polyester elastomer resin, wherein the reactive compatibilizer is poly(ethylene-co-methylacrylate-co-glycidyl methacrylate) or poly(ethylene-co-ethylacrylate-co-maleic anhydride). In the second paragraph,
A thermoplastic polyester elastomer resin, wherein the amount of the reactive compatibilizer used is 0.1 to 10 wt% based on the total weight of the thermoplastic polyester elastomer resin. In paragraph 1,
A thermoplastic polyester elastomer resin, wherein the mixing ratio of the first polyester elastomer resin and the second polyester elastomer resin is a weight ratio of 40:60 to 99:1. In paragraph 1,
A thermoplastic polyester elastomer resin 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. In paragraph 1,
A thermoplastic polyester elastomer resin, wherein the first polyester elastomer resin satisfies the following formula 1:
[Formula 1]
0.5 ≤ a / b ≤ 3.0
In the above equation 1,
a is the weight occupied by the repeating unit (a) represented by the chemical formula 1 in the first polyester elastomer resin,
b is the weight occupied by the repeating unit (b) represented by the chemical formula 2 in the first polyester elastomer resin. In paragraph 1,
The second polyester elastomer resin is a thermoplastic polyester elastomer resin satisfying the following formula 2:
[Formula 2]
0.5 ≤ a / c ≤ 2.5
In the above equation 2,
a is the weight occupied by the repeating unit (a) represented by the chemical formula 1 in the second polyester elastomer resin,
c is the weight occupied by the repeating unit (c) represented by the chemical formula 3 in the second polyester elastomer resin. In paragraph 1,
A thermoplastic polyester elastomer resin satisfying the following formula 3:
[Formula 3]
0.5 ≤ (y + z) / x ≤ 3.0
In the above equation 3,
x is the total weight occupied by the repeating unit (a) represented by the chemical formula 1 in the thermoplastic polyester elastomer resin,
y is the total weight occupied by the repeating unit (b) represented by the chemical formula 2 in the thermoplastic polyester elastomer resin,
z is the total weight occupied by the repeating unit (c) represented by the chemical formula 3 in the thermoplastic polyester elastomer resin. In paragraph 1,
A thermoplastic polyester elastomer resin satisfying the following formula 4:
[Formula 4]
0.3 ≤ y / z ≤ 37
In the above equation 4,
y is the total weight occupied by the repeating unit (b) represented by the chemical formula 2 in the thermoplastic polyester elastomer resin,
z is the total weight occupied by the repeating unit (c) represented by the chemical formula 3 in the thermoplastic polyester elastomer resin. In paragraph 1,
A thermoplastic polyester elastomer resin having a tensile strength of 190 kgf/cm ² or greater as measured according to ASTM D638. In paragraph 1,
A thermoplastic polyester elastomer resin satisfying the following formula 5:
[Formula 5]
H/R ≤ 0.75
In the above equation 5,
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. In paragraph 1,
A thermoplastic polyester elastomer resin satisfying the following formula 6:
[Formula 6]
0.8 ≤ H / CS
In the above equation 6,
H is the Shore D hardness of the thermoplastic polyester elastomer resin as measured according to ASTM D2240,
CS is the compression set of thermoplastic polyester elastomer resins measured according to ISO 816 Method B. In paragraph 1,
The repeating unit (a) represented by the above chemical formula 1 is derived from the reaction of a glycol component including 1,4-butanediol; and a dicarboxylic acid component,
The repeating unit (b) represented by the above chemical formula 2 is derived from the reaction of a dicarboxylic acid component; and a high molecular weight glycol component including polytetramethylene ether glycol,
A thermoplastic polyester elastomer resin, wherein the repeating unit (c) represented by the above chemical formula 3 is derived from the reaction of a dicarboxylic acid component; and a high molecular weight glycol component including ethylene oxide addition polypropylene glycol. In Article 15,
A thermoplastic polyester elastomer resin, wherein the dicarboxylic acid component comprises at least one selected from the group consisting of terephthalic acid and dimethyl terephthalate. In Article 15,
A thermoplastic polyester elastomer resin, wherein the number average molecular weights of the high molecular weight glycol component including the polytetramethylene ether glycol and the high molecular weight glycol component including the ethylene oxide-added polypropylene glycol are each 400 to 5,000 g/mol. (1-1) A step of reacting a first glycol component, a first dicarboxylic acid component, and a first high molecular weight glycol component to obtain a first polyester elastomer resin;
(1-2) a step of reacting a second glycol component, a second dicarboxylic acid component and a second high molecular weight glycol component to obtain a second polyester elastomer resin; and
(1-3) A step of melt mixing the first polyester elastomer resin and the second polyester elastomer resin,
The above first polyester elastomer resin comprises a repeating unit (a) represented by the following chemical formula 1 and a repeating unit (b) represented by the following chemical formula 2,
A method for producing a thermoplastic polyester elastomer resin, wherein the second polyester elastomer resin comprises a repeating unit (a) represented by the following chemical formula 1 and a repeating unit (c) represented by the following chemical formula 3:
[Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

In the above chemical formulas 1 to 3,
R ¹ to R ³ are each independently a C ₁ to C ₁₂ straight-chain, branched, or cyclic divalent aliphatic hydrocarbon group; or a C ₆ to C ₁₂ divalent aromatic hydrocarbon group,
m is an integer from 2 to 6,
n is an integer from 4 to 6,
p is an integer between 10 and 30,
t is an integer from 1 to 30,
s is an integer from 1 to 40. In Article 18,
A method for producing a thermoplastic polyester elastomer resin, wherein the melt mixing of the above step (1-3) is performed in the presence of a reactive compatibilizer. In Article 18,
Each of the first glycol component and the second glycol component contains 1,4-butanediol,
The above first high molecular weight glycol component comprises polytetramethylene ether glycol,
A method for producing a thermoplastic polyester elastomer resin, wherein the second high molecular weight glycol component comprises ethylene oxide addition polypropylene glycol. A composition comprising a thermoplastic polyester elastomer resin according to any one of claims 1 to 17. An article comprising a thermoplastic polyester elastomer resin according to any one of claims 1 to 17. In paragraph 22,
An article wherein the above article is a fiber, foam, or shoe part.