KR101174955B1 - Thermoplastic polyester elastomer resin composite for blow molding - Google Patents

Abstract

The present invention relates to a thermoplastic polyester elastomer composite resin composition having excellent blow moldability, and more particularly to a) i) 50 to 90% by weight of thermoplastic polyester elastomer, ii) polybutylene terephthalate, polyethylene terephthalate, poly At least 5 to 45% by weight of one or more selected from the group consisting of cyclohexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and polytrimethylene terephthalate and iii) glycidyl groups 0.5 to 5 100 parts by weight of a base resin composed of weight percent; b) 0.1 to 1.5 parts by weight of a chain extender; And c) 1 to 3 parts by weight of a heat aging inhibitor. The present invention relates to a thermoplastic polyester elastomer composite resin composition having excellent blow moldability.

According to the present invention, an alloy such as a predetermined thermoplastic polyester elastomer and polybutylene terephthalate, etc., exhibits a balanced expression of flexibility, mechanical strength and heat resistance, and has a viscosity characteristic suitable for blow molding including a chain extender. Excellent melt viscosity (or melt tension), long-term heat aging stability, appearance characteristics, etc. has the effect of providing a thermoplastic polyester elastomer composite resin composition that can be applied to automotive air ducts, constant velocity joint boots, various bellows and the like.

Thermoplastic Polyester Elastomer Resin, Ethylene Copolymer, Chain Extender, Blow Molding, Long-term Heat Aging Stability

Description

Thermoplastic polyester elastomer composite resin composition excellent in blow moldability {THERMOPLASTIC POLYESTER ELASTOMER RESIN COMPOSITE FOR BLOW MOLDING}

The present invention relates to a thermoplastic polyester elastomer composite resin composition having excellent blow moldability, and more specifically, to an alloy including a predetermined thermoplastic polyester elastomer and polybutylene terephthalate, such that flexibility, mechanical strength and heat resistance are balanced. It has a viscosity characteristic suitable for blow molding, including chain extender, and has excellent melt viscosity (or melt tension), long-term heat aging stability, appearance characteristics, etc., so it is suitable for automobile air ducts, constant velocity joint boots, bellows, etc. It relates to a thermoplastic polyester elastomer composite resin composition that can be applied.

Recently, metals and crosslinked rubber parts have been replaced by plastic parts due to the demand for light weight and eco-friendliness in the automobile field. Accordingly, the utilization of thermoplastic elastomer materials having low specific gravity, good processability and recyclability is increasing.

In the TPE material group, thermoplastic polyester elastomers have excellent mechanical properties, low temperature characteristics, heat resistance, chemical resistance, and fatigue resistance, and are used in various parts of automobiles, electronics, and industrial applications requiring flexibility and engineering plastics. .

Automotive air ducts are parts that are connected to the complex structure of the engine room and exposed to high temperature, high pressure, and high vibration environments. Flexibility, cushioning effect, freedom of adhesion, 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.

The air duct for automobiles is manufactured by blow molding, and when the parison length is long during molding, the thermoplastic duct elastomer may have an optimal melt viscosity and melt tension in a molten state. It is essential to make a high viscosity high molecular weight polymer.

The thermoplastic polyester elastomer was generally prepared by melt polymerization, and this method has a limitation in obtaining a polymer having a high melt viscosity suitable for blow molding.

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 a thermoplastic polyester elastomer obtained by melt polymerization again into a solid state called solid phase polymerization. The resin obtained by the solid phase polymerization may have a large dependency on the temperature and residence time of the melt viscosity, and may cause a problem in that the molding conditions are greatly changed when molding after the primary molding.

