KR20130078087A - Thermoplastic elastomer - Google Patents

Abstract

PURPOSE: A thermoplastic polyester elastomer resin composition is provided to have a high elasticity and distortion characteristic with an excellent mechanical property, molding processability, and surface property by having a suitable viscosity on extrusion molding and blow molding. CONSTITUTION: A thermoplastic polyester elastomer resin composition comprises multifunctional monomer selected from the chemical equation (1) or (2) below as 0.01-0.1 parts by weight of cross-linking agent and 0.1-2 parts by weight of thermal ageing preventive according to 100 parts by weight of resin. Here, R1 is (C1-3) alkyl or (C6-20) aryl, and R2 is (C1-C3) alkylene, m and n are 3-6 integers, R3 is (C1-3) alkyl or (C6-C20) aryl, and R4 is hydrogen or (C1-3) alkyl. The resin composition comprises 45-60 weight% of acid component, 30-45 weight% of bifuntional alcohol, and 10-20 weight% of average molecular weight 1000-2000 polyalkylene glycol.

Description

Thermoplastic polyester elastomer {Thermoplastic elastomer}

The present invention relates to a thermoplastic polyester elastomer composition comprising a crosslinking agent, and has a viscosity characteristic suitable for extrusion blow molding, and because it has excellent mechanical properties, molding processability and surface properties, as well as significantly high flexibility and bending characteristics The present invention relates to a thermoplastic polyester elastomer resin composition that can be applied to automobiles, cables, electric electronics, and various industrial parts.

In the field of automobiles, cables, and electronics, conventionally, crosslinked rubbers formed by adding vulcanizing agents to natural rubber or synthetic rubber have been used as main materials, but recently, crosslinked rubber parts have been replaced by plastic products due to the demand for light weight and affinity curing. As a result, the utilization of thermoplastic elastomer materials with low specific gravity, good processability, and recyclability is increasing.

Currently, various kinds of thermoplastic elastomers (TPEs), such as styrene type, urethane type, olefin type, amide type, and the like, have been developed, and in particular, thermoplastic poly Ester elastomers are excellent in mechanical properties, low temperature properties, heat resistance, chemical resistance, and fatigue resistance, and are used in various parts of automobiles, electronics, and industrial applications requiring flexibility and characteristics of engineering plastics at the same time.

Automobiles and cables are connected to other complex structures and exposed to flexural, high temperature, high pressure and high vibration environments. Flexibility, cushioning effect, adhesion to other structures, adhesion and high heat resistance for design and assembly freedom At the same time, the thermoplastic polyester elastomer corresponds to one of a group of materials capable of satisfying these required properties.

When molding the automotive parts and cables, the thermoplastic polyester elastomer may be formed to have an optimum melt viscosity and melt tension in a molten state because the length is shorter than several centimeters to longer than several meters. The process of making a high viscosity high molecular weight body is essential.

The thermoplastic elastomers are generally prepared by melt polymerization, which has limitations in obtaining a polymer having a suitable high melt viscosity.

As a method for increasing the melt viscosity of the thermoplastic polyester elastomer, Japanese Patent Laid-Open No. 1974-013297 discloses a method of polymerizing the thermoplastic polyester elastomer obtained by melt polymerization again into a solid state called solid phase polymerization. The solid phase polymerization method has a large dependency on the melt viscosity temperature and the residence time of the resin and decreases productivity due to a long solid phase polymerization time, which may cause a problem that the b value increases in the color, and when the molding is performed after the primary molding The problem that the molding conditions change significantly may occur.

In addition, by blending a crosslinking agent to improve the melt viscosity of the thermoplastic polyester elastomer resin composition, Japanese Patent Laid-Open No. 1999-323110, Japanese Patent Laid-Open No. 2000-239354, Japanese Patent Laid-Open No. 2000-355650 and Japanese Patent Laid-Open Japanese Patent No. 2001-247752 discloses a method for blending a bifunctional or more epoxy compound with a thermoplastic polyester elastomer, and Japanese Patent Laid-Open Nos. 2005-325220 and 5,383,986 disclose compounding polyisocyanates with thermoplastic polyester elastomers. However, when the epoxy compound is used, the reactivity with the carboxylic acid group may lead to an increase in viscosity, but it must have sufficient reaction time in the reactor to fully react, which leads to a decrease in productivity. Local gels do not control reaction rates properly It is difficult to have a constant melt viscosity during molding by unreacted epoxy, and when the polyisocyanate is used, it is difficult to control the reaction rate because it shows rapid reactivity with hydroxyl groups, and if the reaction is not sufficiently made, unreacted There is a problem that the gas caused by the isocyanate is induced, which also adversely affects the molding conditions during molding.

