KR101008928B1 - Thermoplastic copolyesterester elastomer resins characterized in good long-term thermal resistance and method for producing the same - Google Patents

Abstract

The present invention relates to a thermoplastic copolyester ester elastomer composition having excellent long-term heat aging resistance as a main component of a thermoplastic polyester random copolymer and a method for preparing the same, and more specifically, to polybutylene terephthalate as a hard segment. A thermoplastic elastomer composition comprising a soft segmented polyester diol derived from a dimer fatty acid having a number average molecular weight of 1,500 to 2,500 having excellent weather resistance and hydrolysis resistance. Excellent elasticity, molding processability, hydrolysis resistance, especially heat resistance, constant velocity joint boots including bellows, air, etc. Duct, Protection Hose, it can be advantageously used in all areas where elasticity and high heat resistance requires the use of an apparatus such as tubes.

Thermoplastic Copolyester Ester Elastomer, Heat Aging Resistance, Dimer Fatty Acid Polyester Diol

Description

Thermoplastic copolyesterester elastomer resins characterized in good long-term thermal resistance and method for producing the same

The present invention is a new type of thermoplastic elastomer resin suitable for use in electric and electronic coating parts, automotive constant velocity joint boots, air duct and bellows parts, various industrial sheets, and films because of its excellent elasticity, low temperature, and heat resistance. And a method for producing the same. More specifically, the present invention relates to a thermoplastic copolyester ester elastomer resin having excellent heat resistance property using a polyester diol derived from dimer fatty acid having a hard segment of PBT and a number average molecular weight of 1,500 to 2,500 as a soft segment, and a method for producing the same. will be.

Thermoplastic polyester-based elastomer (TPEE) has excellent low temperature impact characteristics, and has excellent oil resistance, chemical resistance, and mechanical properties, and is widely used in the electric / electronic field and automotive field together with thermoplastic urethane elastomer and thermoplastic polyamide elastomer. Elastomers used in parts of engineering systems. As such TPEE, a block copolymer resin composition of a polyether ester type is typically produced and mainly produced by a polymerization process.

Polyetherester-based TPEE has a long history of polybutylene terephthalate (PBT) as a hard segment of polytetramethylene ether glycol (PTMEG) polyoxyalkylene (Polyoxy alkylene) It is known and made into a soft segment and it is put to practical use.

However, polyether ester-based TPEE using polyoxyalkylenes as soft segments is excellent in water resistance and low temperature characteristics, but inferior in heat aging resistance. In order to solve this problem, attempts to improve long-term heat aging resistance by introducing comonomers having excellent heat resistance in hard or soft segments have been attempted for a long time, and some of them have been commercialized. The hard segment is called polybutylene naphthalate (PBN) and the soft segment is called PTMEG, and the polyethylene naphthalate (PEN) or polycyclohexane terethphalate (PCT) is used as the hard segment. The soft segment as PTMEG is shown in Japanese Patent Laid-Open No. 5-202176.

The hard segment as PBT and the soft segment as polycaprolacone (PCL) are shown in Japanese Patent Application Laid-Open No. 10-17657, and the introduction of polybutylene adipate (PBA) in US Pat. It is shown at -182782. TPEE which uses PCL and PBA as a soft segment is called polyester-ester TPEE separately from polyether ester-type TPEE. That is, the polyester-based TPEE is an ester polymer such as PBT, PBN, PCT, etc., and the soft segment refers to an elastomer produced using a polyester-based rubber component.

However, the polyester-based TPEE using polyester as the soft segment mentioned above is also known to have a disadvantage in that it is excellent in heat aging resistance but inferior in water resistance and low temperature characteristics compared to polyetherester-based TPEE. For example, Japanese Patent Application Laid-Open Nos. 10-182782 and 2001-240663 propose polyester esters using PBA or polycarbonate diols and isocyanate compounds, but the manufacturing process is complicated and it is difficult to control the chain extension reaction through urethanization. It has excellent heat aging resistance but has a problem in hydrolysis resistance. Japanese Patent Application Laid-Open No. 11-302519, Japanese Patent Application No. 2000-143954, Japanese Patent Application 2000-159989, Japanese Patent Application No. 2000-264959, 1,4-cyclohexanedimethanol (1,4-CHDM), Although it has been proposed to use hydrogenated dimerdiol and hydrogenated dimer acid as comonomers, it has high synthesis temperature and high melting point of final TPEE, making it difficult to mold at normal processing temperature and excellent in heat resistance but difficult to commercialize in terms of manufacturing cost.

