KR20140047951A - Thermoplasticity resin composite and method of preparing thermoplasticity resin - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition and a method of preparing a resin using the same, and through a thermoplastic resin composition comprising: polyester elastomers; poly carbodiimide; fatty acid ester lubricant and montan wax; and a thermoplastic polyester elastomer resin and molded products having improved frictional properties and noise properties can be provided.

Description

Thermoplasticity resin composite and Method of preparing thermoplasticity resin

The present invention relates to a thermoplastic resin composition having a low coefficient of friction and low noise and a method of manufacturing a thermoplastic resin using the same.

Conventional thermoplastic resins, in particular, thermoplastic polyester elastomer resins (hereinafter referred to as TPEE resins), are excellent in mechanical properties such as strength, impact resistance, elastic recovery, flexibility, heat resistance, oil resistance, chemical resistance and dimensional stability, and are excellent in electrical and electronics. It has been used in automobiles and various precision parts. In addition, chlorinated rubber (CR), which is widely used for automobile parts, has a durability problem, and is being replaced with TPEE resin due to ease of processing and low cost. In particular, since automotive constant velocity joint boots are produced by blowing in the molten state of TPEE resin, they must have an optimum melt flow index (MFI) and melt tension in the molten state. In general, the base TPEE resin obtained by melt polymerization is usually produced by reaction extrusion because the thickness distribution of the molded article must have a constant parison property during the blow. In addition, since the TPEE resin material for automobile constant velocity joint boots is exposed to excessive wear and physical property change by high-speed driving and steering durability, it is very important to secure durability.

Since the general TPEE resin cannot blow due to the low melt flow index and melt tension in the molten state, the melt polycondensation method has a limitation in obtaining a polymer having a sufficiently high melt flow index. Moreover, even if it takes time to manufacture by melt polycondensation, there exists a problem that the physical property of a polymer falls, and the research for improving the melt fluidity index of TPEE is continuously going on.

For example, Japanese Patent Application Laid-Open No. 49-13297 discloses a solid state polymerization method in which the TPEE obtained by melt polymerization is subjected to high polymerization degree through solid phase polymerization, and the resin prepared by the disclosed method retains a melt flow index. The time dependence is large, and when remolding after molding, there is a problem that adjustment is necessary because the molding conditions significantly change.

In addition, attempts have been made to combine the crosslinking agent and the chain extender to bring up the melt flow index which can be blow molded. For example, Japanese Patent Laid-Open No. 11-323110, Japanese Laid-Open 2000-239354, Japanese Laid-Open 2000-355650, Japanese Laid-Open 2001-247752 The resin composition which mix | blended TPEE and a bifunctional or more epoxy compound is disclosed in Japanese Patent Application Laid-Open No. 52-121699, Japanese Patent Application Laid-Open 57-78413, Japanese Patent Application Laid-Open 2005-325220, and US 5733966. -111318 discloses a resin composition in which liquid diphenylmethane diisocyanate is mixed with TPEE, respectively. By the way, in the case of using the epoxy compound in the TPEE resin composition disclosed in the patent, the reactivity with the carboxylic acid group can induce a viscosity increase, but in order to fully react it must have a sufficient residence time in the extruder, There is a problem that decreases productivity. In addition, if the reaction rate is not properly controlled in the extruder, it is locally gelled or difficult to have a constant melt fluidity index during blow molding by unreacted epoxy. In addition, when polyisocyanate or liquid defenning methane diisocyanate is used, it is difficult to control the reaction rate in the extruder because of its rapid reactivity with hydroxyl groups and, as a result, unreacted isocyanate at blow time. There is a problem caused by the gas. In addition, unreacted isocyanate may cause a continuous reaction in the process of remelting during molding, which has a problem affecting the molding conditions control.