Therefore, it is possible to shorten the solid-state polymerization time, it is necessary to select a new crosslinking agent that does not exhibit the above-mentioned problems of the crosslinking agent, which has a stable formability, and at the same time can meet the properties required for automobile parts and cables, etc. In order to develop a thermoplastic polyester elastomer resin composition.

Japanese Laid-Open Patent No. 1999-323110 (1999.11.26) Japanese Laid-Open Patent No. 2000-239354 (2000.09.05) Japanese Laid-Open Patent No. 2000-355650 (2000.12.26) Japanese Patent Laid-Open No. 2001-247752 (2001.09.11) Japanese Laid-Open Patent No. 2005-325220 (2005.11.24) U.S. Patent # 5733986 (1998.03.31)

According to the present invention, flexibility, mechanical strength, heat resistance, and the like are well-balanced, have viscosity characteristics suitable for extrusion blow molding, and have excellent melt viscosity (or melt tension), long-term heat aging stability, appearance characteristics, and the like. To provide a thermoplastic polyester elastomer resin containing a crosslinking agent that can be applied to constant velocity joint boots for automobiles, various bellows and the like.

The present invention with respect to 100 parts by weight of the resin composition consisting of 45 to 60% by weight of acid components, 30 to 45% by weight of bifunctional alcohol, 10 to 20% by weight of polyalkylene glycol having a number average molecular weight of 1,000 to 2,000,

It relates to a thermoplastic polyester elastomer composition comprising 0.01 to 0.5 parts by weight of a multifunctional monomer selected from the following formula (1) or (2) as a crosslinking agent, and 0.1 to 2 parts by weight of a heat aging inhibitor.

[Formula 1]

(Wherein R ₁ is selected from (C1-C3) alkyl or (C6-C20) aryl, R ₂ is (C1-C3) alkylene and n is an integer selected from 3-6)

[Formula 2]

(Wherein R ₃ is selected from (C1-C3) alkyl or (C6-C20) aryl, R ₄ is selected from hydrogen or (C1-C3) alkyl, m is an integer selected from 3-6)

In addition, the present invention may further comprise 0.01 to 0.5 parts by weight of an acrylic polyol having a number average molecular weight of 2000 to 5000 based on 100 parts by weight of the resin composition.

In addition, the present invention also encompasses a polyester elastomer resin prepared by solid-phase polymerization of the thermoplastic polyester elastomer composition.

The polyester elastomer resin according to the present invention has a Shore D hardness of 40 to 70 D, a melt index of 10 to 20 (240 ° C., 2.16 kg), and a melt viscosity of 2000 to 2800 poise at a solid phase of 30 hours or less. (240 ° C), the color value (b) according to ASTM D6290 satisfies all physical properties of 8 or less.

According to the present invention, it has a viscosity characteristic suitable for extrusion molding and blow molding including a crosslinking agent, and has excellent mechanical properties, molding processability and surface properties, and can be applied to cables and automobile machinery parts having remarkably high flexibility and bending characteristics. Thermoplastic polyester elastomer resin compositions can be provided.

Hereinafter, the present invention will be described in more detail.

The inventors of the present invention have made thermoplastic polymers comprising a crosslinking agent in an elastomer in which crystalline hard segments formed from aromatic dicarboxylic acids or their ester-forming derivatives and aliphatic diols and soft soft segments formed from polyalkylene glycols are randomly arranged. Ester elastomer composition exhibits a good balance of flexibility, mechanical strength, and heat resistance, has a viscosity characteristic suitable for extrusion blow molding, and has excellent melt viscosity (or melt tension), long-term heat aging stability, and appearance characteristics. Experiments confirmed that it can be applied to constant velocity joint boots, various bellows for automobiles and completed the invention.

Specifically, the present invention relates to a thermoplastic polyester elastomer composition, comprising 45 to 60% by weight of an acid component for forming a crystalline hard segment and 30 to 45% by weight of a bifunctional alcohol, and comprising a number average for forming a soft soft segment. 0.01 to 0.5 parts by weight of a polyfunctional monomer selected from the following general formula (1) or (2) as a crosslinking agent, based on 100 parts by weight of a resin composition containing 10 to 20% by weight of a polyalkylene glycol having a molecular weight of 1,000 to 2,000, and heat aging A thermoplastic polyester elastomer composition comprising 0.1 to 2 parts by weight of an inhibitor.