In order to solve the above problems, the present invention provides a copolyether by using a polyester-based diol, which does not cause a strong melting point or deterioration in physical properties due to randomization of a polymer by an ester exchange reaction in the production of a copolyetherester-based TPEE. In addition to being able to easily synthesize ester ester TPEE, it is an object to provide a thermoplastic elastomer that is superior in heat resistance and has no variation in product properties compared to conventional copolyether ester type TPEE.

Another object of the present invention is to use the copolyester-based TPEE in the future automotive parts having excellent melt viscosity, heat resistance, in particular for constant velocity joint boots and bellows and electrical, electronic, automotive parts excellent in electrical insulation, heat resistance, flame resistance It is to provide a thermoplastic elastomer that can be used as industrial parts such as coating materials such as cables and wires, tubes, sheets, and the like.

The present invention provides a thermoplastic copolyester-ester elastomer resin comprising 45 to 65% by weight of aromatic dicarboxylic acid, 20 to 35% by weight of lower diol and 10 to 45% by weight of dimer fatty acid-derived polyester diol. .

The dimer fatty acid-derived polyester diol included in the elastomer resin of the present invention is characterized by being a compound represented by the following Chemical Formula 1.

(n is an integer of 3 to 5)

The aromatic dicarboxylic acid included in the elastomer resin of the present invention is terephthalic acid (TPA), isophthalic acid (IPA), 2,6-naphthalene dicarboxylic acid (2,6-NDCA), 1,5-naphthalene dicarboxylic acid (1,5-NDCA), 1,4-cyclohexane dicarboxylic acid (1,4-CHDA), dimethyl terephthalate (DMT), dimethyl isophthalate (Dimethyl Isophthalate, DMI) in which the diacid is substituted with a dimethyl group, 2,6-dimethyl naphthalene dicarboxylate (2,6-NDC), dimethyl 1,4-cyclohexanedicarboxylate (1,4-DMCD), or any mixture thereof.

Lower diols contained in the elastomer resin of the present invention are ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane diol , 1,4-cyclohexane dimethanol can be any one selected from the group consisting of, or a mixture thereof.

In addition, the elastomer resin of the present invention may further include one or more selected from the group consisting of polyoxyethylene glycol, polyoxypropylene glycol, ethylene oxide addition polypropylene glycol, polyoxytetramethylene glycol. At this time, the glycol compound may be included in 5 to 50% by weight relative to the dimer fatty acid-derived polyester diol.

In addition, the present invention is the product of the first step and the first step of esterifying 45 to 65% by weight of aromatic dicarboxylic acid, 20 to 35% by weight lower diol and 10 to 45% by weight of dimer fatty acid-derived polyester diol It provides a method for producing a thermoplastic copolyester ester thermoplastic elastomer resin comprising a second step of polycondensation reaction.

The dimer fatty acid-derived polyester diol used in the first step is characterized in that the compound represented by the following formula (1).

[Formula 1]

(n is an integer of 3 to 5)

In the second step reaction, N, N'-hexane-1,6-diylbis (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)), which is a hindered phenolic antioxidant as a heat stabilizer, is 0.05 to 0.2. 0.05% to 0.3% by weight of 4,4'-Bis (alpha, alpha-dimethylbenzyl) diphenylamine, which is a weight% and an aromatic amine antioxidant, may be used.

In the second step, 0.03-0.1 wt% of trimellitic anhydride (TMA), a reactive chain extender, may be used.

In the second step reaction, 0.03 to 0.1% by weight of 2,2'-methylenebis (4,6-di-t-butylphenol) phosphate sodium as the nucleating agent may be used.

In the first step reaction, at least one selected from the group consisting of polyoxyethylene glycol, polyoxypropylene glycol, ethylene oxide added polypropylene glycol, and polyoxytetramethylene glycol may be reacted by further including at least one selected. have. In this case, the glycol compound may be used in an amount of 5 to 50 wt% based on the dimer fatty acid-derived polyester diol.

The present invention also provides a thermoplastic copolymer polyester resin in the form of a random copolymer prepared by the above method.

Hereinafter, the present invention will be described in detail.

The present invention provides a thermoplastic copolyester ester-based elastomer including an aromatic dicarboxylic acid, a lower diol, and a polyester diol derived from a dimer fatty acid.

