KR102162482B1 - Environment friendly polyamide resin composition and molded product manufactured the same - Google Patents

Abstract

The present invention relates to an eco-friendly polyamide resin composition and a molded article manufactured using the same. In one embodiment, the polyamide resin composition comprises (A) 20 to 60% by weight of a biopolyamide resin; (B) 20 to 60% by weight of a polyamide resin; (C) 1 to 19% by weight of a modified polyolefin copolymer; (D) 3-25% by weight of 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

Eco-friendly polyamide resin composition and molded product manufactured using it {ENVIRONMENT FRIENDLY POLYAMIDE RESIN COMPOSITION AND MOLDED PRODUCT MANUFACTURED THE SAME}

The present invention relates to an eco-friendly polyamide resin composition and a molded article manufactured using the same.

Plastics used as interior or exterior materials for automobiles are required to have high impact resistance, heat resistance and excellent rigidity. Meanwhile, among the mechanical properties, the impact resistance and the flexural modulus are in a trade-off relationship. That is, when the impact resistance is improved, the flexural modulus is reduced, and the development of a material to satisfy all of these mechanical properties is required. In addition, as plastic materials mainly use raw materials derived from petroleum, the amount of CO ₂ generated during plastic material production increases, causing environmental pollution. Is increasing.

Accordingly, there have been attempts to apply biomass plastic polylactic acid or composite resins using cellulose fibers as automobile interior materials, but the polylactic acid is difficult to apply to automotive interior materials due to low impact strength and heat resistance, and the cellulose fiber In the case of the composite resin using, there is a problem that the processability or appearance quality is not good.

Accordingly, there is a need for development of an eco-friendly material that can be applied to interior materials or exterior materials for automobiles, has excellent impact resistance properties, flexural modulus, and excellent heat resistance.

Japanese Patent Application Publication No. 2009-079215

An object of the present invention is to provide an eco-friendly polyamide resin composition having excellent eco-friendliness and excellent impact resistance and flexural modulus at the same time.

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

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

Another object of the present invention is to provide a method for manufacturing a molded article for automobile interiors using the eco-friendly polyamide resin composition.

Another object of the present invention is to provide a molded article manufactured using the eco-friendly polyamide resin composition.

One aspect of the present invention relates to an eco-friendly polyamide resin composition. In one embodiment, the eco-friendly polyamide resin composition comprises 20 to 60% by weight of the (A) biopolyamide resin; (B) 20 to 60% by weight of a polyamide resin; (C) 1 to 19% by weight of a modified polyolefin copolymer; (D) 3-25% by weight of 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 biopolyamide resin (A) has a biocarbon 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, and a melting temperature of 180 to It may include a 220 ℃ polyamide 1010 resin.

In one embodiment, the polyamide resin (B) may include 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-carbon number 3 or more alpha-olefin copolymer grafted with maleic anhydride.

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

In one embodiment, the inorganic filler (D) may include 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 higher, and a specific gravity of 1 to 1.7.

In one embodiment, the heat-resistant stabilizer (F) may include a diphenyl amine-based heat-resistant 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 further include more than 0 and 10% by weight or less based on the total weight of the eco-friendly polyamide resin composition.

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

In one embodiment, the biopolyamide resin (A), polyamide resin (B), and modified polyolefin copolymer (C) may be included 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 of manufacturing a molded article using an eco-friendly polyamide resin composition. In one embodiment, the method for manufacturing the molded article is (A) 20 to 60% by weight of a biopolyamide resin; (B) 20 to 60% by weight of a polyamide resin; (C) 1 to 19% by weight of a modified polyolefin copolymer; (D) 3-25% by weight of 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; and extruding after melt-kneading an eco-friendly polyamide resin composition containing; includes.

Another aspect of the present invention relates to a molded article manufactured using the eco-friendly polyamide resin composition.

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

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

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 molded article may have a color difference difference (ΔE*) of 2 or less before/after standing in an oven at 80° C. for 300 hours.

In one embodiment, the molded article may have a color difference difference (ΔE*) of 2 or less before/after exposure to ultraviolet rays according to SAE J 2412.

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

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

The eco-friendly polyamide resin composition of the present invention and the molded article manufactured using the same contain more than 25% by weight of bio-based carbon, and are certified as biomass plastic, so that it has excellent eco-friendliness, and has excellent impact resistance and flexural modulus. At the same time, it is excellent, and it can be excellent in heat resistance, light resistance, and economy.

In describing the present invention, if it is determined that a detailed description of a related known technology or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted.

In addition, terms to be described later are terms defined in consideration of functions in the present invention, and since these may vary according to the intention or custom of users or operators, the definitions should be made based on the contents throughout the present specification describing the present invention.

