KR20180056873A - Environment friendly polyamide resin composition and molded product manufactured the same - Google Patents

Abstract

The present invention relates to an environmentally friendly polyamide resin composition and a molded article produced using the same. In one embodiment, the polyamide resin composition comprises (A) 20 to 60% by weight of a bio polyamide resin; (B) 20 to 60% by weight of a polyamide resin; (C) 1 to 19% by weight of a modified polyolefin copolymer; (D) 3 to 25% by weight of an inorganic filler; (E) 0.1 to 5% by weight of a weather stabilizer; And (F) 0.1 to 5% by weight of a heat-resistant stabilizer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an environmentally friendly polyamide resin composition,

The present invention relates to an environmentally friendly polyamide resin composition and a molded article produced using the same.

Plastics used as automobile interior or exterior materials are required to have high impact resistance, heat resistance and excellent rigidity. On the other hand, the impact resistance and the flexural modulus of the mechanical properties are in a trade-off relationship. That is, when the impact resistance property is improved, the flexural modulus is lowered, and it is required to develop a material satisfying all of these mechanical properties. In addition, since plastic materials mainly use raw materials derived from petroleum, there is a problem that the generation of CO ₂ is increased due to the increase of CO ₂ production in the production of plastic materials, and as a result of increasing interest in the environment, demands for environmentally friendly materials .

Accordingly, there has been an attempt to apply composite resins using polylactic acid or cellulose fiber as a biomass plastic as an automobile interior material. However, the polylactic acid has a low impact strength and heat resistance and is difficult to apply to automobile interior materials. There is a problem that the processability or the appearance quality is poor.

Accordingly, development of an environmentally friendly material which is applicable to an automotive interior or exterior material, has excellent impact resistance and flexural modulus at the same time, and is excellent in heat resistance is required.

Japanese Laid-Open Patent No. 2009-079215

An object of the present invention is to provide an environmentally friendly polyamide resin composition which is excellent in environmental friendliness, and which is excellent in both impact resistance and flexural modulus.

Another object of the present invention is to provide an environmentally friendly polyamide resin composition excellent in heat resistance and light resistance.

Another object of the present invention is to provide an eco-friendly polyamide resin composition having excellent economy.

It is still another object of the present invention to provide a method of manufacturing a molded article for an automotive interior decoration using the environmentally friendly polyamide resin composition.

It is still another object of the present invention to provide a molded article produced using the environmentally friendly polyamide resin composition.

One aspect of the present invention relates to an environmentally friendly polyamide resin composition. In one embodiment, the environmentally friendly polyamide resin composition comprises (A) 20 to 60% by weight of a bio polyamide resin; (B) 20 to 60% by weight of a polyamide resin; (C) 1 to 19% by weight of a modified polyolefin copolymer; (D) 3 to 25% by weight of an inorganic filler; (E) 0.1 to 5% by weight of a weather stabilizer; And (F) 0.1 to 5% by weight of a heat-resistant stabilizer.

In one embodiment, the bio-polyamide resin (A) has a biocarbon content of 60 wt% or more, a relative viscosity of 1.9 to 2.3, a glass transition temperature (Tg) of 50 to 60 ° C, Lt; RTI ID = 0.0 > 220 C. < / RTI >

In one embodiment, the polyamide resin (B) may comprise a polyamide 6 resin having a relative viscosity of 2.3 to 2.6, a glass transition temperature (Tg) of 50 to 60 ° C, and a melting temperature of 210 to 230 ° C have.

In one embodiment, the modified polyolefin copolymer (C) may include an ethylene-alpha-olefin copolymer having three or more ethylene-maleic anhydride grafted.

In one embodiment, the modified polyolefin copolymer (C) may have a melt index of 0.5 to 3 g / 10 min (ASTM D1238, 190 캜, 2.16 kg measurement standard).

In one embodiment, the inorganic filler (D) may comprise at least one of talc, olastonite, kaolin, barium sulfate, potassium carbonate and silica.

In one embodiment, the weathering stabilizer (E) may include a benzotriazole-based weathering stabilizer having a weight average molecular weight of 300 to 1000 g / mol, a melting temperature of 120 ° C or more, and a specific gravity of 1 to 1.7.

In one embodiment, the heat-resistant stabilizer (F) may include a diphenylamine-based heat stabilizer having a weight average molecular weight of 300 g / mol or more, a melting temperature of 90 ° C or more, and a specific gravity of 1 to 1.5.