Japanese Patent Application Laid-Open No. 49-13297 Japanese Laid-Open Patent 1999-323110 Japanese Patent Laid-Open No. 2000-239354 Japanese Patent Laid-Open No. 2000-355650 Japanese Laid-Open Patent 2001-247752 Japanese Laid-Open Patent 2001-247752 Japanese Laid-Open Patent 2005-325220 Japanese Patent Application Laid-Open No. 52-121699 Japanese Patent Application Laid-Open No. 57-78413 US Patent 5733966 Japanese Patent Application Laid-Open No. 61-111318

In order to solve the above-mentioned problems, the present inventors have conducted a continuous study, and after melt polymerization, the solid phase polymerization can obtain a thermoplastic polyester elastomer having a high molecular weight and a molecular weight distribution, the composition comprising the thermoplastic polyester elastomer and the like In the production of a molded article by reaction extrusion, preferably blow extrusion, the introduction of polycarbodiimide, which is not an isocyanate compound, as a chain extender can increase the melt flow index and the melt tension. The present invention has been completed by reducing the frictional force of the surface to improve the noise characteristics. That is, an object of the present invention is to provide a new thermoplastic resin composition and a molded article having excellent physical properties using the same.

The present invention for solving the above problems relates to a thermoplastic resin composition, thermoplastic polyester elastomer (TPEE); Polycarbodiimide; Fatty acid ester type lubricants; And montan-based waxes.

In addition, the present invention relates to a method for producing a thermoplastic resin using the composition, by performing melt polymerization and solid-phase polymerization to prepare a thermoplastic polyester elastomer; And a step of mixing and reacting extrusion of thermoplastic polyester elastomer and polycarbodiimide, fatty acid ester lubricant and montan wax.

Moreover, this invention further features the resin molded article containing the said thermoplastic polyester elastomer resin composition.

Since the resin made of the thermoplastic polyester elastomer resin composition of the present invention has an optimum melt fluidity index and a low coefficient of friction, it is very excellent in noise characteristics and excellent in mechanical properties such as tensile strength and bending strength. It is suitable for use in high friction environments, such as constant velocity boots and bellows, where wear resistance and excellent noise characteristics are required.

As used herein, the term 'TPEE' is one of the thermoplastic resin compositions of the present invention, which is a base resin prior to the reaction extrusion, means a thermoplastic polyester elastomer, and 'TPEE resin' is the reaction extrusion using the composition. It means the manufactured thermoplastic resin.

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

The present invention, the thermoplastic resin composition is a thermoplastic polyester elastomer (TPEE); Polycarbodiimide; Fatty acid ester type lubricants; And montan-based waxes.

In addition, the thermoplastic resin composition of the present invention is 90 to 99 parts by weight of the TPEE; 0.05 to 5 parts by weight of the polycarbodiimide; 0.01 to 5 parts by weight of fatty acid ester lubricant; And 0.01 to 5 parts by weight of a montan wax.

The characteristic of each composition which comprises the thermoplastic resin composition of this invention is demonstrated.

The TPEE, which is one of the thermoplastic resin compositions, preferably uses 90 to 99 parts by weight, preferably 94 to 98 parts by weight, in terms of mechanical properties. The TPEE may be obtained by melt polymerizing an aromatic dicarboxylic acid, an aliphatic diol, and a polyalkylene oxide, followed by solid phase polymerization.

The aromatic dicarboxylic acid may be used 40 to 70 parts by weight, preferably 45 to 65 parts by weight within 100 parts by weight of the total TPEE. When the aromatic dicarboxylic acid is less than 40 parts by weight or more than 70 parts by weight, the reaction balance is not well-balanced and the polymerization does not proceed well. The aromatic dicarboxylic acid is 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 dicarboxylic acid, 1,4-CHDA), At least one selected from dimethyl terephthalate (DMT), dimethyl isophthalate (DMI), and dimethyl 1,4-cyclohexanedicarboxylate (DMCD) can be used. It is preferable to use at least one selected from DMT, DMI, and DMCD, and more preferably, DMT.

