KR20220053202A - Thermoplastic resin composition, method for preparing the same and article prepared therefrom - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, a method for preparing the same, and a molded article prepared therefrom, and more specifically, to a thermoplastic resin composition, a method for preparing the same, and a molded article prepared therefrom, which comprises: A) 100 parts by weight of a polyether ester elastomer resin; B) 1.5 to 4.6 parts by weight of a glycidyl group-modified olefin-based rubber polymer; and C) 0.15 to 1.3 parts by weight of a metal complex antioxidant, in which a heat aging resistance tensile strength retention rate calculated by equation 1 is 7 % or more and a heat aging resistance tensile elongation retention rate calculated by equation 2 is 12.5 % or more, in which tensile strength and tensile elongation are measured under the condition of 500 mm/min according to ISO 527 with regard to a specimen before aging, and a specimen after aging, which is taken out and left at room temperature for 24 hours after aging for 500 hours in a 150 ℃ gear oven with air circulation and rotation, the specimen after aging was taken out and left. According to the present invention, there is an effect of providing a thermoplastic resin composition which has excellent mechanical properties such as tensile strength and tensile elongation, and excellent heat aging resistance even after long exposure in high temperature environment, and thus can be applied with high quality in the field of automobile parts, and a molded article produced therefrom.

Description

Thermoplastic resin composition, manufacturing method thereof, and molded article manufactured therefrom

The present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article manufactured therefrom, and more particularly, has excellent mechanical properties such as tensile strength and tensile elongation, and has excellent heat aging resistance even after long-time exposure to a high temperature environment. It relates to a thermoplastic resin composition applicable to the field with high quality, a method for manufacturing the same, and a molded article manufactured therefrom.

Conventional thermoplastic polyester elastomer (thermoplastic polyetherester elastomer, hereinafter referred to as 'TPEE') has excellent heat resistance, chemical resistance, dimensional stability, flexibility, etc., and has been used in the electric, electronic, automobile industries and various precision parts.

Recent technological trends in electric, electronic, and automobile fields can be roughly divided into three categories: light weight, eco-friendliness, and e-mobility. Electric and electronic equipment and systems for automobiles that can pursue consumer convenience and stability are gradually increasing.

Accordingly, electronic equipment such as ADAS and sensors required for automobiles is rapidly increasing. The parts that drive the car and deliver the electricity necessary to operate various functions are the wiring harness, and the part that wraps it from the outside and protects it from external shocks and foreign substances is the Corrugated Tube. )am. Corrugated tubes used in automobile engine rooms are exposed to high-temperature environmental conditions for a long time, so excellent long-term heat aging resistance is required.

Accordingly, there is a demand for the development of a thermoplastic resin composition having satisfactory long-term heat aging resistance under high temperature operating environment conditions.

Korean Patent Publication No. 2009-0062785

In order to solve the problems of the prior art as described above, the present invention has excellent mechanical properties such as tensile strength and tensile elongation, and excellent thermal aging resistance even when exposed to a high temperature environment for a long time. An object of the present invention is to provide a method for manufacturing the same and a molded article manufactured therefrom.

The above and other objects of the present invention can all be achieved by the present invention described below.

In order to achieve the above object, the present invention is A) 100 parts by weight of polyether ester elastomer resin, B) 1.5 to 4.6 parts by weight of a glycidyl group-modified olefinic rubber polymer, and C) 0.15 to 1.3 parts by weight of a metal complex antioxidant Including, wherein B) the glycidyl group-modified olefin-based rubber polymer is represented by the following Chemical Formula 1

[Formula 1]

(In Formula 1, R is an alkyl group having 1 to 10 carbon atoms) containing a compound-derived unit, and after aging for 500 hours in a gear oven at 150 ℃ air circulation and rotation, taken out and left at room temperature for 24 hours The tensile strength and tensile elongation of the specimen after aging and the specimen before aging were measured under the conditions of 500 mm/min in accordance with ISO 527. It provides a thermoplastic resin composition, characterized in that the calculated heat aging resistance tensile elongation retention is 12.5% or more.

[Equation 1]

Heat aging resistance Tensile strength retention (%) = [Tensile strength after aging / Tensile strength before aging] X 100

[Equation 2]

Heat aging resistance Tensile elongation retention (%) = [Tensile elongation after aging / Tensile elongation before aging] X 100

In addition, the present invention includes A) 100 parts by weight of the polyether ester elastomer resin, B) 1.5 to 4.6 parts by weight of a glycidyl group-modified olefinic rubber polymer, and C) 0.15 to 1.3 parts by weight of a metal complex antioxidant 200 to 300° C. and kneading and extruding under 200 to 300 rpm conditions to prepare pellets, wherein B) the glycidyl group-modified olefinic rubber polymer is prepared by the following Chemical Formula 1

[Formula 1]

(In Formula 1, R is an alkyl group having 1 to 10 carbon atoms) containing a compound-derived unit represented by, and the thermoplastic resin composition is aged for 500 hours in a gear oven at 150 ° C. with air circulation and rotation, and then taken out for 24 hours The tensile strength and tensile elongation of the specimens after aging left at room temperature and the specimens before aging were measured under the conditions of 500 mm/min in accordance with ISO 527. It provides a method for producing a thermoplastic resin composition, characterized in that the heat aging resistance tensile elongation retention calculated by Equation 2 is 12.5% or more.