In one embodiment, the (G) ionomer copolymer may be added in an amount of 0 to 10% by weight based on the total weight of the environmentally friendly polyamide resin composition.

In one embodiment, the ionomer copolymer (G) comprises an ethylene methacrylic acid copolymer neutralized with a metal ion, and the ionomer copolymer has a melt index of 0.5 to 3 g / 10 min (ASTM D1238, 190 ° C, 2.16 kg Standard).

In one embodiment, the bipolyamide resin (A), the polyamide resin (B) and the modified polyolefin copolymer (C) may be contained in a weight ratio of 1: 0.5 to 2.5: 0.1 to 1.

Another aspect of the present invention relates to a method for producing a molded article using an environmentally friendly polyamide resin composition. In one embodiment, the molded article manufacturing method comprises (A) 20 to 60% by weight of a bio polyamide resin; (B) 20 to 60% by weight of a polyamide resin; (C) 1 to 19% by weight of a modified polyolefin copolymer; (D) 3 to 25% by weight of an inorganic filler; (E) 0.1 to 5% by weight of a weather stabilizer; And (F) 0.1 to 5% by weight of a heat stabilizer; and melt-kneading and extruding the eco-friendly polyamide resin composition.

Another aspect of the present invention relates to a molded article produced using the environmentally friendly polyamide resin composition.

In one embodiment, the molded article may have an impact strength of 15 to 50 kgf · cm / cm at room temperature according to ASTM D256 and an impact strength of 3 to 20 kgf · cm / cm at -10 ° C.

In one embodiment, the molded article may have a tensile strength in accordance with ASTM D638 of 210 to 600 kgf / cm ² and a tensile elongation of 35 to 150%.

In one embodiment, the molded article may have a flexural strength of 350 to 700 kgf / cm ² and a flexural modulus of 20,000 to 30,000 kgf / cm ^{2 according} to ASTM D790.

In one embodiment, the color difference value difference (DELTA E *) before / after being left in an oven at 80 DEG C for 300 hours may be 2 or less.

In one embodiment, the color difference value difference (DELTA E *) before / after ultraviolet exposure according to the definition of SAE J 2412 may be 2 or less.

In one embodiment, the molded article may have a heat resistance (HDT) according to ASTM D648 of 125 ° C to 170 ° C.

In one embodiment, the molded article may be a glove box, a cowal side cover, or a rear cover for an audio video navigation system.

The eco-friendly polyamide resin composition of the present invention and the molded article produced using the same have a bio-based carbon content of not less than 25% by weight and are certified as biomass plastic, thus being excellent in environmental friendliness and having excellent impact resistance and flexural modulus At the same time, excellent in heat resistance, light resistance and economy.

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.

Environmentally friendly polyamide resin composition

One aspect of the present invention relates to an environmentally friendly polyamide resin composition. In one embodiment, the environmentally friendly polyamide resin composition comprises (A) 20 to 60% by weight of a bio polyamide resin; (B) 20 to 60% by weight of a polyamide resin; (C) 1 to 19% by weight of a modified polyolefin copolymer; (D) 3 to 25% by weight of an inorganic filler; (E) 0.1 to 5% by weight of a weather stabilizer; And (F) 0.1 to 5% by weight of a heat-resistant stabilizer.

Hereinafter, constituent components of the environmentally friendly polyamide resin composition will be described in detail.

(A) a biopolyamide resin

The bipolyamide resin (A) is an eco-friendly resin capable of reducing the amount of carbon dioxide, which is a main cause of global warming, in the process of manufacturing plastics. The bio polyamide resin (A) may be derived from vegetable sources. For example, it is a non-food resource, derived from materials extracted from easy-to-cultivate castor, and satisfying non-food resource utilization and environmental friendliness. One example is polyamide 11 or polyamide 1010.

In one embodiment, the bipolyamide resin (A) is contained in an amount of 20 to 60 wt% based on the total weight of the environmentally friendly polyamide resin composition. When the content is in the above range, it is possible to obtain an excellent biomass plastic which is excellent in dimensional stability, which is excellent in impact strength and heat distortion temperature, The content is satisfied. When the amount of the bio-polyamide resin is less than 20% by weight, the content to be certified as biomass plastic is not satisfied and the physical properties are difficult to secure. When the amount exceeds 60% by weight, impact strength and heat distortion temperature have. For example, 25 to 50% by weight.