In addition, a method of raising the melt viscosity of the thermoplastic polyester elastomer resin composition to a level easy to blow molding by blending a crosslinking agent or a chain extender, Japanese Patent Laid-Open No. 1999-323110, Japanese Laid-Open Patent No. 1999-323110, Japanese Patent Laid-Open No. 2000-239354, Japanese Patent Laid-Open No. 2000-355650, and Japanese Patent Laid-Open No. 2001-247752 disclose a method for blending a bifunctional or more than two functional epoxy compound with a thermoplastic polyester elastomer. 1975-121699, Japanese Patent Laid-Open No. 1982-78413, Japanese Patent Laid-Open No. 2005-325220, and US Pat. No. 5,378,986 disclose a method for blending polyisocyanate with thermoplastic polyester elastomer, and Japanese Patent Laid-Open No. 1986- 111318 et al. Discloses a method of blending liquid diphenylmethane diisocyanate with a thermoplastic polyester elastomer. In the case of using the epoxy compound, the reactivity with the carboxylic acid group may lead to an increase in viscosity, but in order to fully react, it is necessary to have sufficient residence time in the extruder, which leads to a decrease in productivity and also to a proper reaction rate. If it is not controlled by the extruder, it is difficult to have a constant melt viscosity at the time of blow molding by local gelling or unreacted epoxy, and when the polyisocyanate or liquid diphenyl methane diisocyanate is used, the extruder has a fast reactivity with hydroxyl groups. It is difficult to control the reaction rate in the reaction, and if the reaction is not made sufficiently, as a result there is a problem that the gas caused by the unreacted isocyanate when blowing, which can also cause a continuous reaction in the process of remelting during molding there is Adversely affect the adjusting molding conditions.

Therefore, there is a need for development of a thermoplastic polyester elastomer resin composition capable of satisfying blow molding properties and satisfying physical properties required for automobile air ducts.

In order to solve the problems of the prior art as described above, the present invention includes an alloy, such as a predetermined thermoplastic polyester elastomer and polybutylene terephthalate, such that the flexibility, mechanical strength and heat resistance are expressed in a balanced manner, and include a chain extender. Thermoplastic polyester elastomer composite resin that has viscosity characteristics suitable for blow molding and has excellent melt viscosity (or melt tension), long-term heat aging stability, and appearance characteristics, and can be applied to automotive air ducts, constant velocity joint boots, and various bellows. The purpose is to provide.

These and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides a) i) 50 to 90% by weight of thermoplastic polyester elastomer, ii) polybutylene terephthalate, polyethylene terephthalate, polycyclohexylene terephthalate, polyethylene naphthalate, polybutyl 100 parts by weight of a base resin consisting of 0.5 to 5% by weight of at least one selected from the group consisting of ethylene naphthalate and polytrimethylene terephthalate and iii) 0.5 to 5% by weight of an ethylene copolymer comprising a glycidyl group; b) 0.1 to 1.5 parts by weight of a chain extender; And c) 1 to 3 parts by weight of a heat aging inhibitor, to provide a thermoplastic polyester elastomer composite resin composition having excellent blow moldability.

As described above, according to the present invention, an alloy such as a predetermined thermoplastic polyester elastomer and a polybutylene terephthalate is exhibited in a balanced manner, such as flexibility, mechanical strength and heat resistance, and suitable for blow molding including a chain extender. It has a viscosity characteristic and excellent melt viscosity (or melt tension), long-term heat aging stability, appearance characteristics, etc. to provide a thermoplastic polyester elastomer composite resin composition that can be applied to automotive air ducts, constant velocity joint boots, various bellows, etc. It works.

Hereinafter, the present invention will be described in detail.

The thermoplastic polyester elastomer composite resin composition having excellent blow moldability of the present invention comprises a) i) 50 to 90% by weight of thermoplastic polyester elastomer, ii) polybutylene terephthalate, polyethylene terephthalate, polycyclohexylene terephthalate, Basic resin consisting of at least 5 to 45% by weight of at least one selected from the group consisting of polyethylene naphthalate, polybutylene naphthalate and polytrimethylene terephthalate and iii) 0.5 to 5% by weight of ethylene copolymer containing glycidyl groups 100 parts by weight; b) 0.1 to 1.5 parts by weight of a chain extender; And c) 1 to 3 parts by weight of heat aging inhibitor.

