KR20220083189A - Polyamide resin composition, method for preparing the same and molded article therefrom - Google Patents

Abstract

The present invention relates to a polyamide resin composition comprising a polyamide resin, a polyether-ester copolymer, a polyether block amide resin, a metal-based stabilizer, a polyol, and an additive in a predetermined composition ratio, a method for producing the same, and a molded article comprising the same is about
The present invention has the effect of providing a polyamide resin composition excellent in low-temperature impact resistance and long-term thermal stability while having high mechanical properties and heat resistance.

Description

Polyamide resin composition, manufacturing method thereof, and molded article comprising the same

The present invention relates to a polyamide resin composition, a method for producing the same, and a molded article comprising the same, and more particularly, to a polyamide resin, a polyether-ester copolymer, a metal-based stabilizer, a polyether block amide resin, and a polyol. It relates to a polyamide resin composition having excellent long-term heat resistance stability and excellent impact strength at room temperature and low temperature by including in a predetermined weight ratio, and the like.

Polyamide resin, a kind of engineering plastic, is a crystalline and thermoplastic material. It has excellent mechanical strength, abrasion resistance, heat resistance, chemical resistance, electrical insulation and arc resistance, and is used in a wide range of fields such as automobiles, electrical and electronic parts, and industrial materials. have.

However, polyamide resin has a problem in that impact resistance is lowered depending on the usage environment due to water absorption due to amide bond. In particular, when used as automobile parts, high mechanical properties and heat resistance are required. Even after that, the development of a polyamide resin having excellent tensile elongation and excellent impact resistance even at low temperatures has been continuously demanded.

Korean Patent Laid-Open Patent No. 10-1990-0000424

In order to solve the problems of the prior art, the present invention is to provide a polyamide resin composition excellent in impact strength, tensile strength and heat resistance at room temperature and low temperature, and excellent long-term heat resistance stability.

Another object of the present invention is to provide a method for preparing the polyamide resin composition and a molded article including the same.

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 provides 70 to 90% by weight of a polyamide resin, 1 to 25% by weight of a polyether-ester copolymer, 0 to 18% by weight of a polyether block amide resin, 0.4 to 1% by weight of a metallic stabilizer , 0 to 2% by weight of polyol and 1 to 10% by weight of additives, but after aging for 3,000 hours at a temperature of 150°C in a long-term heat-resistant oven, at 23°C according to ASTM D638, a specimen thickness of 3.2 mm and a tensile rate of 10 mm The tensile elongation after long-term thermal aging measured under the /min condition is 8% or more, and the tensile strength measured under the conditions of a specimen thickness of 3.2 mm and a tensile rate of 10 mm/min at 23 ° C according to ASTM D638 is 48 MPa or more. A polyamide resin composition is provided.

In another example, the present invention provides 70 to 90% by weight of a polyamide resin, 1 to 25% by weight of a polyether-ester copolymer, 1 to 10% by weight of a polyether block amide resin, 0.4 to 1% by weight of a metal-based stabilizer, 0.5 to 1% by weight of a polyol It provides a polyamide resin composition comprising 2% by weight and 1 to 10% by weight of an additive.

In addition, the present invention provides 70 to 90% by weight of a polyamide resin, 1 to 25% by weight of a polyether-ester copolymer, 0 to 18% by weight of a polyether block amide resin, 0.4 to 1% by weight of a metallic stabilizer, 0 to 2% by weight of a polyol % and 1 to 10% by weight of additives, including the step of kneading and extruding using an extrusion kneader of 10 to 100 pie at 200 to 330 ° C., Aging for 3,000 hours at a temperature of 150 ° C. in a long-term heat-resistant oven After long-term thermal aging, the tensile elongation after long-term thermal aging measured under the conditions of 3.2 mm in thickness and 10 mm/min tensile rate at 23°C according to ASTM D638 was 8% or more, and the specimen thickness was 3.2 mm at 23°C according to ASTM D638 and It provides a method for producing a polyamide resin composition, characterized in that the tensile strength measured under the condition of a tensile rate of 10 mm/min is 48 MPa or more.

In another example, the present invention provides 70 to 90% by weight of a polyamide resin, 1 to 25% by weight of a polyether-ester copolymer, 1 to 10% by weight of a polyether block amide resin, 0.4 to 1% by weight of a metal-based stabilizer, 0.5 to 1% by weight of a polyol A method of producing a polyamide resin composition comprising the step of kneading and extruding using an extrusion kneader of 10 to 100 pie standard at 200 to 330°C, including 2 wt% and 1 to 10 wt% of additives to provide.

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

According to the present invention, there is provided a polyamide resin composition, a method for manufacturing the same, and a molded article comprising the same, which is excellent in impact strength, tensile strength and heat resistance at room temperature and low temperature, and is excellent in long-term heat resistance to ensure excellent elongation even after long exposure to high temperature has the effect of providing.

The terms used in the present specification and claims should not be construed as being limited to conventional or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Accordingly, the configuration shown in the embodiments described in this specification is only one of the most preferred embodiments of the present invention and does not represent all the technical spirit of the present invention, so various equivalents that can be substituted for them at the time of the present application It should be understood that water and variations are possible.

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

The present inventors included the polyether-ester copolymer and the metal-based stabilizer in a predetermined weight ratio in the polyamide resin composition, and optionally added the polyether block amide resin or polyol in a predetermined weight ratio, thereby increasing the inherent room temperature impact strength of the polyamide resin. , while maintaining tensile strength and heat resistance, it was confirmed that the low-temperature impact strength was greatly improved, and the problem of a decrease in elongation after long-time exposure to high temperature was solved, and based on this, further research was completed and the present invention was completed.

The polyamide resin composition of the present invention comprises 70 to 90% by weight of a polyamide resin, 1 to 25% by weight of a polyether-ester copolymer, 0 to 18% by weight of a polyether block amide resin, 0.4 to 1% by weight of a metal-based stabilizer, and 0% by weight of a polyol to 2% by weight and 1 to 10% by weight of additives, but after aging for 3,000 hours at a temperature of 150°C in a long-term heat-resistant oven, a specimen thickness of 3.2 mm and a tensile rate of 10 mm/min at 23°C according to ASTM D638 Conditions It is characterized in that the tensile elongation after long-term thermal aging measured under In the case of high mechanical properties and heat resistance, there is an advantage of excellent low-temperature impact resistance and long-term heat resistance stability.