In one embodiment, the bio-polyamide resin (A) may have a bio-carbon content of 60 wt% or more. For example, 60 to 100% by weight. In one embodiment, the bipolyamide resin (A) may have a relative viscosity of 1.9 to 2.3, a glass transition temperature of 50 to 60 ° C, and a melting temperature of 180 to 220 ° C. The eco-friendliness, impact resistance, heat resistance and moldability of the present invention can be excellent under the conditions of the above-mentioned bio-carbon content, relative viscosity, glass transition temperature and melting temperature.

In the present invention, the bio-polyamide resin (A) has a bio-carbon content measured according to ASTM D6866, and the relative viscosity may be a result of measuring 1 g of the resin component in 100 ml of 96% sulfuric acid at 20 ° C .

For example, the bio-polyamide resin (A) has a bio-carbon content of 60% by weight or more, a relative viscosity of 1.9 to 2.3, a glass transition temperature (Tg) of 50 to 60 ° C, Lt; 0 > C. The environmentally friendly polyamide resin composition can be excellent in impact resistance, environmental friendliness, rigidity and heat resistance under the above-mentioned conditions of relative viscosity, glass transition temperature and melting temperature.

In one embodiment, the bio polyamide 1010 resin can be prepared by condensation polymerization of sebacic acid prepared from castor oil and 1,10-decamethylene diamine obtained by aminating sebacic acid.

(B) a polyamide resin

The polyamide resin (B) contains an amide group in the main chain of the polymer, and may be polymerized with an amino acid, a lactam or a diamine and a dicarboxylic acid as constituent components. In one embodiment, the polyamide resin (B) includes polyamide 6, polyamide 66, polyamide 12, polyamide 610, and polyamide 612. When the polyamide resin is applied, strength, heat resistance, processability, chemical resistance, etc. of the present invention can be improved.

In one embodiment, the polyamide resin (B) may include a polyamide 6 resin. The polyamide 6 resin includes a C6 organic chain represented by - (CH ₂ ) ₅ CO- in one repeating unit. For example, the polyamide 6 resin can be produced by ring-opening polymerization, which is a reaction of? -Caprolactam in which a ring-shaped compound is ring-opened and polymerized.

In one embodiment, the polyamide 6 resin may have a relative viscosity (based on a measurement of 1 g of polymer in 100 ml of 96% sulfuric acid at 20 캜) of 2.2 to 4.0 dl / g. Within the above range, the impact strength and stiffness of the present invention are excellent, and the fluidity is excellent, so that the appearance quality of the injection molded article is excellent.

In another embodiment, the polyamide resin (B) may comprise a polyamide 6 resin having a relative viscosity of 2.3 to 2.6, a glass transition temperature (Tg) of 50 to 60 ° C, and a melting temperature of 210 to 230 ° C have. Within the above range, the impact strength and stiffness of the present invention are excellent, and the fluidity is excellent, so that the appearance quality of the injection molded article is excellent.

The polyamide resin (B) is contained in an amount of 20 to 60% by weight based on the total weight of the environmentally friendly polyamide resin composition. When the content is included, the heat-deflection temperature, flexural modulus and tensile strength of the environmentally friendly polyamide resin composition may be excellent. When the amount of the polyamide resin (B) is less than 20% by weight, it is difficult to secure physical properties. When the amount of the polyamide resin (B) is more than 60% by weight, the flexural modulus and tensile strength may be lowered. For example, 25 to 55% by weight.

(C) a modified polyolefin copolymer

The modified polyolefin copolymer (C) may include an ethylene-alpha-olefin copolymer having three or more ethylene (alpha) olefins grafted with maleic anhydride. The ethylene-alpha-olefin copolymer having three or more carbon atoms may include an ethylene-propylene copolymer (EPM), an ethylene-butene copolymer (EBM), or an ethylene-octene copolymer (EOM). (A) and the polyamide resin (B) are improved when the modified polyolefin copolymer (C) is applied, the impact strength is excellent, the die swell is reduced The melt tension is improved and the processability is excellent.

In one embodiment, the modified polyolefin copolymer (C) may have a melt index of 0.5 to 3 g / 10 min (ASTM D1238, 190 캜, 2.16 kg measurement standard). In one embodiment, the modified polyolefin copolymer may be obtained by grafting 0.5 to 5% by weight of maleic anhydride with respect to 100% by weight of an ethylene-alpha-olefin copolymer having three or more carbon atoms. Within this range, the compatibility of the polyamide resin with the polyamide resin is improved and the impact strength is excellent.