[Equation 1]

Heat aging resistance Tensile strength retention (%) = [Tensile strength after aging / Tensile strength before aging] X 100

[Equation 2]

Heat aging resistance Tensile elongation retention (%) = [Tensile elongation after aging / Tensile elongation before aging] X 100

In addition, the present invention provides a molded article comprising the thermoplastic resin composition.

According to the present invention, it has excellent mechanical properties such as tensile strength and tensile elongation, and excellent heat aging resistance even after long exposure in a high temperature environment. has the effect of providing.

Hereinafter, the thermoplastic resin composition of the present disclosure, a method for manufacturing the same, and a molded article manufactured therefrom will be described in detail.

The present inventors confirmed the effect of remarkably improved heat aging resistance due to the synergistic effect of these combinations when the polyether ester elastomer resin contains a glycidyl group-modified olefinic rubber polymer and a metal complex antioxidant in a predetermined amount, Based on this, further research has been devoted to complete the present invention.

The thermoplastic resin composition of the present invention comprises A) 100 parts by weight of the polyether ester elastomer resin, B) 1.5 to 4.6 parts by weight of a glycidyl group-modified olefinic rubber polymer, and C) 0.15 to 1.3 parts by weight of a metal complex antioxidant, B) The glycidyl group-modified olefin-based rubber polymer is prepared by the following Chemical Formula 1

[Formula 1]

(In Formula 1, R is an alkyl group having 1 to 10 carbon atoms) containing a compound-derived unit, and after aging for 500 hours in a gear oven at 150 ℃ air circulation and rotation, taken out and left at room temperature for 24 hours The tensile strength and tensile elongation of the specimen after aging and the specimen before aging were measured under the conditions of 500 mm/min in accordance with ISO 527. It is characterized in that the calculated heat aging resistance tensile elongation retention is 12.5% or more.

[Equation 1]

Heat aging resistance Tensile strength retention (%) = [Tensile strength after aging / Tensile strength before aging] X 100

[Equation 2]

Heat aging resistance Tensile elongation retention (%) = [Tensile elongation after aging / Tensile elongation before aging] X 100

In this case, it has excellent mechanical properties such as tensile strength and tensile elongation, and excellent heat aging resistance even after long exposure in a high temperature environment, so that it can be applied in high quality to the automotive parts field.

Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each configuration.

A) Polyetherester elastomer resin

A) The polyether ester elastomer resin has, for example, a melt index of 0.1 to 10 g/10min, preferably 1 to 10 g/10min, more preferably 3 to It may be 7 g/10min, and within this range, the moldability and processability of the final thermoplastic resin composition are excellent, and heat aging resistance is improved. When the melt index exceeds 10 g/10 min, an excess of B) glycidyl group-modified olefinic rubber polymer, which will be described later, may be required, which may result in glycidyl groups remaining during reaction and extrusion, resulting in quality unevenness and problems during molding. can cause

A) The polyether ester elastomer resin is, for example, an aromatic dicarboxylic acid or an ester-forming derivative thereof; aliphatic diols; and polyalkylene oxide; after melt polymerization, it can be obtained by solid-state polymerization of the product. Preferably, the resin is a random copolymer of a hard fraction formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol, and a soft fraction mainly composed of polyalkylene oxide.

The aromatic dicarboxylic acid is, for example, terephthalic acid (TPA), isophthalic acid (IPA), 2,6-naphthalene dicarboxylic acid (2,6-NDCA), 1,5 -naphthalene dicarboxylic acid (1,5-naphthalene dicarboxylic acid, 1,5-NDCA), 1,4-cyclohexane dicarboxylic acid (4-cyclohexane dicarboxylic acid, 1,4-CHDA) and diacid are substituted aromatic with a dimethyl group dimethyl terephthalate (DMT), dimethyl isophthalate (DMI), 2,6-dimethyl naphthalene dicarboxylate (2,6-dimethyl naphthalene dicarboxylate, 2,6- NDC) and dimethyl 1,4-cyclohexane dicarboxylate (dimethyl 1,4-cyclohexanedicarboxylate, DMCD) may be at least one selected from the group consisting of, preferably dimethyl terephthalate.

The aromatic dicarboxylic acid or its ester-forming derivative may be, for example, 25 to 60% by weight, preferably 29 to 55% by weight, more preferably 34 to 45% by weight based on 100% by weight of the total polyether ester elastomer resin, and , there is an effect excellent in the reaction balance within this range.

In addition, the aliphatic diol may preferably be a diol having a number average molecular weight (Mn) of 300 g/mol or less, more preferably ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol (1,4-BG), 1,5-pentanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol (1,4-cycloheanedimethanol, 1 ,4-CHDM) may be at least one selected from the group consisting of, preferably 1,4-butanediol.