As another example, the polyamide resin composition of the present invention may include 70 to 90% by weight of a polyamide resin, 1 to 25% by weight of a polyether-ester copolymer, 1 to 10% by weight of a polyether block amide resin, 0.4 to 1% by weight of a metal-based stabilizer %, 0.5 to 2% by weight of polyol, and 1 to 10% by weight of additives. In this case, there is an advantage in that it has high mechanical properties and heat resistance, but also has particularly excellent low-temperature impact resistance and long-term thermal stability.

In the present description, the component ratio of the copolymer or resin may mean the content of units constituting the copolymer or resin, or may mean the content of monomers added during polymerization of the copolymer or resin.

Hereinafter, each component constituting the polyamide resin composition of the present disclosure will be described in detail as follows.

polyamide resin

The polyamide resin may be included in an amount of 70 to 90% by weight, preferably 75 to 88% by weight, more preferably 78 to 85% by weight, in 100% by weight of the total polyamide resin composition, within this range Although it has high mechanical properties and heat resistance, it exhibits high elongation even after being exposed to high temperatures for a long time and has excellent impact resistance properties even at low temperatures.

The polyamide resin may be used, for example, by condensation polymerization of lactam or w-amino acid having a ring structure alone or two or more types.

The lactam of the ring structure may be, for example, ε-caprolactam or ω-laurolactam, and the w-amino acid is, for example, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraamino acid. It may be at least one selected from the group consisting of methylbenzoic acid.

As another example, a polyamide resin obtained by condensation polymerization of diacids and diamines may be used.

The diacid is, for example, malonic acid, dimethyl malonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3 -Diethylsuccinic acid, azelaic acid, sebacic acid, sveric acid, dodecanedioic acid, eicodioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid , 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, may be at least one selected from the group consisting of aliphatic, alicyclic or aromatic dicarboxylic acids such as diglycolic acid.

The diamine is, for example, tetramethylenediamine, hexamethylenediamine, 2-methylpendamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylene Diamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-amino methyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane; It may be at least one selected from the group consisting of aliphatic, alicyclic or aromatic diamines such as bis(aminopropyl)piperazine and aminoethylpiperazine.

In addition, the polyamide resin may be, for example, a homopolyamide resin, a copolyamide resin, or a mixture thereof, preferably a homopolyamide.

The homopolyamide may be, for example, at least one selected from the group consisting of nylon 6, nylon 66, nylon 610, nylon 1010, nylon 46, nylon 11, nylon 12, nylon MXD6 and polyphthalamide.

The polyamide resin may be, for example, semi-crystalline or amorphous polyamide resin, preferably semi-crystalline, in which case chemical stability is more excellent.

In the present description, semi-crystalline and amorphous may be defined by standards or measurement methods commonly recognized in the art to which the present invention pertains.

The polyamide-based resin may have, for example, a melting temperature (Tm) of 200 to 250° C., preferably 210 to 240° C., and more preferably 210 to 230° C., and has excellent heat resistance within this range.

Unless otherwise specified in this description, the melting temperature of the polyamide resin may be measured using a Differential Scanning Calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument) to measure the melting point of the polymer. Specifically, after heating the polymer to 300°C, the temperature is maintained for 5 minutes, and after cooling to 20°C again, the temperature is increased to 300°C again. At this time, the temperature rise and fall rates during heating and cooling are 20°C, respectively It can be measured by adjusting /min.

The polyamide resin may have, for example, a relative viscosity (R.V.) of 2.5 to 3.5, preferably 2.7 to 3.5, and more preferably 3.0 to 3.4, and within this range, moldability and property balance are excellent.

In this description, the relative viscosity can be measured according to the ISO 307 standard unless otherwise specified. Specifically, using a solution prepared by dissolving 0.5 g of a sample in 100 ml of 96 wt% sulfuric acid aqueous solution, Ubbelohde) viscometer.

The polyamide resin according to the present invention may be prepared by a method known to those of ordinary skill in the art to which the present invention pertains, or may be used by selecting commercially available ones.

polyether-ester copolymer

The polyether-ester copolymer may be included in an amount of 1 to 25% by weight, preferably 5 to 20% by weight, more preferably 8 to 15% by weight to 100% by weight of the total polyamide resin composition, While having high mechanical properties and heat resistance within this range, even after exposure to high temperatures for a long time, it has high toughness and excellent low-temperature impact resistance.

The polyether-ester copolymer is a thermoplastic polyester elastomer (TPEE), for example, a crystalline hard segment containing an ester group formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol, and a poly It may be a random block copolymer of soft segments containing alkylene oxide as a main component, and in this case, low-temperature impact strength and long-term thermal stability are more excellent.

The polyether-ester copolymer may be prepared, for example, by melt polymerization of an aromatic dicarboxylic acid or an ester-forming derivative thereof, an aliphatic diol and a polyalkylene oxide.

As another example, the polyether-ester copolymer may be prepared by first melt-polymerizing an aromatic dicarboxylic acid or an ester-forming derivative thereof, an aliphatic diol, and a polyalkylene oxide, and then secondarily performing solid-state polymerization.

In the present description, the derivative is a compound in which a hydrogen atom or an atomic group of the original compound is substituted with another atom or group, for example, refers to a compound substituted with a halogen or an alkyl group.

The aromatic dicarboxylic acid is, for example, terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, and 1,4-cyclohexane dicarboxyl. It may be at least one selected from the group consisting of acids and the like.

The ester-forming derivative of the aromatic dicarboxylic acid is, for example, selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, 2,6-dimethyl naphthalene dicarboxylate, and dimethyl 1,4-cyclohexane dicarboxylate. It may be one or more, and preferably includes dimethyl terephthalate.