For example, the modified polyolefin copolymer (C) has a melt index of 0.5 to 3 g / 10 min (ASTM D1238, 190 DEG C, based on a measurement of 2.16 kg) and an ethylene-octene copolymer having a grafted maleic anhydride of 0.5 to 5 wt% ≪ / RTI >

The modified polyolefin copolymer (C) is contained in an amount of 1 to 19% by weight based on the total weight of the environmentally friendly polyamide resin composition. When the above content is included, there is an effect of excellent compatibility with the polyamide resin and the polyamide resin, balance in appearance quality and physical properties within this range. When the modified polyolefin copolymer (C) is contained in an amount of less than 1% by weight, it is difficult to ensure compatibility and physical properties. When the modified polyolefin copolymer (C) is contained in an amount exceeding 19% by weight, the impact strength may be lowered. For example, 3 to 17% by weight. For example, 6 to 15% by weight.

In one embodiment, the bipolyamide resin (A), the polyamide resin (B) and the modified polyolefin copolymer (C) may be contained in a weight ratio of 1: 0.5 to 2.5: 0.1 to 1. When included in the above weight range, the compatibility and compatibility of the polyamide resin (A) and the polyamide resin (B) are excellent, and the heat resistance, flexural modulus and impact strength of the present invention can be excellent.

(D) Inorganic filler

The inorganic filler (D) may include at least one of talc, olustonite (wollastonite), kaolin, barium sulfate, potassium carbonate and silica. For example, the inorganic filler may include talc having a specific gravity of 1 to 3.5 and a particle size of 1 to 10 mu m. In the present specification, the particle size can be measured by an ordinary method using an electron microscope. As another example, the weight of the talc particles having passed through 1340 to 2000 mesh of the particle size of 1 to 10 탆 may be 95% by weight or more.

In one embodiment, the inorganic filler (D) is contained in an amount of 3 to 25% by weight based on the total weight of the environmentally friendly polyamide resin composition. Within this range, the appearance quality is maintained and the heat resistance is excellent. When the inorganic filler is contained in an amount of less than 3% by weight, the heat resistance is lowered. When the inorganic filler is contained in an amount exceeding 25% by weight, appearance quality and physical properties may be deteriorated. For example, 5 to 20% by weight.

(E) Weather  stabilizator

In one embodiment, the weathering stabilizer (E) may include at least one of benzotriazole-based, benzophenone-based, and benzotriazine-based weathering stabilizers. For example, a weight average molecular weight of 300 to 1000 g / mol, a melting temperature of 90 占 폚 or higher, for example, 120 占 폚 or higher, another example of 90 to 150 占 폚, and another example of 120 占 폚 to 150 占 폚, 1 to 1.7 benzotriazole-based weathering stabilizers. When the above-mentioned weather resistance stabilizer is included, there is an effect of excellent balance of light resistance and physical properties of the present invention.

In one embodiment, the benzotriazole-based weather stabilizer may include 2-benzotriazole-4,6-bis (1-methyl-1-phenylethyl).

In one embodiment, the weathering stabilizer is included in an amount of 0.1 to 5 wt% based on the total weight of the environmentally friendly polyamide resin composition. Within the above range, the appearance quality is maintained and the processability is excellent. When the weather stabilizer is contained in an amount of less than 0.1% by weight, weatherability and appearance quality are deteriorated, and when it exceeds 5% by weight, processability and physical properties may be deteriorated. For example, 0.2 to 3% by weight.

(F) Heat stabilizer

The heat-resistant stabilizer (F) may include at least one of phosphorus-based, phenol-based, sulfur-based, and amine-based heat stabilizers. When the heat-resistant stabilizer (F) is included, the stability against heat is improved, so that the long-term retention of physical properties is excellent and the effect of preventing discoloration of the molded article, which may occur during processing and molding, is excellent.

In one embodiment, the heat stabilizer (F) may include a diphenylamine heat stabilizer. For example, a diphenylamine-based resin having a weight average molecular weight of 300 g / mol or more, such as 300 to 700 g / mol, a melting temperature of 90 ° C or more, for example, 90 to 120 ° C, and a specific gravity of 1 to 1.5 A heat stabilizer may be included. In this case, it has advantages such as decomposition by heat and oxidation or low volatility at a high temperature, and it can be excellent in the effect of preventing discoloration by heat.