[Formula 1]

(Wherein R ₁ is selected from (C1-C3) alkyl or (C6-C20) aryl, R ₂ is (C1-C3) alkylene and n is an integer selected from 3-6)

[Formula 2]

(Wherein R ₃ is selected from (C1-C3) alkyl or (C6-C20) aryl, R ₄ is selected from hydrogen or (C1-C3) alkyl, m is an integer selected from 3-6)

Aromatic dicarboxylic acid (Dicarboxylic aicd) to form the crystalline hard segment is terephthalic acid (Terephthalic acid), isophthalic acid (Isophthalic acid), 2,6-Naphthalene dicarboxylic acid (2,6-Naphthalene dicarboxylic acid) and It may be at least one selected from the group consisting of 1,4-cyclohexane dicarboxylic acid (1,4-Cyclohexane dicarboxylic acid).

The ester forming derivatives of the aromatic dicarboxylic acid are dimethyl terephthalate, dimethyl isophthalate, 2,6-dimethyl naphthalene dicarboxylate and dimethyl 1,4 It may be at least one selected from the group consisting of -cyclohexane dicarboxylate (Dimethyl 1,4-cyclohexane dicarboxylate) and the like, preferably dimethyl terephthalate.

The aromatic dicarboxylic acid or its ester-forming derivative may be included in 45 to 60% by weight relative to the total weight of the thermoplastic polyester elastomer, preferably 30 to 55% by weight, the reaction balance within this range Excellent reaction proceeds smoothly.

The aliphatic diol which reacts with the aromatic dicarboxylic acid or its ester forming derivative to form a crystalline hard segment may be a diol having a molecular weight of 300 or less, and specific examples thereof include ethylene glycol, propylene glycol, 1 , 2-propanediol (1,2-Propanediol), 1,3-propanediol (1,3-Propanediol), 1,4-butanediol (1,4-Butanediol), 1,5-pentanediol (1,5 -Pentanediol) and 1,6-hexanediol (1,6-Hexanediol) and the like may be one or more selected from the group consisting of, preferably 1,4-butanediol, and with respect to the total weight of the thermoplastic polyester elastomer It may be included in 30 to 45% by weight, preferably contained in 30 to 40% by weight, the reaction is excellent in this range and the reaction proceeds smoothly.

Specifically, the acid component is any one or a mixture of two or more selected from dimethyl terephthalate, dimethyl isophthalate, terephthalic acid and isophthalic acid, the difunctional alcohol is any one selected from ethylene glycol, propylene glycol and butylene glycol Or mixtures of two or more.

The polyalkylene glycol is composed of a soft soft segment of an aliphatic polyether, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol glycol) and ethylene oxide (Ethylene oxide) may be one or more selected from the group consisting of, preferably polytetramethylene glycol is used.

The polyalkylene glycol may be included in an amount of 10 to 20% by weight based on the total weight of the thermoplastic polyester thermoplastic elastomer, and when less than 10% by weight, the hardness of the thermoplastic polyester elastomer to be manufactured is too high, thereby causing a problem in flexibility, and 20% by weight. If it is more than%, problems may occur such as heat resistance and compatibility of the thermoplastic polyester elastomer produced.

The polyalkylene glycol preferably has a number average molecular weight of 600 to 3,000, and more preferably 1,000 to 2,000, and has an effect of obtaining stable polymerization reactivity and physical properties of the polymerization copolymer within this range.

The hardness of the thermoplastic polyester elastomer is generally represented by Shore D, and may be determined by the content of the polyalkylene glycol.

In the thermoplastic polyester elastomer, a crosslinking agent may be used when preparing the polymerization, and when the thermoplastic polyester elastomer is used, the melt viscosity and the melt tension of the elastomer prepared may be increased.

The crosslinking agent may use a compound selected from Formula 1 or Formula 2.

[Formula 1]

(Wherein R ₁ is selected from (C1-C3) alkyl or (C6-C20) aryl, R ₂ is (C1-C3) alkylene and n is an integer selected from 3-6)

[Formula 2]

(Wherein R ₃ is selected from (C1-C3) alkyl or (C6-C20) aryl, R ₄ is selected from hydrogen or (C1-C3) alkyl, m is an integer selected from 3-6)

More specifically, in Formula 1, alkyl includes straight chain or pulverization, and the aryl is preferably phenyl.