The aliphatic diol is preferably 20 to 40 parts by weight within 100 parts by weight of the total TPEE, preferably 25 to 35 parts by weight. If the aliphatic diol is out of the above range, there is a fear that the reaction balance is not well balanced and the polymerization reaction does not proceed well.

The aliphatic diol is preferably a diol having a molecular weight of 300 or less. Examples of the aliphatic diols that can be 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 At least one selected from diol and 1,4-cyclohexanedimethanol may be used, preferably 1,3-propanediol or 1,4-butanediol, and more preferably 1,4-butanediol good.

In general, the hardness of TPEE is expressed as Shore-D (Shore-D), and is affected by the content of polyalkylene oxide, which is 10 to 40 parts by weight within 100 parts by weight of the total TPEE. It can be used, it is preferable to use 15 to 45 parts by weight. If the amount of the polyalkylene oxide is less than 10 parts by weight, the hardness of the TPEE is too high, there is a problem that the flexibility is lowered, if it exceeds 40 parts by weight may cause heat resistance and compatibility problems of the TPEE itself. In addition, the polyalkylene oxide includes an aliphatic polyether as a component constituting the soft soft segment, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol ( polyoxytetrmethylene glycol, polyoxyhexamethylene glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide adducts of polypropylene oxide glycol, and copolymers of ethylene oxide and tetrahydrofuran may be used. Among them, polyoxytetramethylene glycol (hereinafter referred to as PTMEG) is preferably used. Such PTMEG may use a number average molecular weight of 600 to 3,000, preferably, a number average molecular weight of 1,000 to 2,000 may be used.

In addition, the TPEE may further use a branching agent in addition to the aromatic dicarboxylic acid, aliphatic diol and polyalkylene oxide in order to improve the melt flow index and the melt tension. The branching agent is selected from glycerol, pentaerythritol, trimelitic anhydride, trimelitic acid, trimethylol propane and neopentyl glycol. It may include one or more.

The melt fluidity index of the thermoplastic polyester elastomer (TPEE) obtained by melt polymerization of the aforementioned aromatic dicarboxylic acid, aliphatic diol and polyalkylene oxide and then solid state polymerization is 0.5 to 5 g / 10 min (230 ° C., load 2.16). Measured under ASTM D1238 under kg conditions), preferably 0.5-4 g / 10 minutes, most preferably 0.5-3 g / 10 minutes. If the melt flowability index of the TPEE is out of the above range, an improvement in the melt flowability index of the resin and physical property deviations may occur during the reaction extrusion.

Meanwhile, the polycarbodiimide, which is one of the thermoplastic resin compositions of the present invention, is used as a chain extender and a hydrolysis agent, and may be represented by the following Chemical Formula 1.

In Formula 1, n may be an integer of 8 to 15, it is preferable that n is an integer of 9 to 12. If n is less than 8, the mechanical properties of the thermoplastic resin produced may be low, and if n is greater than 15, the melt flow index of the thermoplastic resin produced may be too high.

Conventionally, bifunctional or higher isocyanate compounds, such as toluene diisocyanate, 4,4-diphenyl, in order to increase the molecular weight by extending the polymer chain as well as the alloy for several hours through the reaction with the carboxylic acid at the TPEE end Methane diisocyanate or modified substances thereof, isophorone diisocyanate, polymethylenepolyphenylpolyisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, and the like were used. Although the reactivity was excellent, there was a problem that it is difficult to control the lot-specific deviation of the lot during the reaction extrusion of the composition because the reactivity of the isocyanate and water is too fast. However, in the present invention, by introducing a polycarbodiimide represented by Chemical Formula 1, which is not an isocyanate compound, not only minimizes or prevents physical fluid deviations generated during melt flow index improvement and reaction extrusion of the resin, Hydrolysis effect can also be obtained.

It is preferable to use 0.05-5 weight part with respect to 100 weight part of thermoplastic resin compositions, and, as for the said polycarbodiimide, it is more preferable to use 0.1-3 weight part. In this case, when the polycarbodiimide is less than 0.05 parts by weight, the melt fluidity index may be too low, and when used in excess of 5 parts by weight, physical property deviations due to unreacted polycarbodiimide may occur.