The aromatic dicarboxylic acid or an ester-forming derivative thereof may be included, for example, in an amount of 25 to 65 wt%, preferably 35 to 65 wt%, based on the total weight of the polyether-ester copolymer. There is an advantage that the reaction proceeds smoothly because the reaction balance is excellent in the inside.

The aliphatic diol may be a low molecular weight aliphatic diol having a molecular weight of 300 g/mol or less or 50 to 300 g/mol, and specific examples thereof include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, It may be at least one selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and 1,4-cyclohexanedimethanol, and preferably 1,4-butanediol. and may be included in an amount of 20 to 40% by weight, preferably 25 to 35% by weight, based on the total weight of the polyether-ester copolymer. Within this range, the reaction balance is excellent and the reaction proceeds smoothly There is an advantage to be

The polyalkylene oxide constitutes a soft segment of, for example, an aliphatic polyether, and specific examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol (polytetramethylene ether glycol), polyhexamethylene glycol, ethylene oxide and propylene oxide. may be at least one selected from the group consisting of a copolymer of polypropylene glycol, an ethylene oxide addition polymer of polypropylene glycol, and a copolymer of ethylene oxide and tetrahydrofuran, and preferably polytetramethylene glycol.

The polyalkylene oxide may be included, for example, in an amount of 10 to 50% by weight, preferably 15 to 45% by weight, based on the total weight of the polyether-ester copolymer, within this range the polyether-ester Although the flexibility of the copolymer is adequate, it has excellent heat resistance and compatibility, so that there is an effect of improving chemical resistance without significantly affecting physical properties such as mechanical strength or glossiness of the final resin composition.

The polyalkylene oxide may preferably have a number average molecular weight of, for example, 600 to 3,000 g/mol, more preferably 1,000 to 3,000 g/mol, still more preferably 1,500 to 3,000 g/mol, particularly more Preferably, it may be 1,500 to 2,500 g/mol, and within this range, it is possible to obtain an elastomer resin having excellent polymerization reactivity and a desired hardness and flow index.

In the present description, the weight average molecular weight (Mw) and number average molecular weight (Mn) are tetrahydrofuran as a solvent at a temperature of 40° C. through gel chromatography GPC (Gel Permeation Chromatography, waters breeze) filled with porous silica as a column packing material. (THF) can be used to measure relative to a standard polystyrene (PS) sample. At this time, as a specific example of measurement, solvent: THF, column temperature: 40°C, flow rate: 0.3ml/min, sample concentration: 20mg/ml, injection amount: 5μl, column model: 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing: Agilent ChemStation S/W, test method (Mn, Mw and PDI): It can be measured under the conditions of OECD TG 118.

In addition, the polyether-ester copolymer may be polymerized using a branching agent during polymerization, for example, and in this case, melt viscosity or melt strength may be improved.

The branching agent is, for example, glycerol, pentaerythritol (Pentaerythritol), trimellitic anhydride (Trimellitic Anhydride), trimellitic acid (Trimellitic Acid), trimethylol propane (Trimethylol Propane) and neopentyl glycol (Neopentyl Glycol) It may be at least one selected from the group consisting of, preferably trimellitic anhydride. The branching agent, for example, may be included in an amount of 0.05 to 0.1 wt% based on the total weight of the polyether-ester copolymer, and within this range, melt viscosity is high and productivity is excellent.

The melt polymerization is not particularly limited as long as it is a method commonly used in the art, and preferably titanium butoxide as a catalyst is added to a starting material consisting of aromatic dicarboxylic acid, aliphatic diol and polyalkylene oxide, and then 140 to A BHBT (Bis(4-Hydroxy Butyl) Terephthalate) oligomer was prepared by performing a transesterification reaction at 215° C. for approximately 120 minutes, and titanium butoxide, a catalyst, was added to the prepared oligomer again, and then 760 torr at 215 to 245° C. The polyether-ester copolymer is finally prepared in the form of pellets by carrying out the polycondensation reaction while stepwise reduced pressure from to 0.3 torr, then discharging the product in the form of a strand in the reactor under nitrogen pressure, and pelletizing it.

In the solid-state polymerization, the polyether-ester copolymer prepared by the melt polymerization is put into a solid-state polymerization reactor, and then the polyether is polymerized for 10 to 24 hours while gradually reducing the pressure to high vacuum at about 140 to 200° C. under inert airflow. -ester copolymers can be prepared.

The polyether-ester copolymer may have, for example, a D-type shore hardness measured according to ASTM D2240 of 25D to 40D, preferably 25D to 37D, more preferably 27D to 35D, within this range. There is an advantage that the moldability and heat resistance are more excellent.

The polyether-ester copolymer may have, for example, a melting temperature of 150 to 210°C, preferably 150 to 190°C, more preferably 160 to 180°C, and has better heat resistance and long-term heat resistance stability within this range. There is an advantage.

The polyether-ester copolymer has a flow index (230° C., load 2.16 kg) of 20 to 50 g/10 min, preferably 20 to 40 g/10 min, more preferably 23, measured according to ASTM D1238, for example. to 40 g/10 min, and within this range There is an advantage in that the molding processability and the balance of physical properties are excellent.

In this description, the flow index (230 ° C., load 2.16 kg) measured according to ASTM D1238 is set to 2.16 kg of weight at 230 ° C, and the reference time is 10 minutes, and the melt index can be measured according to ASTM D1238. . More specifically, using GOETTFERT's melting index measuring equipment, the specimen is heated to a temperature of 230°C, placed in a cylinder of a melt indexer, a load of 2.16 kg is applied with a piston, and melted for 10 minutes. It can be obtained by measuring the weight (g) of the resulting resin.

The polyether-ester copolymer may be a commercially available product as long as it follows the definition of the present invention.

polyether block amide resin

The polyether block amide resin is included in an amount of 0 to 18% by weight in 100% by weight of the total polyamide resin composition, and has high mechanical properties and heat resistance within this range, and has toughness and low temperature even after exposure to high temperature for a long time It also has an excellent impact resistance property.