The aliphatic diol may be, for example, 10 to 40% by weight, preferably 15 to 40% by weight, more preferably 20 to 30% by weight, based on 100% by weight of the total polyetherester elastomer resin, and the reaction within this range There is an excellent effect of balance.

The polyalkylene oxide is a unit constituting the soft fraction, and may include an aliphatic polyether as a component. The polyalkylene oxide is, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide addition polymer of polypropylene glycol, and ethylene oxide and tetrahydrofuran It may be a unit derived from at least one selected from the group consisting of a copolymer of, preferably a unit derived from an ethylene oxide addition polymer of polytetramethylene glycol or polypropylene glycol.

The polytetramethylene glycol-derived unit may have a number average molecular weight of, for example, 600 to 3,000 g/mol, preferably 1,000 to 2,500 g/mol, and more preferably 1,800 to 2,200 g/mol.

The unit derived from the ethylene oxide addition polymer of the polypropylene glycol may be, for example, a unit derived from polypropylene glycol capped with ethylene oxide, and preferably has a weight average molecular weight of 2,000 to 3,000 g/mol.

In the present description, the number average molecular weight can be measured by end group analysis or gel permeation chromatography (GPC).

As a specific example of the method for measuring using GPC, it can be measured as a relative value with respect to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent.

The polyalkylene oxide may be, for example, 25 to 60% by weight, preferably 29 to 55% by weight, more preferably 34 to 45% by weight, based on 100% by weight of the total polyetherester elastomer resin, and within this range There is an excellent effect of the reaction balance.

The polyether ester elastomer resin may preferably include a branching agent, and in this case, the melt viscosity and melt strength of the elastomer resin may be increased.

The branching agent is, for example, glycerol, pentaerythritol, trimellitic anhydride, trimellitic acid, trimethylol propane, and neopentyl glycol. ) may be at least one selected from the group consisting of, preferably trimellitic acid anhydride.

The branching agent may be, for example, 0.05 to 0.1% by weight, preferably 0.05 to 0.09% by weight, more preferably 0.06 to 0.09% by weight, based on 100% by weight of the total polyetherester elastomer resin, and the melting point within this range By increasing the degree, the melt viscosity of the elastomer resin is controlled, and consequently, there is an advantage in that it is easy to control the intrinsic viscosity during melt polymerization.

The polyether ester elastomer resin of the present invention may be obtained by, for example, melt-condensation polymerization and then solid-state polymerization.

Preferably, BHBT (bis ( After producing 4-hydroxy) butyl terephthalate) oligomer, the TBT catalyst is re-injected, and the melt polycondensation reaction is performed at 215 to 245° C. for 100 to 150 minutes, specifically for 120 minutes, 700 to 800 torr, for a specific example, 760 torr. to 0.1 to 1 torr, specifically, it can be carried out while reducing the pressure stepwise to 0.3 torr. The melt polycondensation reaction may be performed until the flow flow index (MFI) measured at 230°C and a load of 2.16 kg according to ASTM D1238 is 20 g/10min or less. After completion of the reaction, it can be discharged into the reactor under nitrogen pressure to pelletize the strands through pelletizing.

Then, solid-state polymerization of the pellets in a solid-state polymerization reactor or in a rotatable vacuum dryer at a temperature of 140 to 200° C. for about 10 to 24 hours may be performed under an inert air stream such as nitrogen under vacuum. The solid-state polymerization has a flow-flow index (MFI) of 10 g/10 min or less, preferably 1 to 10 g/10 min (230° C., 2.16 kg), more preferably measured at 230° C. and a load of 2.16 kg according to ASTM D1238. High viscosity can be achieved until 3 to 8 g/10 min (230° C., 2.16 kg).

The vacuum applied during the solid-state polymerization is not particularly limited as long as it is a degree of vacuum generally applied in the technical field to which the present invention pertains.

The polyether ester elastomer resin may include, for example, a unit derived from poly(tetramethylene ether) glycol having a number average molecular weight (Mn) of 600 to 3,000 g/mol, preferably a number average molecular weight (Mn) This is 2,000 to 3,000 g/mol, and may include a unit derived from polypropylene glycol capped with ethylene oxide.

The hardness of the polyether ester elastomer resin is expressed as shore hardness-D (shore D) measured according to ISO 868, and the hardness may be determined by the content of polyalkylene oxide. 10 to 50% by weight, preferably 15 to 50% by weight of polyalkylene oxide based on 100% by weight of the total polyetherester elastomer resin, so that the shore hardness of the polyetherester elastomer resin is 35 to 50D, preferably 40 to 50D 50% by weight, more preferably 15 to 45% by weight may be used. Within the above range, the hardness of the polyether ester elastomer resin is low, so the flexibility is good, and the heat resistance and compatibility of the resin itself are also excellent.

B) Glycidyl group-modified olefinic rubber polymer

The B) glycidyl group-modified olefinic rubber polymer serves as a chain extender to increase the molecular weight by increasing the length of the inner chain of the polyether ester elastomer.