In the present invention, a random copolyester ester-based TPEE is prepared from the melt dipolymer and aromatic dicarboxylic acid and lower diol, wherein the hard segment is polyester and the soft segment is dimer fatty acid-derived polyester diol. Specifically, by polymerizing through an esterification reaction and a polycondensation reaction, a novel thermoplastic copolyester ester-based TPEE having excellent heat aging resistance is provided. Accordingly, the thermoplastic polyester-based TPEE of the present invention includes aromatic dicarboxylic acid, lower diol and polyester diol derived from dimer fatty acid.

The copolyester ester-based TPEE resin of the present invention is a form in which a hard segment and a soft segment are random block copolymerized.

In preparing the copolyester ester-based TPEE according to the present invention, as aromatic dicarboxylic acid, terephthalic acid (Terephthalic acid, TPA), isophthalic acid (Isophthalic acid, IPA), 2,6-naphthalene dicarboxylic acid (2, 6-naphthalene dicarboxylic acid, 2,6-NDCA, 1.5-naphthalene dicarboxylic acid (1,5-NDCA), 1,4-cyclohexane dicarboxylic acid (1,4 -Cyclohexane dicatboxylic acid (1,4-CHDA) and dimethyl terephthalate (DMT), an aromatic dicarboxylate substituted with a dimethyl group, dimethyl isophthalate (DMI), 2,6-dimethyl naphthalene dicarboxylate (2,6-Dimehtyl naphthalene dicarboxylate (2,6-NDC), dimethyl 1,4-cyclohexane dicarboxylate (Dimethyl 1,4-Cyclohexanedicarboxylate, DMCD) or their Mixtures can be used, preferably DMT. The aromatic dicarboxylic acid is used 40 to 70% by weight, preferably 45 to 65% by weight. If the aromatic dicarboxylic acid is used in less than 40% by weight or more than 70% by weight, the reaction is not balanced and the reaction does not proceed well.

Lower diols used in the present invention include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane diol or 1,4-cyclohexanedimethanol (1,4-Cyclohexanedimethanol, 1,4-CHDM) is used, and preferably 1,4-butanediol is used. The lower diol is 20 to 40% by weight, preferably 25 to 35% by weight. If it is less than 20% by weight or more than 40% by weight, the reaction is not balanced and the reaction does not proceed.

In the present invention, in order to improve the long-term heat aging stability of the copolyester ester elastomer, a dimer fatty acid-derived polyester diol (dimeric fatty acid based polyester diol) is prepared by adding as a soft segment component, dimer fatty acid-derived polyester diol 10 ~ 50% by weight, preferably 15 to 45% by weight is used. If the dimer fatty acid-derived polyester diol is less than 10% by weight, the hardness of the TPEE is too high and there is a problem in flexibility, and when it exceeds 50% by weight, the problem of heat resistance and compatibility of the TPEE itself.

The dimer fatty acid-derived polyester diol included in the TPEE of the present invention is prepared from a dimer fatty acid represented by the following formula (2).

Fatty acids are chain-shaped monocarboxylic acids. Most fatty acids found in living organisms have an even numbered carbon number and have a normal chain shape. The carbon chain may be saturated or unsaturated.

Therefore, Chemical Formula 2, in which two fatty acids form a dimer, is represented by a form including a carbon side chain and a side chain including a carboxylic acid group at the terminal. Formula 2 may vary the size of the side chain and the saturation of the carbon bond according to the type of fatty acid, binding sites and conditions. In particular, in the fatty acid binding site represented by the figure circle in the formula (2) isomers are generated according to the reaction conditions so that the dimer fatty acid of the formula (2) is present in the form of various three-dimensional structure.

The dimer fatty acid-derived polyester diol included in the resin of the present invention is synthesized through esterification of the dimer fatty acid and the dimer alcohol of Chemical Formula 2, and is represented by the following Chemical Formula 1.

[Formula 1]

(n is an integer of 3 to 5)

The molecular weight of the dimer fatty acid-derived polyester diol of Chemical Formula 1 is preferably 1,500 to 2,500. The dimer fatty acid-derived polyester diol of Chemical Formula 1 includes a carbon side chain derived from the dimer fatty acid of Chemical Formula 2.

The copolyester ester-based TPEE of the present invention improves long-term heat aging resistance by using a dimer fatty acid-derived polyester diol of Chemical Formula 1 instead of PTMEG which is a conventional ether rubber component.

Hardness of the copolyester-based TPEE synthesized in the present invention is represented by Shore hardness-D (Shore-D), the hardness is determined according to the content of the dimer fatty acid-derived polyester diol. That is, the greater the content of the dimer fatty acid-derived polyester diol, the lower the hardness (Shore hardness-D).