The thermoplastic polyester elastomer composite resin composition may further include carbon black for coloring.

(Iii) The thermoplastic polyester elastomer is 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 oxides are randomly arranged.

(Iii) The thermoplastic polyester elastomer is prepared by melt polymerization of aromatic dicarboxylic acid or its ester forming derivative, aliphatic diol, and polyalkylene oxide, and has Shore hardness of 35 to 50 D, within this range. Flexibility and low temperature characteristics are sufficiently expressed, and the flow index is preferably 10 to 20 (230 ° C., 2.16 kg). Within this range, the stable melt viscosity of the final product by reaction with a chain extender (or Melt tension).

(Iii) The thermoplastic polyester elastomer may preferably be prepared by solid-phase polymerization of the thermoplastic polyester elastomer prepared by the melt polymerization again, the Shore hardness is 35 to 50 D, and the flow index is 3 to 3. 7 (230 ℃, 2.16kg) is preferred, when the solid phase polymerization, there is an effect that can reduce the amount of chain extender used.

The aromatic dicarboxylic acid is terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, or the like. It may be one or more selected from the group consisting of.

The ester forming derivative of the aromatic dicarboxylic acid is at least one selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, 2,6-dimethyl naphthalene dicarboxylate, dimethyl 1,4-cyclohexane dicarboxylate, and the like. And dimethyl terephthalate.

The aromatic dicarboxylic acid or its ester-forming derivative may be included in 25 to 65% by weight, preferably 45 to 65% by weight based on the total weight of the thermoplastic polyester elastomer, excellent reaction balance within this range The reaction proceeds smoothly.

The aliphatic diol may be a diol having a molecular weight of 300 or less, and specific examples include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1 , 6-hexanediol and 1,4-cyclohexanedimethanol may be one or more selected from the group consisting of, preferably 1,4-butanediol, and 20 to 40 with respect to the total weight of the thermoplastic polyester elastomer It may be included in the weight%, preferably contained in 25 to 35% by weight, the reaction is excellent in this range and the reaction proceeds smoothly.

The polyalkylene oxide constitutes a soft soft segment with an aliphatic polyether. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, copolymers of ethylene oxide and propylene oxide, and polypropylene glycol. It may be at least one selected from the group consisting of ethylene oxide adpolymers and copolymers of ethylene oxide and tetrahydrofuran, and is preferably polytetramethylene glycol.

The polyalkylene oxide may be included in an amount of 10 to 50% by weight, preferably 15 to 45% by weight, based on the total weight of the thermoplastic polyester elastomer, and less than 10% by weight of the thermoplastic polyester elastomer If the hardness is too high, there is a problem in flexibility, and if it exceeds 50% by weight, there is a problem in heat resistance and compatibility of the thermoplastic polyester elastomer to be produced.

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

For reference, the hardness of the thermoplastic polyester elastomer is generally represented by Shore hardness (Shore D), and may be determined by the content of the polyalkylene oxide.

As the thermoplastic polyester elastomer, a branching agent or the like may be used when preparing the polymerization, and when used, the melt viscosity and the melt tension of the elastomer to be prepared may be increased.

The branching agent consists of glycerol, pentaerythritol, trimellitic anhydride, trimellitic acid, trimethylol propane, neopentyl glycol, and the like. It may be one or more selected from the group, preferably trimellitic anhydride, and may be included in the range of 0.05 to 0.1% by weight relative to the total weight of the thermoplastic polyester elastomer, if less than 0.05% by weight of the melt viscosity of the elastomer It is difficult to expect an increase, and when it exceeds 0.1% by weight, the degree of polymerization of the elastomer produced is excessively increased, making it difficult to control the melt polymerization reaction and discharge the produced resin.