The B) glycidyl group-modified olefinic rubber polymer is, for example, 0.5 to 5.5 parts by weight, preferably 1 to 5 parts by weight, more preferably 2 to 4 parts by weight, based on 100 parts by weight of the polyether ester elastomer resin, more More preferably, it may be 3 to 3.7 parts by weight, and within this range, fluidity, hardness, tensile strength, and tensile elongation are excellent, and there is an advantage of excellent heat aging resistance. When the above range is exceeded, single yarn occurs during tube extrusion due to reaction non-uniformity.

The B) glycidyl group-modified olefin-based rubber polymer is an example of the following Chemical Formula 1

[Formula 1]

(In Formula 1, R is an alkyl group having 1 to 10 carbon atoms) contains a compound-derived unit, and in this case, fluidity, hardness, tensile strength and tensile elongation are excellent, and there is an advantage of excellent heat aging resistance.

Preferably, B) the glycidyl group-modified olefin-based rubber polymer may be a polyethylene-based copolymer in which the compound represented by Formula 1 and glycidyl (meth) acrylate are grafted, and in this case, fluidity, hardness, and tensile strength There is an advantage in that the strength and tensile elongation are excellent, and the heat aging resistance is more excellent.

More preferably, B) the glycidyl group-modified olefinic rubber polymer may be a glycidyl group-modified ethylene-octene-based copolymer (EOR-GMA), and even more preferably, glycidyl (meth)acrylate is ethylene- It may be an ethylene-octene rubber-glycidyl methacrylate (EOR-GMA) copolymer graft-polymerized with an octene copolymer, and in this case, heat aging resistance is further improved.

The ethylene-octene rubber-glycidyl methacrylate (EOR-GMA) copolymer is, for example, 6 to 20% by weight of glycidyl methacrylate, preferably 6 to 15% by weight, based on 100% by weight of its total weight , more preferably 6 to 10% by weight may be graft polymerization, and the effect of increasing the melt viscosity and melt strength within this range is excellent.

The glycidyl group-modified ethylene-octene-based copolymer (EOR-GMA) has, for example, a melt flow index (MFI) of 1 to 5 g/10min, preferably 2, measured under ASTM D1238 at 190° C. under 2.16 kg. to 4 g/10min, and the effect of increasing the melt viscosity and melt tension within this range is excellent.

In the present description, the content of the monomer in the polymer may mean the weight % of the monomer input during the preparation of the polymer or the weight % of the unit derived from the monomer.

C) metal complex antioxidant

The C) metal complex antioxidant is, for example, 0.15 to 1.3 parts by weight, preferably 0.3 to 1.1 parts by weight, more preferably 0.4 to 1 parts by weight, even more preferably based on 100 parts by weight of the polyether ester elastomer resin. It may be 0.5 to 0.8 parts by weight, and there is an advantage of excellent surface quality while excellent heat aging resistance within this range. When the content exceeds 1.3 parts by weight, heat aging resistance is improved, but carbonized foreign substances are generated by the metal complex (COO ^- M ⁺ ), and the surface properties of the injection-molded article are deteriorated.

The C) metal complex antioxidant is, for example, 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, nickel N,N-dibutyldithiocarbamate or a mixture thereof, preferably nickel It is N,N-dibutyldithiocarbamate, and in this case, heat aging resistance and surface properties are excellent.

In the present invention, including the above B) glycidyl group-modified olefinic rubber polymer and the above C) metal complex antioxidant, there is an effect that heat aging resistance is further increased by a synergistic effect according to a combination thereof.

The thermoplastic resin composition may include, for example, at least one selected from the group consisting of a hindered phenol-based antioxidant, a diphenylamine-based antioxidant, a black master batch, and a lubricant, and in this case, the thermoplastic resin composition of the present disclosure There is an effect that the necessary physical properties are well realized without reducing the physical properties of the product.

The hindered phenolic antioxidant is, for example, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4 ,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene or a mixture thereof, preferably pentaerythritol tetrakis[3-(3,5-di-t-butyl) -4-hydroxyphenyl) propionate], and in this case, there is an effect of contributing to the improvement of heat aging resistance.

The hindered phenolic antioxidant may be included, for example, in an amount of 0.1 to 2 parts by weight, preferably 0.3 to 1.5 parts by weight, more preferably 0.3 to 1 parts by weight, based on 100 parts by weight of the polyether ester elastomer resin, It has the effect of contributing to the improvement of heat aging resistance within the range.

The diphenyl amine antioxidant is, for example, phenylnaphthylamine, 4,4'-dimethoxy diphenyl amine, 4,4'-bis(α,α-dimethylbenzyl) diphenyl amine and 4-isopropoxy di It may be one or more selected from the group consisting of phenylamine, preferably 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (4,4'-(α,α-dimethylbenzyl)diphenylamine) There is an effect that contributes to the improvement of heat aging resistance within this range.

The diphenylamine-based antioxidant may be included, for example, in an amount of 0.1 to 2 parts by weight, preferably 0.3 to 1.5 parts by weight, more preferably 0.3 to 1 parts by weight based on 100 parts by weight of the polyether ester elastomer resin.