One of the thermoplastic resin compositions of the present invention is a fatty acid ester-based lubricant, after molding the thermoplastic resin, eluting to the surface of the product to form a coating to prevent surface wear and noise generation of the product caused by friction due to rotation of the product. The fatty acid ester type lubricant is a fatty acid ester of an alcohol or a polyhydric alcohol, hardened oil, butyl stearate, stearic acid monoglyceride, pentaerythritol tetrastearate, stearyl stearate, ester wax or alkyl phosphoric acid. One or more selected ones of the esters may be used in a mixture, and among them, the use of pentaerythryl tetrastearate is preferred because it can increase the effect of reducing the frictional force of the resin. The fatty acid ester lubricant is preferably used in an amount of 0.01 to 5 parts by weight, and more preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the thermoplastic resin composition. In this case, when the fatty acid ester-based lubricant is less than 0.01 parts by weight, the melt fluidity index improvement effect may be insignificant, and when it exceeds 5 parts by weight, there may be a problem in that efficiency is reduced in terms of hardwood.

Montan wax, which is one of the thermoplastic resin compositions in the present invention, serves to prevent surface abrasion and noise generation of the product together with the lubricant, and the montan wax is montan wax esterified with ethylene glycol and montan acid (Esters). of montanic acids with ethylene glycol, esters of montanic acids with glycerine, calcium montanate containing montanic acid esters, based on montanic acid One or more selected from the complex ester of montanic acid can be used. In addition, the montan wax may preferably use a saponification value of 50 to 300 mg KOH / g, and more preferably 60 to 250 mg KOH / g of montan wax. If the saponification value of such montan-based wax is out of the above range, it is difficult to apply the surface and there may be a problem that surface migration occurs.

In the present invention, the montan wax is preferably used in an amount of 0.01 to 5 parts by weight, and more preferably 0.05 to 2 parts by weight based on 100 parts by weight of the thermoplastic resin composition. If the montan-based wax is less than 0.01 parts by weight, no wear and noise prevention effects are not seen, and it is uneconomical to use more than 5 parts by weight.

The thermoplastic resin composition of the present invention may be a paraffin wax, an antioxidant, an antioxidant aid, a light stabilizer, a UV stabilizer, a hydrolysis stabilizer, a metal deactivator, a pigment, a colorant, an antistatic agent, a conductivity providing agent, or an EMI shielding agent. At least one additive selected from a magnetic imparting agent, a crosslinking agent, an antimicrobial agent, a processing aid and an abrasion resistant agent may be further included within a range that does not significantly affect the physical properties according to the present invention, and preferably a thermoplastic resin composition. 0.1 to 5 parts by weight of the additive may be included based on 100 parts by weight of the total, and more preferably 0.5 to 3 parts by weight of the additive.

For example, N, N'-hexane-1,6-dibis (3- (3,5-di-ter-), which is one of hindered phenolic antioxidants, may be used to improve heat resistance. Butyl-4-hydroxyphenylpropionamide))) [N, N'-hexane-1,6-diylbis (3- (3,5-di-ter-butyl-4-hydroxyphenylpropionamide))] may also be used. As secondary antioxidant and heat aging stabilizer to improve heat aging resistance, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine [4,4'-bis (alpha) which is a diphenyl amine stabilizer , alpha-dimethylbenzyl) diphenylamine] may be used.

In addition, poly [[6- (1,1,3,3-tetramethylbutyl) imino] -1,2,5-triazine-2, which is a high molecular weight hindered amine light stabilizer as a heat-resistant aging aid 4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] -1,6-nucleic acid diyl [(2,2,6,6-tetramethyl-4 piperidinyl Imino]] {Poly [[6- (1,1,3,3-tertramethylbutyl) amino] -1,2,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl -4-piperidinyl) imino] -1,6-hexanediyl [(2,2,6,6-tatramethyl-4 piperidinyl) imino]]} may be used. In the case of using the above-mentioned antioxidant and light stabilizer in combination, long-term heat aging and durability can be obtained by synergistic effect.