In one embodiment, the diphenylamine thermostable stabilizer may include 4,4'-bis (α, α-dimethylbenzyl) diphenylamine.

In one embodiment, the heat stabilizer (F) is contained in an amount of 0.1 to 5% by weight based on the total weight of the environmentally friendly polyamide resin composition. There is an effect that discoloration and deterioration of physical properties are prevented even when the molded article is exposed to high temperature for a long time within the above range. For example, 0.1 to 3% by weight.

(G) ionomer copolymer

In one embodiment of the present invention, the environmentally friendly polyamide resin composition may further comprise an ionomer copolymer.

In one embodiment, the ionomer copolymer (G) may include at least one of an olefin-unsaturated carboxylic acid copolymer and an olefin-unsaturated carboxylic acid ester copolymer in which some or all of the carboxyl groups are neutralized by metal ions.

The ionomer copolymer (G) may comprise 50 to 80% by weight of an olefin and 20 to 50% by weight of an unsaturated carboxylic acid, an ester thereof, or a mixture thereof. The olefin is, for example, an alkene or a diene having 1 to 10 carbon atoms, and may be ethylene, butadiene, and the like.

The unsaturated carboxylic acid may be, for example, (meth) acrylic acid, and the unsaturated carboxylic acid ester may be, for example, an alkyl (meth) acrylate having 1 to 10 carbon atoms in the alkyl group.

The metal ion may include, for example, an amount of substituting at least 10% of the total number of carboxyl groups contained in the ionomer copolymer. For example, 10% to 100%.

The metal ion may be derived, for example, from a metal hydroxide. The metal ion is Zn ² In one example ^{+, Na +, Mg 2 +} , Ba 2 +, Ca 2 +, Li +, K +, Sn 2 +, and may be more than one kinds of the Al ^{+ 3.}

In one embodiment, the ionomer copolymer (G) may be contained in an amount of 0 to 10% by weight based on the total weight of the environmentally friendly polyamide resin composition. In this range, it has an effect of reinforcing the impact strength and has an effect of not only impact strength but also elongation, flexural modulus and appearance quality. For example, 1 to 10% by weight. For example, 1 to 5% by weight.

In one embodiment, the ionomer copolymer (G) may have a melt index of from 0.5 to 3 g / 10 min, for example, from 0.7 to 2.5 g / 10 min based on ASTM D1238 (190 ° C, measurement under a load of 2.16 kg). There is an effect of excellent workability and excellent appearance quality within the range of the melt index. For example, the ionomer copolymer (G) includes an ethylene methacrylic acid copolymer neutralized with a metal ion and may have a melt index of 0.5 to 3 g / 10 min (ASTM D1238, 190 ° C, 2.16 kg measurement standard).

In one embodiment, the environmentally friendly polyamide resin composition further comprises at least one of a colorant, a releasing agent, a pigment, a dye, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a flame retardant agent, a friction / wear- .

In one embodiment, the environmentally friendly polyamide resin composition may have a biocarbon (C14) content of 25% by weight or more as measured according to ASTM D6866. Within the above range, it is certified as biomass plastic and has an excellent balance of physical properties. For example, from 25 to 60% by weight.

Method for manufacturing molded article using environmentally friendly polyamide resin composition

Another aspect of the present invention relates to a method for producing a molded article using an environmentally friendly polyamide resin composition. In one embodiment, the method for producing the molded article comprises (A) 20 to 60% by weight of a bio polyamide resin; (B) 20 to 60% by weight of a polyamide resin; (C) 1 to 19% by weight of a modified polyolefin copolymer; (D) 3 to 25% by weight of an inorganic filler; (E) 0.1 to 5% by weight of a weather stabilizer; And (F) 0.1 to 5% by weight of a heat stabilizer; and melt-kneading and extruding the eco-friendly polyamide resin composition.

The melt kneading can be carried out at 240 to 280 ° C, for example, at 240 to 260 ° C. In the melt-kneading in the above-mentioned range, a molded article having excellent impact strength and low temperature impact strength and excellent flexural modulus can be produced.

A molded article produced by using an environmentally friendly polyamide resin composition

Another aspect of the present invention relates to a molded article produced using the environmentally friendly polyamide resin composition.

In one embodiment, the molded article may have a biocarbon (C14) content of at least 25% by weight measured according to ASTM D6866. Within the above range, it is certified as biomass plastic and has an excellent balance of physical properties. For example, from 25 to 60% by weight.