When the hindered phenol-based antioxidant and the diphenyl amine-based antioxidant are used in combination, a synergistic effect is expressed, thereby further improving heat aging resistance.

The black masterbatch may be, for example, a carbon black masterbatch, in which case layer separation of the composition does not occur and dispersibility is improved.

The carbon black masterbatch is not particularly limited if it is a carbon black masterbatch applicable to a conventional polyetherester elastomer resin.

The black master batch may be, for example, 0.1 to 2.5 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the polyether ester elastomer resin, and within this range, the physical property balance is excellent.

The lubricants include hydrocarbon lubricants such as paraffin wax, polyolefin wax, and polypropylene wax obtained by refining crude oil; fatty acid amide lubricants such as steramide, oleamide, and erucamide; ester lubricants such as butyl stearate, glycerol monostearate, glycerine monooleate, stearyl stearate, and montan-based wax obtained by reacting montanic acid; stearic acid-based metal salt lubricant; fatty acid-based lubricants such as stearic acid and lauryl acid; and alcohol-based lubricants such as cetyl alcohol and stearyl alcohol; may be at least one selected from the group consisting of, preferably, montan-based wax, ethylene bis oleamide, or a mixture thereof.

The lubricant may be, for example, 0.05 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, based on 100 parts by weight of the polyether ester elastomer resin, in which case moldability is improved.

The thermoplastic resin composition optionally includes at least one selected from the group consisting of a flame retardant, a hydrolysis stabilizer, a dye, a pigment, a colorant, an antistatic agent, a crosslinking agent, an antibacterial agent, and a processing aid in 100 parts by weight of the polyether ester elastomer resin 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, even more preferably 0.5 to 1 parts by weight, within this range There is an effect that necessary physical properties are well realized without reducing the original physical properties of the resin composition.

Thermoplastic resin composition

Preferably, the thermoplastic resin composition is aged for 500 hours in a gear oven at 150° C. with air circulation and rotation, and then taken out and left at room temperature for 24 hours. After aging and pre-aging specimens according to ISO 527, 500 mm/min conditions Tensile strength and tensile elongation under The heat aging resistance tensile elongation retention calculated as 12.5% or more, more preferably 18% or more, still more preferably 25% or more, even more preferably 25 to 210%, particularly preferably 25 to 180%. There is an effect of excellent heat resistance and surface properties while excellent balance of all physical properties within this range.

[Equation 1]

Heat aging resistance Tensile strength retention (%) = [Tensile strength after aging / Tensile strength before aging] X 100

[Equation 2]

Heat aging resistance Tensile elongation retention (%) = [Tensile elongation after aging / Tensile elongation before aging] X 100

The thermoplastic resin composition, for example, put a specimen according to ISO37 standard in a gear oven at 150 ° C for air circulation and rotation, aging for 500 hours, and then taking out the specimen left at room temperature for 24 hours and bending it in half around a rod having a diameter of 2 cm. It may not be broken in the fold test, and in this case, the balance of all physical properties is excellent and there is an effect of excellent heat aging resistance.

The thermoplastic resin composition is, for example, by using a hot press (WABASH, G302H-15-ASTM-LPX) at a temperature of 230 ° C. to spread the pellets thinly in the form of a pancake having a diameter of 20 cm and a thickness of 1 mm, and visually observe the surface thereof. After measuring the diameter and number of foreign materials, the foreign material score calculated by the following Equation 3 may be 5 or less, preferably 3 or less, and in this case, the physical property balance is excellent and the surface properties are excellent.

[Equation 3]

Foreign object score = (Number of A X 1 point) + (Number of B X 2) + (Number of C X 4) + (Number of D X 6) + (Number of E X 9)

(The A is the diameter of the foreign material is 0.1 mm or less, B is 0.11 to 0.15 mm, C is 0.16 to 0.20 mm, D is 0.21 to 0.25 mm, E is 0.26 to 0.30 mm.)

For example, if three foreign objects with a diameter of 0.1 mm or less and two foreign objects with a diameter of 0.18 mm are found on a pancake-shaped surface with a diameter of 20 cm, the foreign object score is (3 X 1 point) + (2 X 4 points) ) = 11 points.

In the present substrate, foreign matter is a carbide generated on the surface after injection, which is generated by a metal complex (COO ^- M ⁺ ) and is observed as a black spot. When observing the occurrence of foreign substances, inject with NP (Natural Pigment) that does not contain black masterbatch.

The thermoplastic resin composition is extruded using a blow molding extruder at 220° C. under the condition of 28.3 rpm per meter so that the tube does not break up to 200 m, and in this case, the moldability is excellent.

The thermoplastic resin composition may have a tensile strength of 10 MPa or more, preferably 11 MPa or more, more preferably 11.5 to 15 MPa, measured under a condition of 500 mm/min based on ISO 527 as an example of an injection specimen, Within the range, all physical property balances have an excellent effect.

The thermoplastic resin composition may have a tensile elongation of 400% or more, preferably 420% or more, more preferably 420 to 550%, measured under a condition of 500 mm/min according to ISO 527 as an example of an injection specimen, Within the range, all physical property balances have an excellent effect.