As a preferred example, the polyether block amide resin may be included in an amount of 1 to 15% by weight, more preferably 2 to 10% by weight, more preferably 2 to 8% by weight to 100% by weight of the total polyamide resin composition, In this case, there is an advantage in that room temperature and low temperature impact resistance and long-term heat resistance stability are more excellent.

As another example, the polyether block amide resin may be included in 100% by weight of the total polyamide resin composition in an amount of 1 to 10% by weight, and has excellent impact strength at room temperature and low temperature within this range and excellent long-term heat resistance. Preferably, it may be included in an amount of 1 to 12% by weight, more preferably 2 to 10% by weight, and still more preferably 3 to 8% by weight.

As another example, the polyether block amide resin may be included in an amount of 0 to 10% by weight, more preferably 0 to 5% by weight, more preferably, to 100% by weight of the polyamide resin composition, and more preferably the polyether block amide resin. The resin may be a polyether block amide resin-free composition, and in this case, there is an advantage in that tensile strength and heat resistance are more excellent.

The polyether block amide resin has excellent low-temperature characteristics in the polyamide resin composition of the present base material, and has little change in hardness at low temperature, high elastic recovery rate, and excellent bending resistance and fatigue resistance. In addition, it has excellent molding processability, so injection molding, extrusion molding, and blow molding are easy, and blending with other materials is easy.

The polyether block amide resin is a block copolymer, which means that the monomer groups included in the copolymer form blocks and are copolymerized between blocks, and unless otherwise specified in the present invention, it is understood as a block copolymer known to those skilled in the art. can be

The polyether block amide resin is, for example, a polyamide oligomer having a number average molecular weight of 100 to 8,000 g/mol having a carboxyl group at the terminal and a bisphenol compound having a number average molecular weight of 200 to 5,000 g/mol containing an oxyalkylene unit. of a polyamide oligomer having a number average molecular weight of 200 to 6,000 g/mol, preferably having a carboxyl group at the terminal, and an oxyalkylene unit having a number average molecular weight of 300 to 4,000 g It consists of two components of a bisphenol compound of /mol, more preferably a polyamide oligomer having a number average molecular weight of 1,000 to 4,000 g/mol having a carboxyl group at the terminal, and a number average molecular weight containing an oxyalkylene unit It is made by including two components of a bisphenol compound of 500 to 3,000 g/mol, and in this case, mechanical properties and heat resistance are excellent.

The polyamide oligomer and bisphenol compound are not particularly limited as long as they can be generally used in the art to which the present invention pertains.

The polyether block amide resin may have, for example, a relative viscosity (96% sulfuric acid solution, 20° C.) of 2.0 or less, preferably 0.5 to 2.0, more preferably 1.0 to 1.5, within this range, moldability and heat resistance. There are advantages over this.

The polyether block amide resin may have, for example, a melting temperature of 150 to 200°C, preferably 150 to 180°C, more preferably 160 to 170°C, and has excellent mechanical properties and heat resistance within this range. .

Unless otherwise specified in this description, the melting temperature of the polyether block amide resin may be measured using a Differential Scanning Calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument) to measure the melting point of the polymer. Specifically, after heating the polymer to 220°C, the temperature is maintained for 5 minutes, and after cooling to 20°C again, the temperature is increased again. can be measured by

The polyether block amide resin has an elongation at break of 450% or more, preferably 450 to 700%, more preferably 470 to It may be 650%, more preferably 500 to 650%, and there is an advantage that mechanical strength and low-temperature impact resistance are more excellent without deterioration of other physical properties within this range.

The polyether block amide resin may have, for example, a D-type shore hardness of 20 to 55D, preferably 25 to 50D, more preferably measured 15 seconds after applying a load, according to ASTM D2240, according to ASTM D2240. It may be 30 to 45D, and there is an advantage that long-term heat resistance characteristics and physical property balance are more excellent within this range.

In this description, the D-type shore hardness according to ASTM D2240 is measured according to ASTM D2240 using a shore D hardness tester with a size of 170mmХ10mmХ4mm at 23°C, for example, and a load is applied to the specimen with a conical indenter. It can be measured after maintaining the same load for 15 seconds.

The polyether block amide resin may be a commercially available product as long as it follows the definition of the present invention.

metal stabilizers

The metal-based stabilizer may be included in an amount of 0.4 to 1% by weight, preferably in an amount of 0.4 to 0.8% by weight, more preferably in an amount of 0.4 to 0.6% by weight, based on 100% by weight of the total polyamide resin composition, within this range It has the advantage of being excellent in heat resistance, molding processability, and a balance of physical properties.

The metal-based stabilizer may be, for example, a copper-based stabilizer, a potassium-based stabilizer, or a mixture thereof, and in this case, there is an advantage in that heat resistance and physical property balance are more excellent.

The copper-based stabilizer may be, for example, copper iodide (CuI), and the potassium-based stabilizer may be, for example, at least one selected from the group consisting of potassium iodide (KI) and potassium bromide (KBr), preferably Potassium iodide may be used.

The metal-based stabilizer may include, for example, the copper iodide and potassium iodide in a weight ratio of 1:3 to 1:5, preferably 1:3.5 to 1:4.5, and in this case, there is an advantage in better balance of heat resistance and physical properties. .

polyol

The polyol may be included in an amount of 0 to 2% by weight, preferably 0.5 to 2% by weight, more preferably 1.0 to 1.5% by weight, based on 100% by weight of the total polyamide resin composition, and the tensile strength after heat aging within this range The advantage is that the elongation is excellent and the surface quality is better.

As another example, the polyol may be included in an amount of 0.5 to 2% by weight, preferably 0.8 to 1.8% by weight, more preferably 1.3 to 1.7% by weight, based on 100% by weight of the total polyamide resin composition, within this range It has the advantage of being superior in low-temperature impact strength and long-term heat resistance properties.

Although not specified otherwise, in the present description, "polyol" refers to a polyhydric alcohol compound having two or more hydroxyl groups (-OH) in a molecule.

The polyol may be, for example, at least one selected from the group consisting of pentaerythritol, dipentaerythritol, tripentaerythritol, zitrimethiropropane, D-mannitol, D-sorbitol and xylitol, preferably dipenta It may be erythritol, and in this case, there is an excellent effect of tensile elongation after heat-resistant aging.