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 adding the side, the transesterification reaction was carried out at 140 to 215 ° C. for about 120 minutes to form BHBT (Bis (4-Hydroxy Butyl) Terephthalate) oligomer, and titanium butoxide was added to the oligomer. Then condensation polymerization at 215 to 245 ° C. from 760 torr to 0.3 torr, until the flow index (MFI) according to ASTM D1238 reaches 20 g / 10 min (230 ° C., 2.16 kg) (reaction for approximately 120 minutes) After the reaction proceeds, the product is discharged in the form of strand in the reactor under nitrogen pressure, and pelletized, and finally To produce a plastic polyester elastomer in pellet form.

The solid phase polymerization is a flow index (MFI) according to ASTM D1238 while introducing the thermoplastic polyester elastomer prepared by the melt polymerization into a solid phase polymerization reactor, and then gradually depressurized to high vacuum from the presence of inert air flow at approximately 140 to 200 ℃ The high-viscosity thermoplastic polyester elastomer can be prepared by polymerizing for 10 to 24 hours until it is 10 g / 10 min (230 ° C., 2.16 kg) or less, preferably 5 g / 10 min or less.

The solid phase polymerization reactor may be a vessel vacuum dryer or the like to which a rotatable high vacuum pump is connected, and the inert air stream may be a nitrogen air stream or the like.

The polyalkylene oxide is poly (tetramethylene ether) glycol, and preferably has a molecular weight of 600 to 3,000. Within this range, suitable polymerization reactivity and physical properties can be expected.

In addition, the polyalkylene oxide may be a polypropylene glycol terminal capped with ethylene oxide, and preferably has a molecular weight of 2,000 to 3,000. Within this range, appropriate polymerization reactivity and physical properties can be expected.

Ii) polybutylene terephthalate, polyethylene terephthalate, polycyclohexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and polytrimethylene terephthalate is at least one selected from the group consisting of polybutylene terephthalate It is more preferable, which is excellent in economy, compatibility with the elastomer and reactivity with the chain extender.

The polybutylene terephthalate of ii) is prepared by solid phase polymerization of a low molecular weight polybutylene terephthalate resin prepared by melt polymerization, and has a flow index (MFI) of 3 to 10 g / 10 min (250 ° C., 2.16). kg), but less than 3 g / 10min, the terminal carboxyl and terminal hydroxyl groups that can react with the chain extender is small, leaving unreacted chain extender, and constant production quality cannot be obtained during blow molding. If it exceeds 10 g / 10min, a large amount of chain extender is required to obtain sufficient blowing properties, which leads to inefficiency, poor workability, long reaction extrusion time, and quality unevenness due to unreacted material after the extrusion.

Solid phase polymerization of the polybutylene terephthalate is a low molecular weight polybutylene terephthalate pellet prepared by melt polymerization in a solid phase polymerization reactor in the same manner as the solid phase polymerization of the thermoplastic polyester elastomer at 190 to 210 ℃, ASTM D1238 By the polymerization reaction until the flow index (MFI) by 10 g / 10min (250 ℃, 2.16kg) or less, preferably 3 to 10 g / 10min or less, to prepare a high viscosity polybutylene terephthalate can do.

(Iii) The ethylene-based copolymer containing glycidyl group functions as a reactive compatibilizer and a quencher, and is preferably ethylene-glycidyl methacrylate, ethylene-glycidyl methacrylate-vinyl acetate, or a mixture thereof. And, it is contained in 0.5 to 5% by weight relative to the total weight of the base resin, preferably contained in 1 to 3% by weight, if less than 0.5% by weight of the resin between the compatibility and no matting effect, 5% by weight If it exceeds, there is a problem that the long-term heat aging stability is sharply lowered.

The b) chain extender is preferably a polycarbodiimide, an acrylic epoxy copolymer or a mixture thereof, which is easy to handle as a solid at room temperature, can greatly increase the melt viscosity, and is easy to mix and input. As it has excellent long-term storage, it has the effect of minimizing the property deviation of each lot of product.

The polycarbodiimide may be used in an amount of 0.2 to 3 parts by weight, preferably 0.5 to 2 parts by weight, and more preferably 0.5 to 1.5 parts by weight, based on 100 parts by weight of the basic resin. It is advisable to minimize the polycarbodiimide content as much as possible in order to reduce the viscosity deviation of the product or to take into account economics.