Hereinafter, the manufacturing method of the thermoplastic resin of this invention is demonstrated in detail.

Method for producing a thermoplastic resin of the present invention (hereinafter referred to as TPEE resin) comprises the steps of preparing a thermoplastic polyester elastomer by performing melt polymerization and solid phase polymerization; And mixing and reacting extruding thermoplastic polyester elastomer and polycarbodiimide, fatty acid ester lubricant, and montan wax, and further comprising drying and injection processing the reactant extrudate. . In addition, the components used in the preparation method are the same as described above.

The melt polymerization is a mixture of aromatic dicarboxylic acid, aliphatic diol, polyalkylene oxide and titanium butoxide (TBT) as a catalyst, and then polymerized at 200 to 250 ℃ for 60 to 200 minutes, and the polymerization reaction At the same time or after the polymerization reaction, these may be subjected to solid phase polymerization to prepare a thermoplastic polyester elastomer. In this case, the solid phase polymerization is carried out under an inert gas, it is performed for 10 to 30 hours at 100 to 250 ℃, has an optimal melt fluidity index and low coefficient of friction, excellent mechanical properties such as tensile strength and flexural strength TPEE A resin can be obtained.

The reaction extrusion step is to prepare a TPEE resin by using a conventional reaction extruder or reaction extrusion means such as a twin-screw extruder, a single screw extruder, a roll mill, a kneader or a half-barrier mixer, and the like prepared by thermoplastic polymer elastomer and other compositions prepared by solid phase polymerization. Can be.

The above-mentioned thermoplastic resin composition of the present invention can be processed to produce a resin molded article, and such resin-like products can be used as constant velocity boots, bellows, tubes, sheets or the like. It may be a resin molded article of. Further, as a processing method of the resin molded article using the thermoplastic resin composition, melt processing through a mold may be mentioned.

Hereinafter, the present invention will be described in more detail with reference to examples of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example  1 to 6 and Comparative Example  1 to 6

After mixing the thermoplastic polyester elastomer (TPEE), chain extender, lubricant, montan wax and additives shown in Table 1 and Table 2, using a twin screw extruder at 200 ℃, screw rotation speed of 210 rpm Reaction extrusion was carried out to prepare a thermoplastic resin.

division Example (unit: parts by weight) One 2 3 4 5 6 TPEE ⁽¹⁾ 95.7 95.5 95.3 94.8 94.3 91.9 Chain Extenders ⁽²⁾ One One 1.2 One One 2.5 Lubricant ⁽³⁾ 0.3 0.5 0.5 One One 1.7 Montan Wax ⁽⁴⁾ 0.3 0.3 0.5 0.5 One 1.2 additive Paraffin Wax ⁽⁵⁾ - - - - - - Antioxidants ⁽⁶⁾ One One One One One One Light stabilizers ⁽⁷⁾ 0.2 0.2 0.2 0.2 0.2 0.2 Dispersants ⁽⁸⁾ 1.5 1.5 1.5 1.5 1.5 1.5 (1) TPEE: Keyflex BT 214D
(2) Chain extender: Polycarbodiimide, trade name Carbodilite HMV-8CA from NISSHINBO
(3) Lubricant: Pentaerythritol tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), trade name PETS-AHS of FACI ASIA PACIFIC PTE LTD
(4) Montan wax: trade name Licowax of clariant
(5) Paraffin wax: Nippon Seiro company name EP-1400
(6) Antioxidant: Naugard 445 by Chemtura Corporation
(7) Light stabilizer: Chimassorb 944 by Ciba specialty chemical
(8) Dispersant: Carbon black masterbatch, brand name M40C of LG Chemical Corporation