Specifically, for example, it may be at least one selected from the group having a hydroxy group of at least three functional groups, such as glycerol, pentaerythritol, trimethylol propane, and the like, and trimellitic anhydride ( May be one or more from the group having carboxylic acid groups of at least three functional groups, such as Trimellitic Anhydride, Trimellitic acid, Trimesic aicd, and the like, and trimethyl 1,3,5-benzene carboxylate (Trimethyl 1,3,5-benzen tricarboxylatye), triethyl methanetricarboxylate and the like may be one or more selected from the group having alkoxy groups of three or more functional groups, preferably 1,3,5- Benzene carboxylate (Trimethyl 1,3,5-benzen tricarboxylatye).

With respect to 100 parts by weight of the thermoplastic polyester elastomer resin composition, 0.01 to 0.5 parts by weight based on the total weight of the multifunctional monomer, 0.01 to 0.5 parts by weight, if less than 0.01 parts by weight of the melt is not expected to rise, When the amount exceeds 0.5 parts by weight, the degree of polymerization of the elastomer to be produced may be excessively increased, making it difficult to control the melt polymerization reaction and to discharge the produced resin.

The anti-aging agent is to impart the long-term anti-aging properties required for automobiles, cables and various engineering plastic parts to the thermoplastic polyester elastomer composition to be produced, hindered phenolic antioxidants, diphenylamine antioxidants, metals It may be at least one selected from the group consisting of a complex antioxidant and a hindered amine light stabilizer, preferably a hindered phenolic antioxidant as N, N′-propane-1,3-dibis (3-3,5 -Di-tert-butyl-4-hydroxyphenyl) propionamide, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocyanide).

In addition, the present invention further comprises 0.01 to 0.5 parts by weight of an acrylic polyol having a number average molecular weight of 2000 to 5000, based on 100 parts by weight of the resin composition, to further improve transparency and strength. The acrylic polyol is preferably used because the glass transition temperature (Tg) of 25 to 65 ℃, the hydroxyl content of 1.5 to 5% and the acid value of 5 to 30 mgKOH / g can express transparency and high strength.

The present invention also encompasses polyester elastomer resins prepared by solid-phase polymerization of the thermoplastic polyester elastomer composition.

The melt polymerization is not particularly limited in the case of the conventional melt polymerization method that can be used in the preparation of the thermoplastic polyester elastomer, and in particular, titanium butoxide as a catalyst for the starting material consisting of aromatic dicarboxylic acid, aliphatic diol and polyalkylene oxide. After the side was introduced, a transesterification reaction was carried out at 140 to 215 ° C. for about 120 minutes to form a bis (4-Hydroxy Butyl) Terephthalate (BHBT) oligomer, and a titanium butoxide was added to the oligomer. , The polycondensation reaction was carried out until the melt flow index (Melt Flow Index, MFI) according to ASTM D1238 became 20g / 10min 230 ℃, 2.16kg at 215 to 245 ℃ and 760 torr to 0.3 torr. , The product was discharged in the reactor by nitrogen pressure and pelletized to finally thermoplastic polyester ella To produce a tomeo in a pellet form.

The polyester elastomer resin has a Shore D hardness of 40 to 70 D, a melt index of 10 to 20 (240 ° C., 2.16 kg), and a melt viscosity at solid phase polymerization of 30 hours or less at 2000 to 2800 poise (240 ° C.). ), Satisfies the physical property of the color value (b) of 8 or less according to ASTM D6290. If the Shore hardness is less than 40D, there is a problem in heat resistance, compatibility, and pelletization of the thermoplastic elastomer, and in the case of more than 70D, there is a problem in flexibility, and there is a problem in producing a product. If the melt index is less than 10 (240 ℃, 2.16kg), the melt viscosity is high and not suitable for extrusion blow molding. If the melt index is higher than 20 (240 ℃, 2.16kg), the melt viscosity is low, so that the tensile strength, elongation and flexural modulus, etc. Low mechanical properties are not suitable for extrusion blow molding. If the melt viscosity is less than 2000 poise (240 ℃), the mechanical properties are low, and the melt viscosity is low, so it is not suitable for extrusion blow molding. If the melt viscosity is higher than 2800 poise (240 ℃), the melt viscosity is high. And this impairs the heat resistance of the thermoplastic polyester elastomer. In addition, it is preferable that the color value (b) is 8 or less, and if it exceeds 8, it may cause a color problem after molding the product.