The pentaerythritol may be prepared by condensing, for example, one molecule of acetaldehyde and four molecules of formaldehyde using an alkali catalyst such as sodium hydroxide or potassium hydroxide.

The dipentaerythritol and tripentaerythritol can be obtained by, for example, heating monopentaerythritol to a melting point of 260° C. or higher, which is the melting point of monopentaerythritol, and condensing them.

The polyol may have, for example, a weight average molecular weight of 50 g/mol to 10,000 g/mol, preferably 100 g/mol to 7,500 g/mol, more preferably 200 g/mol to 3,000 g/mol, within this range. There is an advantage that long-term heat resistance stability is more excellent in the interior.

additive

The additive may be included in an amount of 1 to 10% by weight, preferably 2 to 8% by weight, more preferably 2 to 6% by weight to 100% by weight of the total polyamide resin composition, and within this range, desired There is an advantage in that the physical property balance with other properties is excellent while sufficiently expressing the effect.

The additive is, for example, at least one selected from the group consisting of a lubricant, a flame retardant, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, a mold release agent, an inorganic filler, a pigment, a metal desulfurizing agent, a coupling agent, and carbon black, preferably may be one or more selected from the group consisting of a flame retardant, a colorant, and a lubricant.

The flame retardant may be, for example, a melamine-based flame retardant, and in this case, there is an advantage of being non-toxic, eco-friendly and low in corrosion.

The melamine-based flame retardant may be, for example, at least one selected from the group consisting of melamine polyphosphate, melamine cyanurate and melamine phosphate, preferably melamine cyanurate, in which case it is environmentally friendly and corrosive while excellent in flame retardancy. This has a low effect.

The flame retardant may be included, for example, in an amount of 0.1 to 3.5% by weight, preferably 0.3 to 3% by weight, based on the total weight of the polyamide resin composition, and has excellent mechanical properties and flame retardancy within this range.

The lubricant may be, for example, at least one selected from the group consisting of ethylene bisstearoamide, stearic acid, alkali metal stearate, and low molecular weight polyethylene.

The alkali metal stearate may be at least one selected from the group consisting of calcium stearate, magnesium stearate, barium stearate, and sodium stearate, preferably sodium stearate, in this case mechanical properties and heat There is an advantage that the original effect of the lubricant is well expressed without degrading the stability.

The lubricant may be included, for example, in an amount of 0.05 to 2 wt%, preferably 0.1 to 1.5 wt%, based on the total weight of the polyamide resin composition, and within this range, the lubricant without degrading the mechanical properties and thermal stability of the resin There is an advantage that the original effect is well expressed.

The colorant may be used, for example, in the form of a master batch (M/B), based on at least one of polyamide 6 and polyolefin, that is, may be prepared with a carrier resin, and in this case, uniformly It is dispersed and has excellent color expression.

The colorant is a colorant in which organic dyes are combined; colorants in which organic dyes and inorganic pigments are combined; or a mixture thereof.

The colorant may include, for example, 35 to 95% by weight of at least one selected from the group consisting of polyamide 6 and polyolefin; and organic dyes, inorganic pigments, or a mixture thereof in an amount of 5 to 35% by weight, in which case dispersibility and color expression are excellent.

The polyamide 6 included in the colorant may be selected within the same range as the above-described polyamide resin.

The polyolefin is, for example, a polymer prepared by polymerization from an olefin having the formula C _n H _2n , specifically polyethylene, polypropylene, polymethylenetene, polybutene-1, polyolefin elastomer, polyisobutylene, and ethylenepropylene rubber. It may be at least one selected from the group consisting of.

The inorganic pigment may preferably be at least one selected from the group consisting of ultramarine-based pigments, titanium dioxide, zinc sulfide, tetracyclic zinc, iron oxide, and carbon black, and in this case, both physical property balance and color expression are excellent. have.

The organic dye is, for example, perinone-based, anthraquinone-based, azo-based, quinolone-based, quinacridone-based, perylene-based, phthalocyanine-based ), and may be at least one selected from the group consisting of methane-based dyes, and in this case, both the physical property balance and color expression have excellent effects.

As a preferred example, the heat stabilizer may be included in an amount of 0.05 to 2% by weight, more preferably 0.1 to 1.5% by weight, based on the total weight of the polyamide resin composition, and within this range, the heat resistance is improved.

The thermal stabilizer may be, for example, at least one selected from the group consisting of a phenol-based thermal stabilizer, a phosphite-based thermal stabilizer, and a thioether-based thermal stabilizer, and preferably a phenol-based thermal stabilizer and a phosphite-based thermal stabilizer.

The phenolic heat stabilizer is, for example, tetrakis methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate methane, 1,3,5-tris-(4-t-butyl- 3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and 1,3,5-tris-(3, It may be at least one member selected from the group consisting of 5-di-t-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)-trione.

The phosphite-based heat stabilizer is, for example, trisnonylphenylphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol depot Spite, or a mixture thereof.

The thioether-based heat stabilizer is, for example, dilauryl thiodipropionate, dimyristyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodipropionate, dimethyl thiodipropionate It may be at least one selected from the group consisting of nate, 2-mercaptobenzimidazole, phenothiazine, octadecyl thioglycolate, butyl thioglycolate, octyl thioglycolate, and thiocresol.

The polyamide resin composition may optionally contain one or more selected from the group consisting of an antistatic agent and a rheology modifier, if necessary, in an amount of 0.01 to 5% by weight, preferably 0.05 to 3% by weight, more than the total weight of the polyamide resin composition. Preferably, it may be further included in an amount of 0.1 to 2% by weight, and within this range, there is an effect that necessary physical properties are well realized without reducing the original properties of the polyamide resin composition of the present invention.

The flow modifier may be preferably 0.05 to 2 wt%, more preferably 0.1 to 1.5 wt%, based on the total weight of the polyamide resin composition, and within this range, processability is improved.

The rheology modifier may be, for example, a dendritic polymer, and the dendritic polymer has a reactive group at each end group, thereby preventing entanglement between polyamide chains and minimizing deterioration of mechanical properties of the polyamide resin composition. .