division Comparative example (unit: parts by weight) One 2 3 4 5 6 TPEE ⁽¹⁾ 96.3 95.3 95.3 95.3 95.3 95.3 Chain Extenders ⁽²⁾ One One One One One One Lubricant ⁽³⁾ - One - - 0.5 - Montan Wax ⁽⁴⁾ - - One - - 0.5 additive Paraffin Wax ⁽⁵⁾ - - - One 0.5 0.5 Antioxidants ⁽⁶⁾ One One One One One One Light stabilizers ⁽⁷⁾ 0.2 0.2 0.2 0.2 0.2 0.2 Dispersants ⁽⁸⁾ 1.5 1.5 1.5 1.5 1.5 1.5 (1) TPEE: Keyflex BT 214D
(2) Chain extender: Polycarbodiimide, trade name Carbodilite HMV-8CA from NISSHINBO
(3) Lubricant: Pentaerythritol tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), trade name PETS-AHS of FACI ASIA PACIFIC PTE LTD
(4) Montan wax: trade name Licowax of clariant
(5) Paraffin wax: Nippon Seiro company name EP-1400
(6) Antioxidant: Naugard 445 by Chemtura Corporation
(7) Light stabilizer: Chimassorb 944 by Ciba specialty chemical
(8) Dispersant: Carbon Black Masterbatch, LG Chemicals M40C

Experimental Example

After the specimens were prepared by injection molding each of the TPEE resins prepared in Examples and Comparative Examples, their melt flow index, tensile strength, flexural strength, coefficient of friction, and noise characteristics were measured. 3 is shown.

(1) Melt fluidity index measurement method

It measured at 230 degreeC and a 2.16 kg load based on ASTMD 1238.

(2) How to measure tensile strength

Tensile strength (kg / cm 2) at break was measured according to ASTM D 638.

(3) How to measure flexural strength

Flexural strength ((kg / cm 2) was measured according to ASTM D 790.

(4) Friction Coefficient Measurement Method

The coefficient of friction was measured according to ASTM D 1894 and measured 24 hours after the injection of the specimen.

(5) How to measure noise characteristics

Two injection-molded 2 mm disk specimens were placed in a low temperature chamber at −20 ° C., left for 24 hours, removed, and then subjected to forced friction between two specimens a total of five times to determine whether noise was generated. (◎: excellent noise characteristics, ○: noise characteristics normal, ×: noise characteristics poor)

division Melt flow index
(g / 10 min) The tensile strength
(Kg / cm2) Flexural strength
(Kg / cm2) Coefficient of friction Noise characteristics Example 1 2 243 620 0.28 ○ Example 2 1.8 245 622 0.25 ○ Example 3 1.9 243 620 0.15 ◎ Example 4 1.9 242 620 0.15 ◎ Example 5 1.9 243 621 0.15 ◎ Example 6 2.2 239 619 0.13 ◎ Comparative Example 1 1.9 242 622 0.76 × Comparative Example 2 1.9 242 622 0.52 × Comparative Example 3 1.9 244 623 0.45 × Comparative Example 4 1.9 243 621 0.45 × Comparative Example 5 2 243 621 0.50 × Comparative Example 6 2 243 622 0.45 ×

Looking at the experimental results of Table 3, the physical properties of the melt flow index, tensile strength and flexural strength of the molded specimen prepared from the thermoplastic resin of Examples 1 to 6 and Comparative Examples 1 to 6 of the present invention showed all excellent or similar results. . In particular, in the case of Examples 1 to 6, the friction coefficient is not only very low, 0.3 or less, but also excellent noise characteristics, while in the fatty acid ester type lubricant (pentaerythryl tetrastearate compound) and montan wax In the case of Comparative Examples 1 to 6 not using the selected one or two compositions, it was very high as 0.5 or more, and it can be seen that the noise characteristics are not very good.

Through the above examples and experimental examples, the thermoplastic resin prepared by the reaction extrusion of the TPEE resin composition of the present invention not only has excellent mechanical properties of tensile strength and flexural strength, but also has a low melt flow index, friction characteristics and noise characteristics. It is suitable for use as molded materials such as bars, constant velocity boots, bellows, tubes or sheets.