Eco-friendly polyamide resin composition

One aspect of the present invention relates to an eco-friendly polyamide resin composition. In one embodiment, the eco-friendly polyamide resin composition comprises 20 to 60% by weight of the (A) biopolyamide resin; (B) 20 to 60% by weight of a polyamide resin; (C) 1 to 19% by weight of a modified polyolefin copolymer; (D) 3-25% by weight of 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, the constituent components of the eco-friendly polyamide resin composition will be described in detail.

(A) Biopolyamide resin

The biopolyamide resin (A) is an eco-friendly resin capable of reducing the amount of carbon dioxide, which is the main cause of global warming, emitted during the plastic manufacturing process. The biopolyamide resin (A) may be derived from vegetable resources. For example, it is a non-food resource and is derived from a material extracted from castor, which is easy to cultivate, and is a resin that is satisfactory in terms of use of non-food resources and environment-friendly. Examples are polyamide 11 or polyamide 1010.

In one embodiment, the bio-polyamide resin (A) is contained in an amount of 20 to 60% by weight based on the total weight of the eco-friendly polyamide resin composition. When included in the above range, it has excellent impact strength and heat deflection temperature, and its low moisture absorption rate prevents deformation during molding, has excellent dimensional stability, and can be certified as internationally recognized biomass plastic. Content is satisfied. When the biopolyamide resin is included in an amount of less than 20% by weight, the content for certification as a biomass plastic is not satisfied, it is difficult to secure physical properties, and when it is included in an amount exceeding 60% by weight, the impact strength and the heat deflection temperature may decrease. have. For example, it may be included in 25 to 50% by weight.

In one embodiment, the biopolyamide resin (A) may have a biocarbon content of 60% by weight or more. For example, it may be 60 to 100% by weight. In one embodiment, the biopolyamide 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. In the conditions of the biocarbon content, relative viscosity, glass transition temperature, and melting temperature, the present invention may have excellent eco-friendliness, impact resistance, heat resistance and moldability.

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

For example, the biopolyamide resin (A) has a biocarbon 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, and a melting temperature of 180 to 220 It may include a polyamide 1010 resin in °C. Under the conditions of the relative viscosity, glass transition temperature, and melting temperature of the above conditions, the environmentally friendly polyamide resin composition may have excellent impact resistance, environmental friendliness, stiffness and heat resistance.

In one embodiment, the biopolyamide 1010 resin may be prepared by condensation polymerization of sebacic acid prepared from castor oil and 1,10-decamethylene diamine amination of the sebacic acid.

(B) polyamide resin

The polyamide resin (B) contains an amide group in the polymer main chain, and may be polymerized using amino acids, lactams or diamines, and dicarboxylic acids 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, the strength, heat resistance, processability and chemical resistance of the present invention may be improved.

In one embodiment, the polyamide resin (B) may include polyamide 6 resin. The polyamide 6 resin contains a C6 organic chain represented by -(CH ₂ ) ₅ CO- in one repeating unit. For example, polyamide 6 resin can be prepared through ring-opening polymerization, which is a reaction in which a ring-shaped compound of ε-caprolactam is polymerized while ring-opening.

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

In another embodiment, the polyamide resin (B) may include 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 rigidity of the present invention are excellent, and the fluidity is excellent, so that the appearance quality of the injection-molded product is excellent.

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

(C) modified polyolefin copolymer

The modified polyolefin copolymer (C) may include an ethylene-carbon number 3 or more alpha (α) olefin copolymer grafted with maleic anhydride. The ethylene-carbon number 3 or more alpha-olefin copolymer may include an ethylene-propylene copolymer (EPM), an ethylene-butene copolymer (EBM), or an ethylene-octene copolymer (EOM). When the modified polyolefin copolymer (C) is applied, the compatibility between the biopolyamide resin (A) and the polyamide resin (B) is improved, the impact strength is excellent, and die swell is reduced during extrusion processing or It has an effect of excellent processability by improving the melt tension.

In one embodiment, the modified polyolefin copolymer (C) may have a melt index of 0.5 to 3 g/10 min (ASTM D1238, 190° C., based on 2.16 kg measurement). In one embodiment, the modified polyolefin copolymer may be grafted with 0.5 to 5% by weight of maleic anhydride based on 100% by weight of an ethylene-carbon number 3 or more alpha-olefin copolymer. Within this range, the compatibility between the bio-polyamide resin and 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°C, based on 2.16 kg measurement), and an ethylene-octene copolymer grafted with maleic anhydride 0.5 to 5% by weight. May include coalescence.