In one embodiment, the molded article may have an impact strength at room temperature of 15 to 50 kgf · cm / cm 2 according to ASTM D256 and a low temperature impact strength of 3 to 20 kgf · cm / cm at -10 ° C. Within the above range, the impact strength and the low temperature impact strength are excellent, and the flexural modulus is also excellent. For example, the impact strength at room temperature may be 17 to 40 kgf · cm / cm. Other examples may be 20 to 35 kgf cm / cm. For example, the low temperature impact strength may be 3 to 20 kgf · cm / cm. Other examples may be 4 to 18 kgf cm / cm. Another example may be 5 to 16 kgf cm / cm.

In one embodiment, the molded article may have a tensile strength in accordance with ASTM D638 of 210 to 600 kgf / cm ² and a tensile elongation of 35 to 150%. Within this range, there is an effect of excellent balance of mechanical properties and physical properties. In one embodiment, the tensile strength of the molded article may be 280 to 500 kgf / cm ² , for example 300 to 450 kgf / cm ² . For example, the tensile elongation of the molded article may be 35 to 150%, such as 40 to 120%, and other examples may be 45 to 100%.

In one embodiment, the molded article may have a flexural strength of 350 to 700 kgf / cm ² and a flexural modulus of 20,000 to 30,000 kgf / cm ^{2 according} to ASTM D790. In this range of flexural strength, excellent balance of mechanical properties and physical properties are exhibited, and excellent flexural modulus at a flexural modulus in the above range is obtained, and impact strength and low temperature impact strength are excellent. For example, the bending strength of the molded article may be 400 to 650 kgf / cm ² . Another example may be 450 to 600 kgf / cm ² . For example, the flexural modulus of the molded article may be 21,000 to 27,000 kgf / cm ² . In another example, the flexural modulus of the molded article may be 22,000 to 25,000 kgf / cm < ² >.

In one embodiment, the molded article may have a heat resistance (HDT) according to ASTM D648 of at least 120 ° C. Within this range, there is an effect of excellent balance of heat resistance and physical properties. For example, 125 ° C or higher. For another example, it may be 125-170 < 0 > C.

In one embodiment, the color difference value difference (DELTA E *) before / after being left in an oven at 80 DEG C for 300 hours may be 2 or less. Within this range, there is an effect of excellent appearance quality and balance of physical properties.

In one embodiment, the color difference value difference (DELTA E *) before / after ultraviolet exposure according to the definition of SAE J 2412 may be 2 or less. Within this range, there is an effect of excellent balance of appearance quality and physical properties.

In one embodiment, the molded article may be a molded article for an automotive interior material. In one embodiment, the molded article may be a glove box, a cowal side cover, or a rear cover for an audio video navigation system.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Example  And Comparative Example

The ingredients used in the following Examples and Comparative Examples are as follows.

(A) BioPolyamide resin: 100% by weight of the bio-polyamide resin measured in accordance with ASTM D6866, relative viscosity (1 g of resin component in 100 ml of 96% sulfuric acid at 20 캜) of 1.9 to 2.3, glass transition temperature of 55 Lt; 0 > C and a melting temperature of 200 [deg.] C.

(B) Polyamide resin: A polyamide 6 resin having a relative viscosity of 2.3 to 2.6 dl / g and a glass transition temperature of 55 캜 and a melting temperature of 220 캜 was used at 20 캜, 1 g of a resin component in 100 ml of 96% sulfuric acid) Respectively.

(C) a modified polyolefin copolymer

(C-1): A modified polyolefin polymer in which maleic anhydride was grafted to an ethylene-octene copolymer at a grafting rate of 0.5 to 1% by weight was used.

(C-2): A modified polyolefin polymer obtained by grafting glycidyl methacrylate to an ethylene-octene copolymer at a grafting rate of 5 to 10% by weight was used.

(C-3): An ethylene-octene copolymer having a melt index of 0.5 to 5 g / 10 min based on ASTM D1238 (190 캜, load 2.16 kg) was used.

(D) Inorganic filler: Talc having a specific gravity of 2.7 and a particle size of 1 to 10 mu m was used.

(E) Weather stabilizer

(E-1): 2-benzotriazole-4,6-bis (1-methyl) -benzonitrile having a weight average molecular weight of 448 g / mol -1-phenylethyl) weathering stabilizer was used.