Method for producing a thermoplastic resin composition

The method for preparing the thermoplastic resin composition of the present disclosure includes A) 100 parts by weight of polyether ester elastomer resin, B) 1.5 to 4.6 parts by weight of glycidyl group-modified olefinic rubber polymer, and C) 0.15 to 1.3 parts by weight of metal complex antioxidant and kneading and extruding under the conditions of 200 to 300 ° C and 200 to 300 rpm to prepare pellets, wherein B) the glycidyl group-modified olefin-based rubber polymer is prepared by the following Chemical Formula 1

[Formula 1]

(In Formula 1, R is an alkyl group having 1 to 10 carbon atoms) containing a compound-derived unit represented by, and the thermoplastic resin composition is aged for 500 hours in a gear oven at 150 ° C. with air circulation and rotation, and then taken out for 24 hours The tensile strength and tensile elongation of the specimens after aging left at room temperature and the specimens before aging were measured under the conditions of 500 mm/min in accordance with ISO 527. It is characterized in that the heat aging resistance tensile elongation retention calculated by Equation 2 is 12.5% or more.

[Equation 1]

Heat aging resistance Tensile strength retention (%) = [Tensile strength after aging / Tensile strength before aging] X 100

[Equation 2]

Heat aging resistance Tensile elongation retention (%) = [Tensile elongation after aging / Tensile elongation before aging] X 100

In this case, it has excellent mechanical properties such as tensile strength and tensile elongation, and excellent heat aging resistance even after long exposure in a high temperature environment, so that it can be applied in high quality to the automotive parts field.

The kneading and extrusion may be performed by, for example, a single screw extruder, a twin screw extruder, or a Banbury mixer, and in this case, the composition is uniformly dispersed to have excellent compatibility.

The kneading and extrusion is, for example, a barrel temperature of 200 to 300 ° C., preferably 210 to 290 ° C., more preferably 210 to 280 ° C., even more preferably 220 to 250 ° C. In this case, while the throughput per unit time is adequate, sufficient melt-kneading may be possible, and there is an effect that does not cause problems such as thermal decomposition of the resin component.

The kneading and extrusion may be performed under the condition that the screw rotation speed is, for example, 200 to 300 rpm, preferably 220 to 280 rpm, more preferably 230 to 270 rpm. While excellent, it has an effect of suppressing excessive cutting.

molded product

The molded article of the present substrate may include the thermoplastic resin composition of the present substrate, and in this case, there is an advantage in that both heat aging resistance are excellent.

The molded article may be, for example, a corrugated tube of an automobile, and in this case, there is an advantage that the thermoplastic resin composition of the present invention can provide higher quality than the quality required in the market.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such variations and modifications fall within the scope of the appended claims.

[Example]

* TPEE: KEYFLEX BT2140D (LG Chem) with a melt index of 5 g/10min (230℃, 2.16kg) and a shore D hardness of 40D

* Glycidyl group-modified olefinic rubber polymer: EOR-GMA (K&A TRADD, KT20; glycidyl methacrylate content 6-9 wt%)

* Metal complex antioxidant: Nocrac NBC (Ouchi Shinko Chemical Industrial)

* Hindered phenolic antioxidant: IR1010 (BASF)

* Diphenylamine antioxidant: Naugard445 (Jiansu FeiyaChemical Industry)

* Lubricant: OP-WAX (Hoechst)

* Black Masterbatch: KBT M-40C (LG Chem)

Examples 1 to 6 and Comparative Examples 1 to 8

Pellets were prepared by kneading and extruding the components and contents shown in Tables 1 and 2, respectively, in an extruder (SM Twin screw extruder, 25Φ) at an extrusion temperature of 230° C., a feed rate of 50 kg/hr, and a screw speed of 250 rpm. The flow index was measured with the prepared pellets. In addition, injection specimens were prepared from the pellets using an injection machine (ENGEL 120MT) at an injection temperature of 230°C, a mold temperature of 40°C, and an injection speed of 20 mm/min.

[Test Example]

The properties of the pellets and injection specimens prepared in Examples 1 to 6 and Comparative Examples 1 to 8 were measured by the following method, and the results are shown in Tables 1 and 2 below.

* Tensile strength (MPa), tensile elongation (%): Tensile strength and tensile elongation were measured with a specimen thickness of 2 mm under the conditions of 500 mm/min according to ISO 527.

* Heat aging resistance tensile strength retention (%): Put the specimen (thickness 2mm) in a gear oven at 150°C with air circulation and rotation, and after aging for 500 hours, take it out and leave it at room temperature for 24 hours. Tensile strength of all specimens was measured under a condition of 500 mm/min in accordance with ISO 527, and the following Equation 1 was calculated.

[Equation 1]

Heat aging resistance Tensile strength retention (%) = [Tensile strength after aging / Tensile strength before aging] X 100

* Heat aging resistance tensile elongation retention (%): Put a specimen (thickness 2mm) in a gear oven at 150°C with air circulation and rotation, and after aging for 500 hours, take it out and leave it at room temperature for 24 hours. Tensile elongation of all specimens was measured under a condition of 500 mm/min in accordance with ISO 527 and calculated by Equation 2 below.