The invention is explained in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

The physical properties were measured by the following measurement method.

The thermoplastic polyester elastomer composition in pellet form prepared in Examples 1 to 5 and Comparative Example 1 was prepared as a test piece for measuring physical properties by using an injection molding machine, and the physical properties thereof were measured by the following method, and the results are as follows. Table 1 shows.

(1) Surface hardness: measured by Shore D type in accordance with ASTM D2240.

(2) Melt Index: Measured at 240 ℃ and 2.16kg according to ASTM D1238. Unit is g / 10min.

(3) Tensile strength and tensile elongation: measured at room temperature according to ASTM D638, and measured the tensile strength (kgf / cm ² ) and tensile elongation (%) at the break point.

(4) Flexural modulus: measured according to ASTM D790, and the unit is kgf / cm ² .

(5) Solid state polymerization time: Time taken to reach the target flow index at 180 ~ 190 ℃ after depressurization to 0.3 torr after being put into rotatable reactor

(6) Color measurement: It measured using Spectrophotometer SA4000 of Nippon Denshoku of Japan according to ASTM D6290.

Example 1

<Production of Thermoplastic Polyester Elastomer by Melt Polymerization>

Trimethyl 1,3,5-benzene as a crosslinking agent based on 100 parts by weight of a resin composition containing 50% by weight of dimethyl terephthalate, 38% by weight of 1,4-butanediol and 10% by weight of polytetramethylene glycol having a number average molecular weight of 1,000. 0.01 parts by weight of tricarboxylate was placed in an ester interchange reactor, 0.1 parts by weight of titanium butoxide, and the temperature was raised from 120 ° C. to 180 ° C. for 120 minutes, followed by reaction at 180 ° C. for 60 minutes. The reaction amount was converted into the reaction rate of methanol, and the reaction was terminated when the reaction rate was 90% or more to obtain an oligomer.

The oligomer is transferred to a polycondensation reactor, whereby N, N'-propane-1,3-dibis (3-3,5-di-tert-butyl-4-hydroxyphenyl is used as a phenolic antioxidant. After adding 1.0 part by weight of propionamide, the polycondensation reaction was carried out while raising the temperature to 245 ° C. for 120 minutes (reaction pressure was reduced from 760 torr to 0.3 torr for 60 minutes, and then maintained at 0.3 torr or less for 60 minutes). When the reaction reached 2.13 kgf · m (Torque), the reaction was terminated, and the prepared thermoplastic polyester elastomer was discharged out of the reactor using nitrogen pressure to prepare a pellet after cooling.

<Production of Thermoplastic Polyester Elastomer by Solid State Polymerization>

The thermoplastic polyester elastomer pellets prepared by melt polymerization were put in a rotatable reactor, and the polymerization was carried out while heating and rotating at 190 ° C. for 28 hours after reducing the pressure in the reactor to 0.3 torr, and the melt viscosity reached 2700 poise. The reaction was completed at the time point to prepare a thermoplastic polyester elastomer by solid phase polymerization.

Measured physical properties of the resin is shown in Table 1 below.

[Example 2]

A thermoplastic polyester elastomer was prepared in the same manner as in Example 1, except that 0.05 part by weight of the crosslinking agent was added.

In solid phase polymerization, the reaction was completed when the melt viscosity reached 2800 poise, and the solid phase polymerization time was 17 hours.

Measured physical properties of the resin is shown in Table 1 below.

[Example 3]

A thermoplastic polyester elastomer was prepared in the same manner as in Example 1 except for adding 0.1 part by weight of the crosslinking agent content.

In solid phase polymerization, the reaction was completed when the melt viscosity reached 2400 poise, and the solid phase polymerization time was 16 hours.

Measured physical properties of the resin is shown in Table 1 below.

Example 4

A thermoplastic polyester elastomer was prepared in the same manner as in Example 1 except for adding 0.3 part by weight of the crosslinking agent content.

In solid phase polymerization, the reaction was completed when the melt viscosity reached 2100 poise, and the solid phase polymerization time was 13 hours.

Measured physical properties of the resin is shown in Table 1 below.

[Example 5]

A thermoplastic polyester elastomer was prepared in the same manner as in Example 1 except for adding 0.5 parts by weight of the crosslinking agent content.