(2,2,6,6-tetramethyl-4-piperidyl) sebacate (E-2) was obtained in a hindered amine-type weathering stabilizer (HALS system) having a weight average molecular weight of 481 g / mol. 2,2,6,6-tertamethyl-4-piperidyl sebaceate) was used.

(F) Heat-resistant stabilizer: A heat-resistant stabilizer: 4,4'-bis (?,? Stabilizers were used.

(G) Ionomer Copolymer: A zinc metal ion neutralized ethylene methacrylic acid copolymer having a melt index of 0.5 to 1 g / 10 min according to ASTM D1238 (190 ° C, measurement under a load of 2.16 kg) was used.

Example  One

The components and the contents as shown in the following Table 1 were applied, mixed by a mixer, melted and kneaded at 250 ° C using a twin-screw extruder, and extruded to prepare pellets of an environmentally friendly polyamide resin composition. The pellets were again manufactured using an injection molding machine Respectively.

Example  2 to 7

Specimens were prepared in the same manner as in Example 1, except that the components and the contents shown in Table 1 were applied.

Comparative Example  1 to 9

Specimens were prepared in the same manner as in Example 1 except that the ingredients and the contents shown in Table 2 were applied.

[Test Example]

The properties of the molded body specimens produced in Examples 1 to 7 and Comparative Examples 1 to 9 were measured by the following methods, and the results are shown in Tables 3 and 4.

Impact strength (kgf · cm / cm): Notch Izod impact strength was measured in accordance with ASTM D256. Specimen thickness was 6.4 mm and measured at room temperature (23 ° C) after notching the specimen.

* Low-temperature impact strength (kgf · cm / cm): measured according to ASTM D256, specimen thickness is 6.4 mm, measured at low temperature (-10 ° C) after notching the specimen.

Tensile strength (kgf / cm ² ) and elongation (%): Measured according to ASTM D638, specimen thickness was 3.2 mm, and measurement speed was 50 mm / min.

Flexural Strength (kgf / cm ² ): Measured according to ASTM D790, specimen thickness was 6.4 mm, and measurement speed was 30 mm / min.

Flexural modulus (kg / cm ² ): A specimen thickness of 6.4 mm was measured at a measurement speed of 30 mm / min in accordance with ASTM D790 standard.

Heat deformation temperature (캜): Measured according to ASTM D648, specimen thickness is 6.4 mm and measured under 4.6 kgf stress.

* Light fastness: According to SAE J 2412, color difference values before and after irradiation were measured (L * a * b *) using a spectrophotometer after irradiation at 700 KJ / m2 (340 nm) The difference DELTA E * was obtained.

* Heat aging resistance: The sample was allowed to stand in an oven set at 80 ° C for 300 hours, and the color difference value before and after being left standing (L * a * b *) was measured using a spectrophotometer to determine ΔE * .

As shown in Tables 3 and 4, Examples 1 to 7 according to the present invention have excellent impact strengths, particularly low-temperature impact strengths, which are incompatible with each other, and have excellent flexural modulus, heat distortion temperature, tensile strength and tensile elongation And particularly excellent in light resistance and heat aging resistance, and it was confirmed that there was an effect of beautiful appearance for a long time.

On the other hand, Comparative Examples 4 and 5 including other types of copolymers other than the modified olefin copolymer according to the present invention had poor impact strength and low temperature impact strength, and did not contain a modified olefin copolymer or contained a small amount of 0.5 wt% , The mechanical properties such as impact strength, low temperature impact strength, tensile strength and tensile elongation were remarkably lowered.

In Comparative Example 8 containing 20% by weight of the modified olefin copolymer, the tensile strength, the flexural strength, the flexural modulus and the heat distortion temperature were particularly significantly lowered. In Comparative Example 3 containing 30% by weight of the inorganic filler, Strength, low-temperature impact strength, and tensile elongation were decreased.

In addition, in Comparative Examples 1 to 3 and 6 to 9 in which the heat-resistant stabilizer and the weather-resistant stabilizer were not included, it was confirmed that the light resistance and the heat aging resistance deteriorated. In comparison with the benzotriazole-based weather- 9 showed a decrease in heat aging resistance.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (20)