The dendritic polymer may be, for example, a dendrimer, a hyperbranched polymer, or a mixture thereof.

The dendrimer refers to a polymer in which molecular chains are regularly spread in three dimensions from the center to the outside according to a certain rule.

In addition, the hyperbranched polymer refers to a multi-branched polymer having a branched structure in a repeating unit, and has a chemical structure similar to that of a dendrimer, but has a highly regular branching structure similar to that of a dendrimer or a high degree of control of molecular weight is not made. , that is, there are some branch deletions in the dendrimer structure, branches are formed according to a probability distribution, and have a broad molecular weight distribution.

The dendrimer has a core unit located at the center of the entire spherical structure and a bridge unit, which is a unit structure that is constantly repeated and extended around the core unit, increases in generation (generation), and is located at the end connected to the bridge unit. dendron units (above, it means "terminal functional group").

In the description of the dendrimer in the present description, a generation follows the definition of a generation generally recognized in the art to which the present invention belongs, and specifically refers to a repeating order of a regularly repeating unit structure.

Preferably, the flow modifier may have a number of generations of 1 to 15, preferably 1 to 10, and more preferably 1 to 7, and in this case, the polyamide resin composition has excellent mechanical properties, gloss and appearance properties. have.

For example, in the dendrimer, the terminal functional group may be selected from the group consisting of a hydroxyl group, a sulfohydryl group, an amino group, a carboxy group, an aldehyde group and an epoxy group. Considering mechanical properties, gloss and appearance characteristics, it is preferable that the terminal functional group is an amino group. do.

The dendrimer may be, for example, a compound represented by the following Chemical Formula 1, and in this case, it has excellent mechanical properties such as impact strength, and has an effect of improving fluidity, gloss and appearance characteristics.

[Formula 1]

In Formula 1, R is an alkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, m is an integer of 1 to 5, and n is an integer of 1 to 10.

As a specific example, the dendrimer may be a compound represented by the following Chemical Formula 2 or Chemical Formula 3, and in this case, there is an effect of improving fluidity, gloss and appearance characteristics while having excellent mechanical properties such as impact strength.

[Formula 2]

[Formula 3]

As another example, in the hyperbranched polymer, the terminal functional group may be at least one selected from the group consisting of a hydroxyl group, a sulfohydryl group, an amino group, a carboxy group, an aldehyde group, and an epoxy group. In this case, fluidity, gloss and appearance characteristics are has an improving effect.

The hyperbranched polymer may have a highly branched (branched) structure as a core part and an acid group (eg, carboxylic acid) and an acid-decomposable group (eg, carboxylic acid ester) at the molecular terminus, in which case it appears in a linear polymer There is an effect that the entanglement between molecules is small and the degree of swelling by the solvent is small compared to the molecular structure that bridges the main chain.

Preferably, the hyperbranched polymer may be a hyperbranched polyester in which the terminal functional group is a carboxyl group, and in this case, mechanical properties such as impact strength are excellent while improving fluidity, gloss and appearance properties.

The antistatic agent may include, for example, one or more anionic surfactants, non-ionic surfactants, and the like, but is not limited thereto.

The release agent may be used, for example, at least one selected from glycerin sterate, polyethylene tetra sterate, and the like, but is not limited thereto.

The antioxidant, light stabilizer, and inorganic filler are not particularly limited if they are commonly used in the technical sale to which the present invention belongs.

polyamide resin composition

The polyamide resin composition is preferably aged for 3,000 hours at a temperature of 150° C. in a long-term heat-resistant oven. According to ASTM D638, the tensile elongation measured under the conditions of a specimen thickness of 3.2 mm and a tensile rate of 10 mm/min at 23° C. It may be 8% or more, preferably 8 to 30%, more preferably 10 to 30%, even more preferably 13 to 25%, and there is an advantage in that long-term heat resistance properties and physical property balance are more excellent within this range. .

The polyamide resin composition preferably has a tensile strength of 48 MPa or more, preferably 48 to 80 MPa, more preferably measured under the conditions of a specimen thickness of 3.2 mm and a tensile rate of 10 mm/min at 23° C. according to ASTM D638. may be 50 to 75 MPa, more preferably 55 to 75 MPa, particularly more preferably 60 to 73 MPa, and there is an advantage in that mechanical strength and physical property balance are excellent within this range.

The polyamide resin composition may be prepared at 23° C. according to ASTM D256, for example. The measured impact strength may be 90 J / m or more, preferably 90 to 110 J / m, more preferably 93 to 105 J / m, and within this range, all properties have an excellent balance.

The polyamide resin composition has, for example, a low-temperature impact strength of 50 J/m or more, preferably 50 to 80 J/m, measured at 23° C. according to ASTM D256 after standing in a chamber at -40° C. for 6 hours, More preferably, it may be 52 to 75 J/m, and within this range, the balance of all physical properties has an excellent effect.

Method for producing polyamide resin composition

The polyamide resin composition comprises 70 to 90% by weight of a polyamide resin, 1 to 25% by weight of a polyether-ester copolymer, 0 to 18% by weight of a polyether block amide resin, 0.4 to 1% by weight of a metal-based stabilizer, 0 to 2% by weight of a polyol Aging for 3,000 hours at a temperature of 150° C. in a long-term heat-resistant oven, comprising the step of preparing pellets using an extrusion kneader of 10 to 100 pie size at 200 to 330° C., including 1 to 10 weight percent of additives and 1 to 10 weight percent After long-term thermal aging, the tensile elongation after long-term thermal aging measured under the conditions of 3.2 mm in thickness and 10 mm/min tensile rate at 23 °C according to ASTM D638 was 8% or more, and the specimen thickness was 3.2 mm at 23 °C according to ASTM D638 and It is characterized in that the tensile strength measured under the condition of a tensile rate of 10 mm/min is 48 MPa or more. In this case, while having high mechanical properties and heat resistance, even after exposure to high temperatures for a long time, it has toughness and excellent impact resistance properties even at low temperatures.