Claims (20)

Thermoplastic polyester elastomers; Polycarbodiimide; Fatty acid ester type lubricants; And montan-based waxes.
The method according to claim 1,
Polycarbodiimide is a thermoplastic resin composition represented by the following formula (1).
[Chemical Formula 1]

In Chemical Formula 1, n is an integer of 8 to 15.
The method according to claim 1,
90 to 99 parts by weight of thermoplastic polyester elastomer; 0.05 to 5 parts by weight of polycarbodiimide; 0.01 to 5 parts by weight of fatty acid ester lubricant; And 0.01 to 5 parts by weight of montan wax.
The method according to claim 1,
The thermoplastic polyester elastomer comprises 40 to 70 parts by weight of aromatic dicarboxylic acid, 20 to 40 parts by weight of aliphatic diol, and 10 to 40 parts by weight of polyalkylene oxide.
5. The method of claim 4,
Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, and Thermoplastic resin composition which is 1 or more types chosen from dimethyl 1, 4- cyclohexane dicarboxylate.
5. The method of claim 4,
Aliphatic diols are ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and 1,4-cyclohexanedi At least one thermoplastic resin composition selected from methanol.
5. The method of claim 4,
Polyalkylene oxides include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide addition polymers of polypropylene oxide glycol, and ethylene oxide and tetra 1 or more types of thermoplastic resin composition selected from the copolymer of hydrofuran.
5. The method of claim 4,
The polyalkylene oxide is a polyoxytetramethylene glycol having a number average molecular weight of 600 to 3,000.
5. The method of claim 4,
The thermoplastic polyester elastomer further comprises at least one branching agent selected from glycerol, pentaerythritol, trimellitic anhydride, trimellitic acid, trimethylolpropane and neopentylglycol.
3. The method of claim 2,
N in Formula 1 is an integer of 9 to 12 thermoplastic resin composition.
The method according to claim 1,
The fatty acid ester type lubricant is pentaerythryl tetrastearate.
The method according to claim 1,
Montan-based wax has a saponification value of 50 to 300 mg KOH / g thermoplastic resin composition.
The method according to claim 1,
Paraffin wax, antioxidant, antioxidant, light stabilizer, UV stabilizer, hydrolysis stabilizer, metal deactivator, pigment, colorant, antistatic agent, conductivity imparting agent, EMI shielding agent, magnetic imparting agent, crosslinking agent, antibacterial agent, processing aid and rubbing The thermoplastic resin composition further comprising at least one additive selected from among abrasives.
14. The method of claim 13,
Based on 100 parts by weight of the total thermoplastic resin composition, the thermoplastic resin composition further comprises 0.1 to 5 parts by weight of the additive.
The method according to claim 1,
The thermoplastic polyester elastomer has a melt fluidity index of 0.5 to 5 g / 10 min (at 230 ° C., measured by ASTM D1238 at 2.16 kg under load).
Preparing a thermoplastic polyester elastomer by performing melt polymerization and solid phase polymerization; And
A method for preparing a thermoplastic resin comprising mixing and reacting extrusion of thermoplastic polyester elastomer and polycarbodiimide, fatty acid ester lubricant and montan wax:
17. The method of claim 16,
Melt polymerization is characterized in that the polymerization is carried out for 60 to 200 minutes at 200 to 250 ℃ after mixing the aromatic dicarboxylic acid, aliphatic diol, polyalkylene oxide and titanium butoxide (TBT) catalyst Method for producing a thermoplastic resin.
17. The method of claim 16,
Solid phase polymerization is carried out under an inert gas, the method for producing a thermoplastic resin, characterized in that carried out for 10 to 30 hours at 100 to 250 ℃.
The resin molded article of the thermoplastic resin composition of any one of Claims 1-15.
19. The method of claim 18,
The resin molded article is a resin molded article which is a constant velocity boots, bellows, a tube, or a sheet.