[Equation 2]

Heat aging resistance Tensile elongation retention (%) = [Tensile elongation after aging / Tensile elongation before aging] X 100

* Specimen fold test: A specimen according to ISO37 standard is placed in a 150℃ gear oven with air circulation and rotation, aged for 500 hours, taken out, left at room temperature for 24 hours, and bent in half around a tube with a diameter of 2cm. The fracture was observed and evaluated as follows.

No break: the specimen does not break

Break: the specimen is broken

* Foreign matter score: Using a hot press (WABASH company, G302H-15-ASTM-LPX) with a temperature of 230 ° C, the pellets are spread thinly in the form of a pancake having a diameter of 20 cm and a thickness of 1 mm. After measuring the diameter and number, it was calculated by Equation 3 below.

[Equation 3]

Foreign object score = (Number of A X 1 point) + (Number of B X 2) + (Number of C X 4) + (Number of D X 6) + (Number of E X 9)

(The A is the diameter of the foreign object is 0.1 mm or less, B is 0.11 to 0.15 mm, C is 0.16 to 0.20 mm, D is 0.21 to 0.25 mm, E is 0.26 to 0.30 m.)

* Tube extrusion moldability: After extruding the tube up to 200 m at 220 °C at 28.3 rpm per meter using a blow molding extruder, fracture and moldability were evaluated as follows.

○ : Extruded without breaking up to 200m, excellent formability

X: fractured during extrusion, resulting in poor formability

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 TPEE 100 100 100 100 100 100 KT20 2.06 3.09 4.12 4.12 4.12 4.12 Nocrac NBC 0.31 0.31 0.31 0.51 0.72 1.03 IR1010 0.5 0.5 0.5 0.5 0.5 0.5 Naugard445 0.5 0.5 0.5 0.5 0.5 0.5 KBT M-40C 1.51 1.51 1.51 1.51 1.51 1.51 OP Wax 0.3 0.3 0.3 0.3 0.3 0.3 Properties heat aging resistance
150℃,
500Hr Tensile strength retention 8 9 9.5 10 11.6 13.3 Tensile Elongation Retention 14.4 20 25.6 28 81.5 176.2 tube extrudability ○ ○ ○ ○ ○ ○ bow score 0 0 0 0 0 1-5 Specimen Fold Test no break no break no break no break no break no break The tensile strength 12.5 12.1 11.8 12.4 12.5 12.4 tensile elongation 515.3 498.7 427.3 487.6 487.0 483.6

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 TPEE 100 100 100 100 100 100 100 100 KT20 - - 1.03 5.15 6.18 4.12 4.12 - Nocrac NBC - 0.31 0.31 0.31 0.31 1.54 - 0.3 IR1010 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Naugard445 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 KBT M-40C 1.51 1.51 1.51 1.51 1.51 1.51 1.51 1.51 OP-Wax 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Properties heat aging resistance
150℃,
500Hr Tensile strength retention Measure
impossible Measure
impossible 5 12 14 15.1 Measure
impossible Measure
impossible Tensile Elongation Retention Measure
impossible Measure
impossible 10 28 25 244.8 Measure
impossible Measure
impossible tube extrudability ○ ○ ○ X ^* X ^* ○ ○ ○ bow score 0 0 0 0 0 6-10 0 0 Specimen Fold Test Measure
impossible Measure
impossible break no break no break no break break break The tensile strength 16.4 17.7 13.4 21.3 25.9 12.3 14.4 15.0 tensile elongation 661.4 668.7 501.2 397.1 284.5 480.7 507.8 627.7

X ^* : tube breaks at 40m

As shown in Tables 1 and 2, the thermoplastic resin compositions (Examples 1 to 6) according to the present invention have excellent surface properties while being excellent in heat aging resistance and tube extrusion moldability compared to Comparative Examples 1 to 8. could

Specifically, in Comparative Examples 1 and 2, which did not include the glycidyl-modified ethylene-octene copolymer and the metal complex antioxidant, the specimens were damaged after heat-resistant aging, so that the physical properties could not be measured.

In Comparative Example 3, in which the glycidyl group-modified ethylene-octene copolymer was used below the scope of the present invention, the specimen was broken in the specimen fold test, and the glycidyl group-modified ethylene-octene copolymer was used in excess of the scope of the present invention. In Comparative Example 4, the tube was broken at a point 40 m in the tube extrusion moldability evaluation.

In addition, in Comparative Example 6, in which the metal complex antioxidant was used beyond the scope of the present invention, the foreign material score was greatly increased and the surface properties were poor, and thus it could not be applied to the product.