In another example, the polyamide resin composition includes 70 to 90% by weight of a polyamide resin, 1 to 25% by weight of a polyether-ester copolymer, 1 to 10% by weight of a polyether block amide resin, 0.4 to 1% by weight of a metal-based stabilizer, It characterized in that it comprises the step of preparing pellets using an extrusion kneader of 10 to 100 pie size at 200 to 330 ° C. including 0.5 to 2 wt % of polyol and 1 to 10 wt % of additives. In this case, while having high mechanical properties and heat resistance, even after exposure to high temperature for a long time, it has toughness and has particularly excellent impact resistance properties even at low temperatures.

The method for producing the polyamide resin composition shares all the technical characteristics of the polyamide resin composition described above. Therefore, a description of the overlapping portion will be omitted.

The step of preparing the pellets using the extrusion kneader may be preferably carried out in a standard of 25 to 75 pie under 200 to 300 ° C, and more preferably to be carried out in a standard of 20 to 80 pie at 220 to 280 ° C. In this range, stable extrusion is possible and the kneading effect is excellent. At this time, the temperature is the temperature set in the cylinder, and pi means the outer diameter (unit: mm).

The extrusion kneader is not particularly limited if it is an extrusion kneader commonly used in the art to which the present invention belongs, and may preferably be a twin-screw extrusion kneader.

molded product

The molded article of the present disclosure contains the polyamide resin composition, and has excellent mechanical properties such as impact resistance, tensile strength, flexural strength, and thermal stability, and has toughness even after being exposed to high temperatures for a long time. can indicate

The molded article may be an automobile part, specifically, a corrugated tube (CORRUGATE TUBE).

The molded article may be molded by, for example, injection, extrusion, or the like, of the polyamide resin composition.

The molded article is manufactured using a generally known method such as injection and extrusion, and may be post-processed by a generally known method such as heat aging. Accordingly, a detailed description of the manufacturing method of the molded article or the post-production processing method will be omitted.

The method for manufacturing the molded article comprises injecting the pellets prepared by the method for preparing the polyamide resin composition at an injection temperature of 200 to 270 °C, an injection pressure of 60 to 100 bar, and a holding pressure of 30 to 65 bar, and , in this case, there is an advantage in that it is possible to easily manufacture an injection-molded article having excellent impact strength and heat resistance.

The injection temperature is preferably 210 to 260 ℃, more preferably 230 to 255 ℃, there is an advantage that can easily manufacture a large injection molded article having high impact strength within this range.

The injection pressure is preferably 70 to 90 bar, more preferably 75 to 85 bar, and there is an advantage in that a large injection molded article having high impact strength can be easily manufactured within this range.

The holding pressure may be preferably 35 to 60 bar, more preferably 40 to 55 bar, and there is an advantage in that a large-area injection-molded article having high impact strength can be easily manufactured within this range.

In describing the polyamide resin composition of the present invention, its manufacturing method and molded article, other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art, and it is not particularly limited. specify

Hereinafter, preferred examples are presented to help the understanding of the present disclosure, but the following examples are merely illustrative of the present disclosure, 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 disclosure, It goes without saying that such variations and modifications fall within the scope of the appended claims.

[Example]

Raw materials used in the following Examples and Comparative Examples are as follows.

* Polyamide resin: Melting temperature Polyamide 6 at 220°C, relative viscosity (96% sulfuric acid solution, 20°C) 3.3

* Polyether-ester copolymer: containing 60% by weight of aromatic dicarboxylic acid, 25% by weight of aliphatic diol and 15% by weight of polyalkylene oxide based on the total weight of aromatic dicarboxylic acid, aliphatic diol and polyalkylene oxide A thermoplastic polyester elastomer resin having a flow index (230℃, 2.16kg) of 25 g/10min and a shore hardness of 30 D.

* Polyether block amide resin A: Type D Shore hardness (according to ASTM D2240, 15 sec delay shore) 35D, melting temperature 160℃, relative viscosity (96% sulfuric acid solution, 20℃) 1.43 polyether blockamide (PEBA)

* Ethylene-octene rubber: Ethylene-octene rubber with flow index (according to ASTM D 1238, 190°C and 2.16 kg load) 1.6 g/10min, melting temperature 50°C, density (according to ASTM D 792) 0.87 g/cm ³

* Metal-based stabilizer A: potassium iodide (KI)

* Metal-based stabilizer B: copper iodide (CuI)

* Polyol: dipentaerythritol

* Additives: Melamine Cyanurate (Flame Retardant) and Sodium Stearate (Lubricant)

Examples 1 to 4 and Comparative Examples 1 to 8

Each component was mixed using a super mixer at the content shown in Table 1 below, and the extrusion temperature was 250° C. and the screw rotation speed was 600 rpm with a twin-screw extruder (screw diameter 26 mm, L/D = 40). It was extruded under extrusion conditions to prepare pellets.

After drying the prepared thermoplastic resin composition in the form of pellets at 100° C. for 4 hours or more, injection molding was performed in an injection machine under the conditions of an injection temperature of 240° C., a mold temperature of 60° C., and an injection speed of 30 mm/sec. to 26° C.) for at least 48 hours, and then the physical properties were measured.

[Test Example]

The physical properties of the specimens prepared in Examples and Comparative Examples were measured in the following manner, and the results are shown in Table 1 below.

* Room temperature impact strength (J/m): In accordance with ASTM D256 standard, the notch impact strength was measured under 23℃ temperature condition.

* Low-temperature impact strength (J/m): The prepared specimen was left in an in-chamber at -40°C for 6 hours, and then, according to ASTM D256, the notch impact strength was measured under a temperature condition of 23°C.

* Long-term heat-resistant tensile elongation (%): After long-term thermal aging by leaving the prepared specimen at a temperature of 150 ° C in a gear oven for 3,000 hours, in accordance with ASTM D638 at 23 ° C. temperature, 3.2 mm specimen thickness and Tensile elongation was measured under 10 mm/min tensile rate conditions.

* Tensile strength (MPa): According to ASTM D638, the tensile strength was measured under the conditions of 23°C temperature, 3.2 mm specimen thickness, and 10 mm/min tensile rate.