In solid phase polymerization, the reaction was completed when the melt viscosity reached 2000 poise, and the solid phase polymerization time was 12 hours.

Measured physical properties of the resin is shown in Table 1 below.

[Example 6]

In the case of polycondensation, the number average molecular weight is 2000, Tg 48 ° C., the hydroxyl content is about 3.5%, the acid value is 11.5 mgKOH / g, the solid content is 70.5%, the viscosity Z₃ (Gardner viscosity), and the Gardner color is 1 or less based on 100 parts by weight of the resin composition. A thermoplastic polyester elastomer was prepared in the same manner as in Example 1, except that 0.02 parts by weight of transparent acrylic polyol was further added.

In solid phase polymerization, the reaction was completed when the melt viscosity reached 2800 poise, and the solid phase polymerization time was 14 hours.

Measured physical properties of the resin is shown in Table 1 below.

Comparative Example 1

A thermoplastic polyester elastomer was prepared in the same manner as in Example 1 except that no crosslinking agent was added.

Comparative Example 2

A thermoplastic polyester elastomer was prepared in the same manner as in Example 1 except for adding 1.0 part by weight of the crosslinking agent content.

Table 1 Results of Test Example

As shown in Table 1, the thermoplastic polyester elastomer composition (Examples 1 to 5) of the present invention was confirmed that most of the physical properties such as melt viscosity, flexibility, mechanical strength and elongation are balanced, but does not include a crosslinking agent. (Comparative Example 1) Although most of the physical properties are good, but the solid phase polymerization time is long, productivity decreases, and the b value increases in the color, and the crosslinking agent content is included in excess (Comparative Example 2) without the solid phase polymerization process. Although the desired flow index was reached, it was confirmed that the melt viscosity was not suitable for extrusion blow molding.

Claims (8)

To 100 parts by weight of the resin composition consisting of 45 to 60% by weight of the acid component, 30 to 45% by weight of the bifunctional alcohol, 10 to 20% by weight of the polyalkylene glycol having a number average molecular weight of 1,000 to 2,000,
A thermoplastic polyester elastomer composition comprising 0.01 to 0.5 parts by weight of a multifunctional monomer selected from the following general formula (1) or (2) as a crosslinking agent, and 0.1 to 2 parts by weight of a heat aging inhibitor.
[Formula 1]

(Wherein R ₁ is selected from (C1-C3) alkyl or (C6-C20) aryl, R ₂ is (C1-C3) alkylene and n is an integer selected from 3-6)
(2)

(Wherein R ₃ is selected from (C1-C3) alkyl or (C6-C20) aryl, R ₄ is selected from hydrogen or (C1-C3) alkyl, m is an integer selected from 3-6) The method of claim 1,
A thermoplastic polyester elastomer composition further comprising 0.01 to 0.5 parts by weight of an acrylic polyol having a number average molecular weight of 2000 to 5000, based on 100 parts by weight of the resin composition. The method of claim 1,
The acid component is any one or a mixture of two or more selected from dimethyl terephthalate, dimethyl isophthalate, terephthalic acid and isophthalic acid, the difunctional alcohol is any one or two or more selected from ethylene glycol, propylene glycol and butylene glycol A thermoplastic polyester elastomer composition that is a mixture. The method of claim 1,
The polyalkylene glycol is a thermoplastic polyester elastomer composition of any one or two or more selected from polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol and ethylene oxide. The method of claim 1,
Wherein said multifunctional monomer is selected from trimethyl 1,3,5-benzenetricarboxylate, triethylmethane tricarboxylate, trimethylol propane, pentaerythritol and glycerol. The method of claim 1,
The anti-aging agent is a hindered phenol-based antioxidant, and N, N`-propane-1,3-dibis (3-3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, N, A thermoplastic polyester elastomer composition comprising N`-hexamethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocyanide) alone or in combination. A polyester elastomer resin prepared by solid-phase polymerization of the thermoplastic polyester elastomer composition of any one of claims 1 to 6. 8. The method of claim 7,
The polyester elastomer resin has a Shore D hardness of 40 to 70 D, a melt index of 10 to 20 (240 ° C., 2.16 kg), and a melt viscosity at solid phase polymerization of 30 hours or less at 2000 to 2800 poise (240 ° C.). ), Polyester elastomer resin having a color value (b) of 8 or less according to ASTM D6290.