Claims (13)

A) 100 parts by weight of polyether ester elastomer resin,
B) 1.5 to 4.6 parts by weight of a glycidyl group-modified olefinic rubber polymer, and
C) containing 0.15 to 1.3 parts by weight of a metal complex antioxidant,
The B) glycidyl group-modified olefin-based rubber polymer is represented by the following Chemical Formula 1
[Formula 1]

(In Formula 1, R is an alkyl group having 1 to 10 carbon atoms) comprising a compound-derived unit,
After aging for 500 hours in a 150℃ gear oven with air circulation and rotation, take out and leave at room temperature for 24 hours. After aging and pre-aging specimens, the tensile strength and tensile elongation are measured under the conditions of 500 mm/min according to ISO 527. Thus, the heat aging resistance tensile strength retention calculated by the following Equation 1 is 7% or more, and the heat aging resistance tensile elongation retention calculated by the following Equation 2 is 12.5% or more
Thermoplastic resin composition.
[Equation 1]
Heat aging resistance Tensile strength retention (%) = [Tensile strength after aging / Tensile strength before aging] X 100
[Equation 2]
Heat aging resistance Tensile elongation retention (%) = [Tensile elongation after aging / Tensile elongation before aging] X 100
The method of claim 1,
A) The polyether ester elastomer resin has a melt index of 0.1 to 10 g/10min measured at 230°C under 2.16 kg according to ASTM D1238
Thermoplastic resin composition.
The method of claim 1,
A) The polyether ester elastomer resin is an aromatic dicarboxylic acid or an ester-forming derivative thereof; aliphatic diols; And polyalkylene oxide; after melt polymerization, characterized in that the resin obtained by solid-state polymerization of the product
Thermoplastic resin composition.
The method of claim 1,
A) The polyether ester elastomer resin has a number average molecular weight (Mn) of 600 to 3,000 g/mol, characterized in that it contains units derived from poly (tetramethylene ether) glycol
Thermoplastic resin composition.
The method of claim 1,
A) The polyether ester elastomer resin has a number average molecular weight (Mn) of 2,000 to 3,000 g/mol, and comprises a unit derived from polypropylene glycol capped with ethylene oxide at the end
Thermoplastic resin composition.
The method of claim 1,
B) The glycidyl group-modified olefin-based rubber polymer is a polyethylene-based copolymer grafted with glycidyl (meth)acrylate.
Thermoplastic resin composition.
7. The method of claim 6,
The glycidyl (meth) acrylate-grafted polyethylene-based copolymer is ethylene-octene rubber-glycidyl methacrylate (EOR) obtained by graft polymerization of glycidyl (meth) acrylate to an ethylene-octene copolymer. -GMA) characterized in that it is a copolymer
Thermoplastic resin composition.
The method of claim 1,
C) the metal complex antioxidant is 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, nickel N,N-dibutyldithiocarbamate, or a mixture thereof
Thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition is characterized in that it comprises at least one selected from the group consisting of hindered phenolic antioxidants, diphenylamine-based antioxidants, black master batches, and lubricants.
Thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition puts a specimen according to the ISO37 standard in a gear oven at 150° C. for air circulation and rotation, aging for 500 hours, and then taking the specimen out and leaving it at room temperature for 24 hours. Fold) characterized in that it did not break in the test
Thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition is spread thinly in the form of a pancake having a diameter of 20 cm and a thickness of 1 mm using a hot press (WABASH Corporation, G302H-15-ASTM-LPX) having a temperature of 230 ° C. After measuring the diameter and number of
Thermoplastic resin composition.
[Equation 3]
Foreign object score = (Number of A X 1 point) + (Number of B X 2) + (Number of C X 4) + (Number of D X 6) + (Number of E X 9)
(The A is the diameter of the foreign material is 0.1 mm or less, B is 0.11 to 0.15 mm, C is 0.16 to 0.20 mm, D is 0.21 to 0.25 mm, E is 0.26 to 0.30 mm.)
A) 100 parts by weight of the polyether ester elastomer resin, B) 1.5 to 4.6 parts by weight of a glycidyl group-modified olefinic rubber polymer, and C) 0.15 to 1.3 parts by weight of a metal complex antioxidant 200 to 300° C. and 200 to 300 rpm Including the step of kneading and extruding under conditions to prepare pellets,
The B) glycidyl group-modified olefin-based rubber polymer is represented by the following Chemical Formula 1
[Formula 1]

(In Formula 1, R is an alkyl group having 1 to 10 carbon atoms) containing a compound-derived unit,
The thermoplastic resin composition is aged for 500 hours in a gear oven at 150 ° C with air circulation and rotation, then taken out and left at room temperature for 24 hours. Characterized in that the tensile elongation is measured and the heat aging resistance tensile strength retention calculated by the following Equation 1 is 7% or more, and the heat aging resistance tensile elongation retention calculated by the following Equation 2 is 12.5% or more
A method for producing a thermoplastic resin composition.
[Equation 1]
Heat aging resistance Tensile strength retention (%) = [Tensile strength after aging / Tensile strength before aging] X 100
[Equation 2]
Heat aging resistance Tensile elongation retention (%) = [Tensile elongation after aging / Tensile elongation before aging] X 100
Claims 1 to 11, characterized in that it comprises the thermoplastic resin composition according to any one of
molded article.