The TPEE of the present invention may include additives such as branching agents to increase the melt tension of the elastomer melt viscosity. The branching agents include glycerol, pentaerythritol, trimellitic anhydride, trimellitic acid, trimethylol propane, pentyl glycol, and the like. It can be used at 0.05 to 0.1% by weight based on the total weight. Preferably trimellitic anhydride is used. When the content of the branching agent is less than 0.05% by weight, it is difficult to expect an increase in the melt viscosity. When the content of the branching agent is more than 0.1% by weight, the melt viscosity of the TPEE is excessively increased, making it difficult to control the intrinsic viscosity during melt polymerization.

In order to improve the long-term heat aging resistance of TPEE, instead of hard segment PBT, rigid and heat resistant polyester polymers such as PBN, PEN, PCT, and PET, such as naphthalene or cyclohexane, are used. (Polyalkylene carbonate), polycaprolactone (Polycaprolactone) and polybutylene adipate (Polybutylene adiphate) copolymerization component of a polyester-based diol selected from the group consisting of, or a mixture thereof may be introduced. However, when the hard segment is made of PBN and PEN, the resin price due to the NDC monomer is high and economic efficiency is low. In the case of PCT and PET, the polymerization temperature is high, so that copolymerization with other polyester soft segments is not easy. Therefore, in most cases, a method of introducing a polyester-based component as a soft segment while making the hard segment PBT is adopted. On the other hand, in the case of using polyester diols such as polyalkylene carbonate, polycaprolactone, and polybutylene adipate having good heat resistance instead of PTMEG as the hard segment is PBT and soft segment, ester bonds and polyester in PBT during the reaction Mutual transesterification between the ester bonds in the terdiol causes the resin to be randomized, which does not have the desired physical properties of TPEE, leading to melting point drop and physical property deterioration. Even amorphous polymers are formed.

Accordingly, in order to introduce a polyester-based soft segment component while suppressing the transesterification reaction, a block copolymer type TPEE was prepared by first making a hard segment PBT prepolymer and then introducing the soft segment component. However, the manufacturing process is complicated and the reaction time is long, in particular, there is a disadvantage that precise polymerization control is required.

However, the present invention has the advantage that the transesterification reaction does not occur by using the dimer fatty acid-derived polyester diol as a soft segment. Therefore, according to the present invention, it is possible to manufacture copolyester-based TPEE excellent in high melting point and heat aging resistance as a simple manufacturing process without having to control separate process conditions.

That is, the present invention comprises the step of esterifying 45 to 65% by weight of aromatic dicarboxylic acid, 20 to 35% by weight of lower diol and 10 to 45% by weight of dimer fatty acid-derived polyester diol and polycondensation of the product of the reaction. The block copolymer can be prepared without randomizing the resin by the transesterification reaction.

The present invention will be described in detail through the following examples.

Example  One

26.0% by weight of DMT 46.0%, 1,4-butanediol, 27.8% by weight, and dimer fatty acid-derived polyester diol (Uniqema, trade name: Priplast 3199) with a molecular weight of 2,000 were placed in an ester interchange reactor and TBT was used as a catalyst. 0.02% by weight was added. The reaction temperature is in the range of 140 to 215 ° C., and the temperature is raised from 140 ° C. to 215 ° C. for 120 minutes, and the reaction is carried out for 60 minutes while maintaining 215 ° C. to convert the amount of methanol, which is a reaction effluent, into a reaction rate. Was terminated.

The oligomer was then transferred to a polycondensation reactor and additionally 0.1 wt% of TBT catalyst, 0.05 wt% of TMA as a chain extender, and 2,2'-Methylenebis (4,6-di-tert-butylphenol) phosphate sodium salt as nucleating agent. 0.05 wt% and 0.12 wt% of N, N'-hexane-1,6-diylbis (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)), a hindered phenolic antioxidant, aromatic amine-based oxidation 4, 4'-Bis (alpha, alpha-dimethylbenzyl) diphenylamine 0.14% by weight of the inhibitor was added together to perform a polycondensation reaction. The polycondensation reaction was carried out at 215 ° C. to 245 ° C. for 120 minutes, at which time the pressure was reduced from 760 tor to 0.3 torr for 1 hour, and the remaining 1 hour to prepare TPEE under high vacuum conditions of 0.3 torr or less. The end point of the reaction was caught with the torque applied to the stirrer, and when the developer reached the desired torque, the reaction was terminated, discharged out of the system using nitrogen pressure, stranded, and pelletized after cooling. . The composition and physical properties of the copolyester-based TPEE thus prepared are shown in Tables 1 and 2 below.