The acrylic epoxy copolymer compound may be used in 0.1 to 3 parts by weight based on 100 parts by weight of the base resin, preferably used in 0.1 to 1.0 parts by weight, more preferably used in 0.1 to 0.5 parts by weight.

For reference, when the isocyanate-based chain extender is used as the chain extender, the reactivity of the thermoplastic polyester elastomer and the polybutylene terephthalate is excellent, but it is not easy to handle in a liquid state, and it is easily reacted with moisture to store it. It is difficult and difficult to control the reaction during the reaction extrusion, there is a problem that it is difficult to control the property deviation of each lot of the product.

The c) heat aging inhibitor is to impart long-term heat aging resistance properties required by automotive air ducts and various engineering plastic parts to the thermoplastic polyester elastomer composite resin produced, hindered phenolic antioxidant, diphenylamine It may be one or more selected from the group consisting of an antioxidant, a metal complex antioxidant, and a hindered amine light stabilizer, and preferably include all of the antioxidants and the light stabilizer. Long-term heat aging characteristics and durability of the thermoplastic polyester elastomer composite resin composition are greatly improved.

As the hindered phenol-based antioxidant, N, N'-hexane-1,6-diylbis (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)) and the like are preferable, As the diphenylamine antioxidant, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine and the like are preferable, and as the hindered amine light stabilizer, poly [[6- (1,1, 3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] -1 , 6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidinyl) imino] and the like, and the metal complex compound antioxidant is nickel N, N-dibutyldithiocarba Mate and the like are preferred.

 The thermoplastic polyester elastomer composite resin composition may further include other additives such as lubricant according to the use, but in the following examples, the use of the lubricant is excluded in consideration of the surface and glossiness of the blow molded article, adhesiveness between resins, and the like. .

Air duct for automobiles of the present invention is characterized by being manufactured by blow molding the thermoplastic polyester elastomer composite resin composition.

Hereinafter, a method of preparing the thermoplastic polyester elastomer and the polybutylene terephthalate by the melt polymerization and the solid phase polymerization and the compounding method including the same will be described in detail.

<Production of Thermoplastic Polyester Elastomer by Melt Polymerization>

 25 to 60 parts by weight of dimethyl terephthalate, 15 to 30 parts by weight of 1,4-butanediol and 25 to 60 parts by weight of polytetramethylene glycol having a molecular weight of 1,000 to 2,000 were placed in an ester interchange reactor and the catalyst titanium butoxide 0.03 parts by weight was added, the reaction mixture was heated at 140 ° C. to 215 ° C. for 120 minutes, and then reacted while maintaining 215 ° C. for 60 minutes, and the reaction effluent was converted into a reaction rate at a reaction rate of 90% or more. Termination yields oligomers.

The oligomer is transferred to a polycondensation reactor, and 0.03 to 0.04 parts by weight of chain extender trimellitic anhydride, 0.08 parts by weight of titanium butoxide as catalyst, 0.14 to 0.15 parts by weight of hindered phenolic antioxidant, Add 0.15 to 0.2 parts by weight of an aromatic amine antioxidant or a sulfur stabilizer, and then increase the temperature from 215 ° C to 245 ° C for 120 minutes (reaction pressure is reduced from 760 torr to 0.3 torr for 60 minutes, then 0.3 torr or less for 60 minutes). High vacuum holding) to terminate the reaction when the developer reaches the desired stirrer torque and discharge the prepared thermoplastic polyester elastomer out of the reactor using a nitrogen pressure to strand the mixture, followed by cooling. It is then prepared into pellets.

<Production of Thermoplastic Polyester Elastomer by Solid State Polymerization>

The thermoplastic polyester elastomer pellets prepared by melt polymerization were put into a rotatable reactor, and the pressure in the reactor was reduced to 0.3 torr, followed by polymerization while heating and rotating at 170 to 180 ° C. for about 15 to 20 hours to give solid phase polymerization. Thermoplastic polyester elastomer is prepared.