* Thermal deformation temperature (℃): The thermal deformation temperature was measured under the conditions of a 6.4 mm specimen thickness, a 1.8 MPa load, and a temperature increase rate of 120 °C/Hr according to ASTM D648.

Category (wt%) Example comparative example One 2 3 4 One 2 3 4 5 6 7 8 PA6 84.1 82.6 77.6 72 94.6 94.1 93.1 84.6 92.6 83.1 77.6 67.6 PTEE 10 10 10 5.6 10 10 10 0 PEBA A 5 15 25 EOR-MAHL 5 KI 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 CuI 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 DPE 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 additive 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 impact strength
(23℃, J/m) 94 93 100 107 53 52 52 95 53 93 102 115 impact strength
(-40℃, J/m) 51 52 68 73 28 27 28 53 29 53 68 80 elongation
(150℃,
3,000h, %) 11 15 20 15 <1 <1 <1 <1 <2 <3 7 16 The tensile strength
(MPa) 66 67 64 54 83 83 82 67 83 66 58 45 heat deflection temperature
(℃) 168 168 163 150 182 181 182 167 181 167 157 139

As shown in Table 1, in the case of Examples 1 to 4 prepared according to the present invention, the impact strength at room temperature and low temperature is 93 to 107 J/m and 51 to 73 J/m, respectively, and the tensile strength is 54 to 67 MPa and the long-term heat-resistant tensile elongation measured after long-term thermal aging at 150° C. for 3,000 hours is 11 to 20%, and the thermal deformation temperature is 150 to 168° C., compared to Comparative Examples 1 to 8 outside the scope of the present invention. And it was confirmed that mechanical rigidity, heat resistance, and long-term heat resistance were all excellent at low temperatures. In particular, in the case of Examples 1 to 4, compared to Comparative Examples 1 to 8, the tensile strength, thermal deformation temperature, and long-term heat resistance tensile elongation were all excellent, and it was confirmed that mechanical rigidity, heat resistance and long-term heat resistance were simultaneously secured.

Claims (16)

70 to 90% by weight of polyamide resin;
1 to 25% by weight of a polyether-ester copolymer;
0 to 18% by weight of polyether block amide resin;
0.4 to 1% by weight of a metal-based stabilizer; and
0 to 2% by weight of polyol; and
Additives 1 to 10% by weight; including,
After aging for 3,000 hours at a temperature of 150°C in a long-term heat-resistant oven, the tensile elongation after long-term thermal aging measured under the conditions of a specimen thickness of 3.2 mm and a tensile rate of 10 mm/min at 23°C according to ASTM D638 is 8% or more, Characterized in that the tensile strength measured under the conditions of a specimen thickness of 3.2 mm and a tensile rate of 10 mm/min at 23° C. according to ASTM D638 is 48 MPa or more
A polyamide resin composition.
The method of claim 1,
The polyamide resin is a homopolyamide resin, a copolyamide resin, or a mixture thereof, characterized in that
A polyamide resin composition.
The method of claim 1,
The polyamide resin is characterized in that the melting temperature (Tm) is 200 to 250 ℃
A polyamide resin composition.
The method of claim 1,
The polyamide resin has a relative viscosity (96% sulfuric acid solution, 20° C.) 2.5 to 3.5
A polyamide resin composition.
The method of claim 1,
The polyether-ester copolymer is Flow index (230℃, load 2.16kg) 20 to 50 g/10min characterized
A polyamide resin composition.
The method of claim 1,
The polyether-ester copolymer has a melting temperature of 150 to 210 °C. characterized
A polyamide resin composition.
The method of claim 1,
The polyether-ester copolymer is characterized in that the D-type shore hardness measured according to ASTM D2240 is 25D to 40D
A polyamide resin composition.
The method of claim 1,
The polyether block amide resin is characterized in that the relative viscosity (96% sulfuric acid solution, 20 ℃) is 2.0 or less
A polyamide resin composition.
The method of claim 1,
The polyether block amide resin is characterized in that the melting temperature is 150 to 220 ℃
A polyamide resin composition.
The method of claim 1,
The polyol is at least one selected from the group consisting of pentaerythritol, dipentaerythritol, tripentaerythritol, zitrimethiropropane, D-mannitol, D-sorbitol and xylitol.
A polyamide resin composition.
According to claim 1,
The metal-based stabilizer is characterized in that copper iodide, potassium iodide, or a mixture thereof
A polyamide resin composition.
According to claim 1,
The metal-based stabilizer comprises copper iodide and potassium iodide in a weight ratio of 1:3 to 1:5
A polyamide resin composition.
The method of claim 1,
The additive is one selected from the group consisting of at least one selected from the group consisting of lubricants, flame retardants, colorants, antioxidants, heat stabilizers, light stabilizers, mold release agents, inorganic fillers, pigments, metal inactivators, coupling agents, and carbon black characterized by more than
A polyamide resin composition.
The method of claim 1,
The polyamide resin composition is aged for 3,000 hours at 150 ℃, characterized in that the tensile elongation measured under the condition of 5 mm / min according to ASTM D638 is 10% or more
A polyamide resin composition.
polyamide resin 70 to 90% by weight, 1 to 25% by weight of polyether-ester copolymer, 0 to 18% by weight of polyether block amide resin, metallic stabilizer Including 0.4 to 1% by weight, 0 to 2% by weight of polyol, and 1 to 10% by weight of additives, and kneading and extruding at 200 to 330°C using an extrusion kneader having a size of 10 to 100 pie;
After aging for 3,000 hours at a temperature of 150°C in a long-term heat-resistant oven, the tensile elongation after long-term thermal aging measured under the conditions of a specimen thickness of 3.2 mm and a tensile rate of 10 mm/min at 23°C according to ASTM D638 is 8% or more, Characterized in that the tensile strength measured under the conditions of a specimen thickness of 3.2 mm and a tensile rate of 10 mm/min at 23° C. according to ASTM D638 is 48 MPa or more
A method for producing a polyamide resin composition.
15. A polyamide resin composition comprising the polyamide resin composition of any one of claims 1 to 14.
molded article.