Example  2

TPEE was prepared in the same manner as in Example 1, but in the oligomer reaction, 23.1 wt% of DMT 47.7 wt%, 1,4-butanediol 28.8 wt%, and dimer fatty acid-derived polyester diol (Uniqema, Priplast 3199) In the polycondensation reaction, the reaction was performed without using a nucleating agent and a chain extender. The composition and physical properties of the copolyester-based TPEE thus prepared are shown in Tables 1 and 2 below.

Comparative example  One

44.9% by weight of DMT, 24.8% by weight of 1,4-butanediol, and 29.7% by weight of PTMEG having a molecular weight of 1,000 were used, except that the nucleating agent used in Example 1 was not used. TPEE was prepared. The compositions and physical properties thus obtained are shown in Tables 1 and 2.

Comparative example  2

It was prepared in the same manner as in Example 1, except that polycaprolactone diol having a molecular weight of 2,000 was used instead of the dimer fatty acid-derived polyester diol, and was reacted in the same manner as in Example 1. The composition and physical properties of the TPEE thus obtained were It is shown in Table 1 below.

Comparative example  3

It was prepared in the same manner as in Example 1, except that polycarbonate diol having a molecular weight of 2,000 was used instead of the dimer fatty acid-derived polyester diol, and was reacted in the same manner as in Example 1. The composition and physical properties of the TPEE thus obtained were Table 1 shows.

Comparative example  4

The physical properties of the commercially available thermoplastic copolyester ester elastomer resin UM-551 (DSM Co., Ltd.) product was evaluated and presented as comparative data in Tables 1 and 2.

Physical properties of the Example and Comparative Example compositions are evaluated through the following test.

(1) melting point and crystallization temperature

DSC was used and the temperature rising rate was measured from room temperature to 20 ° C / min.

(2) hardness measurement

Hardness was measured by the Shore D type by the method of ASTM D 2240.

(3) melt index

It measured at 220 degreeC and 2.16 kg load based on ASTMD 1238.

(4) tensile strength and elongation

Specimens molded according to DIN 53504-85 STAB 2 were measured at room temperature, and the tensile strength at yield point (Kg / cm ² ) and tensile elongation at break (%) were measured.

(5) Long-term heat aging resistance

Put the DIN 53504-85 STAB type 2 tensile specimen in the gear oven at 150 ℃ where air circulation and rotation occurs, and then take it out after a certain time and leave it at room temperature for about 1 day, and measure the tensile property to maintain 50% of the initial physical property. It is set as the time (or days) to reach.

division Weight ratio (% by weight)
(HS: SS) ¹⁾ Soft segment type Melting point
(Tm, ℃) Crystallization temperature
(Tc, ℃) Example 1 67: 33 Polyester diols derived from dimer fatty acids ²⁾ 195 135 Example 2 70: 30 Polyester diols derived from dimer fatty acids ²⁾ 201 132 Comparative Example 1 62: 38 PTMEG ³⁾ 200 148 Comparative Example 2 67: 33 PCL ⁴⁾ N.D. N.D. Comparative Example 3 67: 33 PCDL ⁵⁾ N.D. ND ⁷⁾ Comparative Example 4 UM-551 ⁶⁾ 191 131

1) HS: hard segment

   SS: soft segment

2) Polyester diols derived from dimer fatty acids: Priplast 3199 from Uniqema

3) PTMEG: BASF PolyTHF 1,000

4) PCL: Polycaprolactone diol, Solvay CAPA 2200A

5) PCDL: Polycarbonate diol, Asahi Kasei T4692

6) UM-551 (trademark): Copolyester ester elastomer prepared from Polybutylene terephthalate and Polybutylene adipate diol, DSM

7) N.D .: No Detected

division Hardness
(Shore Hardness-D) Melt index
(g / 10 minutes) The tensile strength
(Kg / cm ² ) Tensile elongation
(%) Long-term heat aging resistance
(50% retention) Example 1 52 15 320 620 20 Example 2 55 18 360 590 13 Comparative Example 1 51 15 400 730 6 Comparative Example 4 51 14 360 600 13

It can be seen from the above table that the polyether ester elastomer obtained in Comparative Example 1 has a high melting point of 200 ° C. but its long-term heat resistance is inferior. On the other hand, the polymers obtained in Comparative Examples 2 and 3 were amorphous copolyester ester resins in which the melting point and the crystallization temperature were not measured as the amorphous polymer.