(A) 20 to 60% by weight of a bio polyamide resin;
(B) 20 to 60% by weight of a polyamide resin;
(C) 1 to 19% by weight of a modified polyolefin copolymer;
(D) 3 to 25% by weight of an inorganic filler;
(E) 0.1 to 5% by weight of a weather stabilizer; And
(F) 0.1 to 5% by weight of a heat-resistant stabilizer.
The polyimide resin composition according to claim 1, wherein the bio polyamide resin (A) has a bio-carbon content of 60 wt% or more, a relative viscosity of 1.9 to 2.3, a glass transition temperature (Tg) of 50 to 60 ° C, And a polyamide 1010 resin having a melting point of 180 to 220 ° C.
The polyamide resin composition according to claim 1, wherein the polyamide resin (B) comprises a polyamide 6 resin having a relative viscosity of 2.3 to 2.6, a glass transition temperature (Tg) of 50 to 60 ° C and a melting temperature of 210 to 230 ° C By weight based on the total weight of the polyamide resin composition.
The eco-friendly polyamide resin composition according to claim 1, wherein the modified polyolefin copolymer (C) comprises an ethylene-alpha-olefin copolymer having three or more ethylene-maleic anhydride grafted.
The environmentally friendly polyamide resin composition according to claim 1, wherein the modified polyolefin copolymer (C) has a melt index of 0.5 to 3 g / 10 min (ASTM D1238, 190 DEG C, 2.16 kg measurement standard).
The eco-friendly polyamide resin composition according to claim 1, wherein the inorganic filler (D) comprises at least one of talc, olustonite, kaolin, barium sulfate, potassium carbonate and silica.
The weather resistant stabilizer (E) according to claim 1, wherein the weather stabilizer (E) comprises a benzotriazole type weathering stabilizer having a weight average molecular weight of 300 to 1000 g / mol, a melting temperature of 120 ° C or more, and a specific gravity of 1 to 1.7 (EN) An environment - friendly polyamide resin composition.
The heat stabilizer (F) according to claim 1, wherein the heat stabilizer (F) comprises a diphenylamine heat stabilizer having a weight average molecular weight of 300 g / mol or more, a melting temperature of 90 ° C or more, and a specific gravity of 1 to 1.5 (EN) An environment - friendly polyamide resin composition.
The eco-friendly polyamide resin composition according to claim 1, further comprising (G) an ionomer copolymer in an amount of 0 to 10% by weight based on the total weight of the environmentally friendly polyamide resin composition.
The method according to claim 9, wherein the ionomer copolymer (G) comprises an ethylene methacrylic acid copolymer neutralized with a metal ion,
Wherein the ionomer copolymer has a melt index of 0.5 to 3 g / 10 min (ASTM D1238, 190 DEG C, 2.16 kg measurement standard).
The eco-friendly polyamide resin composition according to claim 1, wherein the bipolyamide resin (A), the polyamide resin (B) and the modified polyolefin copolymer (C) are contained in a weight ratio of 1: 0.5 to 2.5: Resin composition.
(A) 20 to 60% by weight of a bio polyamide resin; (B) 20 to 60% by weight of a polyamide resin; (C) 1 to 19% by weight of a modified polyolefin copolymer; (D) 3 to 25% by weight of an inorganic filler; (E) 0.1 to 5% by weight of a weather stabilizer; And (F) 0.1 to 5% by weight of a heat stabilizer; and melt-kneading and extruding the eco-friendly polyamide resin composition.
11. A molded article comprising the environmentally-friendly polyamide resin composition according to any one of claims 1 to 11.
The molded article according to claim 13, wherein the molded article has an impact strength at room temperature of 15 to 50 kgf · cm / cm 2 according to ASTM D256 and an impact strength at 3 to 20 kgf · cm / cm at -10 ° C. .
The molded article according to claim 13, wherein the molded article has a tensile strength of 210 to 600 kgf / cm ² according to ASTM D638 and a tensile elongation of 35 to 150%.
The method of claim 13, wherein the molded article is a bending strength of 350 ~ 700 kgf / cm ² according to ASTM D790, the flexural modulus is 20,000 to the molded article, characterized in that 30,000 kgf / cm ^2.
14. The molded article according to claim 13, wherein the color difference value difference (DELTA E *) before / after being left in an oven at 80 DEG C for 300 hours is 2 or less.
14. The molded article according to claim 13, wherein the molded article has a color difference value difference (DELTA E *) before / after ultraviolet exposure based on the definition of SAE J 2412 is 2 or less.
The molded article according to claim 13, wherein the molded article has a heat resistance (HDT) of 125 ° C to 170 ° C according to ASTM D648.
14. The molded article of claim 13, wherein the molded article is a glove box, a cowal side cover, or a rear cover for an audio video navigation system.