<Preparation of polybutylene terephthalate by melt polymerization>

60 parts by weight of dimethyl terephthalate and 38 parts by weight of 1,4-butanediol were added to a transesterification reactor, 0.02 parts by weight of titanium butoxide was added, the temperature was raised from 140 ° C to 215 ° C for 120 minutes, and then 215 ° C for 60 minutes. The reaction is carried out while maintaining, the amount of methanol as the reaction effluent is converted into the reaction rate, and the reaction is terminated when the reaction rate is 90% or more to obtain an oligomer.

The oligomer was transferred to a polycondensation reactor, 0.03 parts by weight of titanium butoxide, a small amount of magnesium acetate, 0.02 parts by weight of hindered phenolic antioxidant, and 0.03 parts by weight of sulfur stabilizer were added. The temperature was raised from 215 ° C to 250 ° C, the reaction pressure was reduced from 760 torr to 0.3 torr, and then condensation polymerization was carried out under high vacuum conditions of 240 to 245 ° C and 0.3 torr until the reaction was completed. When the torque is reached, the reaction is terminated, and the produced polybutylene terephthalate is discharged out of the reactor by using nitrogen pressure to be stranded, and then cooled into pellets.

<Production of Polybutylene Terephthalate by Solid State Polymerization>

The polybutylene terephthalate pellet drawn by melt polymerization was put into a rotatable reactor, and the pressure in the reactor was reduced to 0.3 torr, followed by polymerization while heating and rotating at 200 to 215 ° C. for about 8 to 12 hours to obtain solid phase polymerization. Polybutylene terephthalate is prepared.

<Compounding>

A chain extender, a heat aging inhibitor, a carbon black masterbatch, and the like are mixed with a basic resin including the thermoplastic polyester elastomer, a polybutylene terephthalate, and an ethylene copolymer including a glycidyl group, and then a diameter of 40 mm and a compression ratio. The thermoplastic polyester elastomer composite resin composition is prepared by performing reaction extrusion at a dosage of 40 kg / h and a screw speed of 250 rpm at 230 to 260 ° C. using a 40 twin screw extruder.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

1) TPEE-A: thermoplastic polyester elastomer [melt polymerization, hardness 42D, flow index 15 (230 ℃, 2.16kg) including poly (tetramethylene ether) glycol with number average molecular weight 2,000), manufacturer: LG Chemical

2) TPEE-B: thermoplastic polyester elastomer [manufactured by solid-phase polymerization of the TPEE-A, hardness 42D, flow index 5 (230 ℃, 2.16kg)], manufacturer: LG Chemical

3) TPEE-C: Thermoplastic Polyester Elastomer (Polymerization, 55D, Flow Index 15 (230 ℃, 2.16kg) with Poly (tetramethylene ether) Glycol with Number Average Molecular Weight 1,000)], Manufacturer: LG Chemical

4) PBT-A: polybutylene terephthalate [melt polymerization, flow index 15 (250 ℃, 2.16kg)], manufacturer: LG Chem

5) PBT-B: polybutylene terephthalate [manufactured by solid-phase polymerization of the PBT-A, flow index 3 (250 ℃, 2.16kg)], manufacturer: LG Chemical

6) EGMA: ethylene-glycidyl methacrylate (RA-3150), manufacturer: DuPont Elastomer

7) EGMA-VA: Ethylene-glycidyl methacrylate-vinylacetate (IGETA BOND 2B), manufacturer: Sumitomo Chemical

CE-1: Chain extender (Polycarbodiimide, Carbodilite HMV-8CA), Nissinbo Industries

9) CE-2: Chain extender (Joncryl ADR 4300), manufacturer: BASF

10) Anti-aging agent: Irganox 1098 (manufacturer: Ciba Specialty Chemicals), Naugard 445 (manufacturer: Crompton), Nocrac NBC (manufacturer: Ouchi Shinko Chemical Industrial), Chimassorb 944 (manufacturer: Ciba Specialty Chemicals)

11) Black color masterbatch: KEYFLEX BT M-40C, manufacturer: LG Chem

Examples 1-4 and Comparative Examples 1-6

The resins and additives described in Table 1, respectively, were mixed according to their contents, followed by melt kneading and extrusion at 230 to 260 ° C. using a twin screw extruder, and the extruded melt was cooled by passing through a cooling bath, followed by pellets. By sizing, thermoplastic polyester elastomer composite resin compositions were prepared in pellet form.