On the other hand, unlike conventional polyester-based diols, thermoplastic copolyester-ester elastomers of the present invention polymerized using polyester diols derived from dimer fatty acids produce amorphous polymers or melting points by transesterification. No degradation occurred. In addition, as shown in Table 2, it was very excellent in long-term heat aging resistance at high temperature, and it was confirmed that it had excellent mechanical properties even when compared with conventional general copolyether ester elastomers or commercialized copolyester ester elastomer products. .

The thermoplastic polyester ester elastomer of the present invention has an advantage of being easy to manufacture because no transesterification reaction occurs in the manufacturing process. In addition, the mechanical properties and long-term heat aging resistance is excellent.

Accordingly, the thermoplastic polyester elastomer of the present invention can be used in various molding materials including fibers, films, sheets. Especially, it is elastic and high in device for constant velocity joint boots, bellows, air duct, protective hose, tube and etc. It can be usefully used in all fields where heat resistance is required.

Claims (12)

A thermoplastic copolyester ester elastomer resin comprising 45 to 65% by weight of an aromatic dicarboxylic acid, 20 to 35% by weight of a lower diol, and 10 to 45% by weight of a dimer fatty acid-derived polyester diol represented by the following Chemical Formula 1. . [Formula 1]

(n is an integer of 3 to 5) delete The method of claim 1, The aromatic dicarboxylic acid is terephthalic acid (TPA), isophthalic acid (IPA), 2,6-naphthalene dicarboxylic acid (2,6-NDCA), 1,5-naphthalene dicarboxylic acid (1,5-NDCA) , 1,4-cyclohexane dicarboxylic acid (1,4-CHDA), dimethyl terephthalate (DMT), didimethyl substituted with dimethyl group, dimethyl isophthalate (DMI), 2,6-dimethyl naphthalene Thermoplastic copolyester ester, characterized in that any one or a mixture thereof in the group consisting of dicarboxylate (2,6-NDC), dimethyl 1,4-cyclohexanedicarboxylate (1,4-DMCD) Elastomer resin. The method of claim 1, The lower diol is ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane diol, 1,4-cyclohexane The thermoplastic copolyester ester thermoplastic elastomer resin, characterized in that any one selected from the group consisting of dimethanol, or a mixture thereof. In claim 1, Polyoxyethylene glycol, polyoxypropylene glycol, ethylene oxide addition polypropylene glycol, polyoxytetramethylene glycol, including one or more selected from the group consisting of 5 to 50% by weight based on the dimer fatty acid-derived polyester diol Thermoplastic copolyester ester thermoplastic elastomer resin, characterized in that. A first step of esterifying 45 to 65% by weight of an aromatic dicarboxylic acid, 20 to 35% by weight of a lower diol, and 10 to 45% by weight of a dimer fatty acid-derived polyester diol represented by Formula 1 below; A method for producing a thermoplastic copolyester ester thermoplastic elastomer resin comprising a second step of polycondensing the product of the first step reaction. [Formula 1]

(n is an integer of 3 to 5) delete The method of claim 6, N, N'-hexane-1,6-diylbis (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)) which is a hindered phenolic antioxidant as a heat stabilizer in the second step reaction 0.05 ~ 0.2 A method for producing a thermoplastic copolyester ester elastomer resin, characterized by using 0.05 to 0.3% by weight of 4,4'-Bis (alpha, alpha-dimethylbenzyl) diphenylamine which is a weight% and an aromatic amine antioxidant. The method of claim 6, Method of producing a thermoplastic copolyester ester elastomer resin, characterized in that 0.03 ~ 0.1% by weight of trimellitic anhydride (TMA) which is a reactive chain extender in the second step reaction. The method of claim 6, Preparation of the thermoplastic copolyester ester elastomer resin, characterized in that 0.03 ~ 0.1% by weight of 2,2'- methylenebis (4,6-di-t-butylphenol) phosphate sodium as nucleating agent in the second step reaction Way. The method of claim 6, The first step of the reaction is at least one selected from the group consisting of polyoxyethylene glycol, polyoxypropylene glycol, ethylene oxide addition polypropylene glycol, polyoxytetramethylene glycol, 5 to 50 with respect to the dimer fatty acid-derived polyester diol A method for producing a thermoplastic copolyester elastomer resin, characterized in that the reaction is added by weight%. delete