[Test Example]

The thermoplastic polyester elastomer composite resin composition of the pellet form prepared in Examples 1 to 4 and Comparative Examples 1 to 6 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. The results are shown in Table 1 below.

(1) Surface hardness: The hardness was measured by the Shore D type by the method of ASTM D2240.

(2) Melt index: measured after 4 min and 8 min stay at 230 ° C and 5 kg load, respectively, in accordance with ASTM D1238.

(3) Parison stability: While performing blow molding, the retention stability of the parison was visually observed and represented by (excellent), (good), and x (not moldable).

(4) Surface gloss (matte property): A blow molded article was produced, and whether or not partial gloss occurred on its outer surface was visually observed and represented by? (Matt),? (Semi-gloss), and × (partially glossy).

(5) Tensile strength and elongation: The specimens were injection molded according to DIN 53504-85 STAB 2 and measured at room temperature, and the tensile strength (Kg / cm ² ) and tensile elongation (%) at the break point were measured.

(6) Long-term heat aging stability: After inserting the DIN 53504-85 STAB type 2 injection molded specimen into the gear oven at 150 ° C, which is air circulation and rotation, it is taken out after 300 hours and left at room temperature for about 24 hours. Was measured.

division Example Comparative example One 2 3 4 One 2 3 4 5 6 Furtherance Suzy TPEE-A ¹⁾ 79 79 TPEE-B ²⁾ 79 79 79 79 80 79 74 TPEE-C ³⁾ 99 PBT-A ⁴⁾ 20 PBT-B ⁵⁾ 20 20 20 20 20 20 20 20 EGMA ⁶⁾ One One One One 6 One One EGMA-VA ⁷⁾ One One sub Total 100 100 100 100 100 100 100 100 100 100 additive
CE-1 ⁸⁾ 1.2 0.6 0.6 0.6 0.6 0.6 2.0 1.5 CE-2 ⁹⁾ 0.3 Heat Aging
Inhibitor ¹⁰⁾ 1.4 1.4 1.4 1.4 1.4 1.4 0.7 1.4 1.4 1.4 Carbon black
Masterbatch ¹¹⁾ 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Properties Surface hardness 48 48 48 48 48 48 48 47 48 53 Melt index (4 minutes stay) 3.0 3.5 3.5 3.2 6.2 3.6 3.4 2.7 2.3 2.5 Melt Index (8 minutes stay) 2.9 3.6 3.6 3.3 6.4 3.7 3.4 2.6 1.8 2.3 Parison stability ○ ◎ ◎ ◎ × ○ ◎ ◎ × ○ Surface gloss (matte characteristic) ◎ ◎ ◎ ◎ ○ × ◎ ◎ ◎ × Tensile Strength (kg / cm ² ) 280 265 271 249 292 285 276 255 252 402 Tensile Elongation (%) 485 463 469 431 530 491 470 428 440 695 Tensile Elongation (%)
(150 ℃, after 300 hours) 411 403 410 358 415 433 0 0 373 182

As shown in Table 1, the thermoplastic polyester elastomer composite resin compositions (Examples 1 to 4) of the present invention are excellent in blow molding properties (parison stability and matting properties, etc.) and long-term heat aging stability, flexibility, mechanical strength And it was confirmed that the elongation, etc. are expressed in a balanced manner, but in the case of not containing a chain extender (Comparative Example 1), the melt viscosity is low, the parison stability is greatly reduced and is not suitable for blow molding, and contains a glycidyl group In the case of not containing the ethylene copolymer (Comparative Example 2), most of the properties were good, but the matte properties were not shown in the blow molded article, and the glycidyl group was included in the case of containing less heat aging inhibitor (Comparative Example 3). In the case where the ethylene-based copolymer contained in an excessive amount (Comparative Example 4), the long-term heat aging stability was significantly decreased, and the chain extender When the amount is included (Comparative Example 5), the melt viscosity is high, but the reaction is not terminated, the retention stability is lowered, and the parison stability is very poor. And it was confirmed that the long-term heat aging stability is significantly reduced.

Claims (12)

a) i) 50 to 90% by weight of thermoplastic polyester elastomer resin, ii) with polybutylene terephthalate, polyethylene terephthalate, polycyclohexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and polytrimethylene terephthalate 100 parts by weight of a base resin consisting of 0.5 to 5% by weight of at least one selected from the group consisting of 5 to 45% by weight and iii) an ethylenic copolymer comprising a glycidyl group; b) 0.1 to 1.5 parts by weight of at least one chain extender selected from polycarbodiimide and acrylic epoxy copolymer compound; And c) 1 to 3 parts by weight of a hindered phenol-based antioxidant, a diphenylamine-based antioxidant, a metal complex compound antioxidant, and a hindered amine-based light stabilizer which is at least one selected from the group consisting of A thermoplastic polyester elastomer composite resin composition having excellent blow moldability. The method of claim 1, The thermoplastic polyester elastomer resin is prepared by melt polymerization of aromatic dicarboxylic acid or its ester-forming derivative, aliphatic diol and polyalkylene oxide, Shore hardness is 35 to 50 D, flow index of 10 to 20 ( 230 ° C, 2.16kg) A thermoplastic polyester elastomer composite resin composition having excellent blow moldability. The method of claim 1, The thermoplastic polyester elastomer resin is prepared by solid-phase polymerization of a resin prepared by melt polymerization from an aromatic dicarboxylic acid or its ester-forming derivative, aliphatic diol and polyalkylene oxide, and has a Shore hardness of 35 to 50 D. , Flow index is 3 to 7 (230 ℃, 2.16kg) characterized in that A thermoplastic polyester elastomer composite resin composition having excellent blow moldability. The method of claim 2 or 3, The polyalkylene oxide is poly (tetramethylene ether) glycol, characterized in that the horizontal average molecular weight is 600 to 3,000 A thermoplastic polyester elastomer composite resin composition having excellent blow moldability. The method of claim 2 or 3, The polyalkylene oxide is a polypropylene glycol terminal capped with ethylene oxide, the number average molecular weight is 2,000 to 3,000, characterized in that A thermoplastic polyester elastomer composite resin composition having excellent blow moldability. The method of claim 1, The polybutylene terephthalate of ii) is prepared by solid phase polymerization of low molecular weight polybutylene terephthalate resin prepared by melt polymerization, and has a flow index of 1 to 5 (250 ° C., 2.16 kg). By A thermoplastic polyester elastomer composite resin composition having excellent blow moldability. The method of claim 1, The ethylene-based copolymer containing a glycidyl group is ethylene-glycidyl methacrylate, ethylene-glycidyl methacrylate-vinyl acetate or a mixture thereof. A thermoplastic polyester elastomer composite resin composition having excellent blow moldability. delete delete The method of claim 1, The anti-aging agent is N, N'-hexane-1,6-diylbis (3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)), 4,4'-bis ( α, α-dimethylbenzyl) diphenylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2 , 2,6,6-tetramethyl-4-piperidinyl) imino] -1,6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidinyl) imino] and nickel N, N-dibutyldithiocarbamate is a mixture of A thermoplastic polyester elastomer composite resin composition having excellent blow moldability. The method of claim 1, The thermoplastic polyester elastomer composite resin composition, characterized in that it further comprises carbon black A thermoplastic polyester elastomer composite resin composition having excellent blow moldability. An automotive part manufactured by blow molding the thermoplastic polyester elastomer composite resin composition of claim 1.