The modified polyolefin copolymer (C) is contained in an amount of 1 to 19% by weight based on the total weight of the eco-friendly polyamide resin composition. When included in the above content, compatibility between the bio-polyamide resin and the polyamide resin, appearance quality, and physical property balance within this range are excellent. When the modified polyolefin copolymer (C) is included in an amount of less than 1% by weight, it is difficult to secure compatibility and physical properties, and when it is included in an amount exceeding 19% by weight, impact strength may decrease. For example, 3 to 17% by weight may be included. For another example, 6 to 15% by weight may be included.

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

(D) inorganic filler

The inorganic filler (D) may include at least one of talc, olastonite (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 μm. In the present specification, the particle size can be measured by a conventional method using an electron microscope. As another example, in the particle size of 1 to 10 μm, the weight of talc particles passing through 1340 to 2000 mesh may be 95% by weight or more.

In one embodiment, the inorganic filler (D) is included in an amount of 3 to 25% by weight based on the total weight of the eco-friendly polyamide resin composition. While maintaining the appearance quality within this range, there is an effect of excellent heat resistance. When the inorganic filler is included in an amount of less than 3% by weight, heat resistance is deteriorated, and when it is included in an amount exceeding 25% by weight, appearance quality and physical properties may be deteriorated. For example, it may be included in 5 to 20% by weight.

(E) Weathering stabilizator

In one embodiment, the weathering stabilizer (E) may include one or more of benzotriazole-based, benzophenone-based, and benzotriazine-based weathering stabilizers. For example, the weight average molecular weight is 300~1000g/mol, the melting temperature is 90℃ or more, for example, 120℃ or more, for example, 90~150℃, another example, 120℃~150℃, and the specific gravity is It may contain 1 to 1.7 benzotriazole-based weathering stabilizers. When the weathering stabilizer is included, there is an excellent effect in the balance of light resistance and physical properties of the present invention.

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

In one embodiment, the weathering stabilizer is contained in an amount of 0.1 to 5% by weight based on the total weight of the eco-friendly polyamide resin composition. While maintaining appearance quality within the above range, there is an effect of excellent processability. When the weathering stabilizer is included in an amount of less than 0.1% by weight, weather resistance and appearance quality are deteriorated, and when it is included in an amount exceeding 5% by weight, processability and physical properties may be deteriorated. For example, it may be contained in 0.2 to 3% by weight.

(F) Heat-resistant stabilizer

The heat-resistant stabilizer (F) may include at least one of phosphorus-based, phenol-based, sulfur-based, and amine-based heat-resistant stabilizers. When the heat-resistant stabilizer (F) is included, it has excellent long-term physical property retention by improving stability against heat, and is excellent in preventing discoloration of molded products that may occur during processing and molding.

In one embodiment, the heat-resistant stabilizer (F) may include a diphenyl amine-based heat-resistant stabilizer. For example, a diphenyl amine having a weight average molecular weight of 300 g/mol or more, for example 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 It may contain a heat-resistant stabilizer. In this case, it has advantages such as decomposition by heat and oxidation or low volatility at high temperatures, and an effect of preventing discoloration due to heat may be excellent.

In one embodiment, the diphenyl amine-based heat-resistant stabilizer may include 4,4'-bis(α,α-dimethylbenzyl)diphenylamine.

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

(G) ionomer copolymer

In one embodiment of the present invention, the eco-friendly polyamide resin composition may further include 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 include 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 may be, for example, an alkene or 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)acrylic acid ester having 1 to 10 carbon atoms in the alkyl group.

The metal ions may be included in an amount replacing 10% or more of the total number of carboxyl groups included in the ionomer copolymer. For example, it may be included in an amount replacing 10% to 100%.

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

In one embodiment, the ionomer copolymer (G) may be included in an amount greater than 0 and 10% by weight or less based on the total weight of the eco-friendly polyamide resin composition. It serves to reinforce the impact strength in the above range, and has excellent effects not only in impact strength but also in elongation, flexural modulus, and appearance quality. For example, 1 to 10% by weight, may be included. For another example, it may be included in 1 to 5% by weight.

In one embodiment, the ionomer copolymer (G) may have a melt index of 0.5 to 3 g/10min, for example, 0.7 to 2.5 g/10min, based on ASTM D1238 (190°C, load 2.16kg measurement). It has excellent workability within the melting index range, so that the appearance quality is excellent. For example, the ionomer copolymer (G) may include an ethylene methacrylic acid copolymer neutralized with metal ions, 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 eco-friendly polyamide resin composition further comprises one or more of a colorant, a release agent, a pigment, a dye, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a flame retardant, a friction/abrasion resistance, and a coupling agent as an additive. I can.

In one embodiment, the eco-friendly polyamide resin composition may have a bio-carbon (C14) content of 25% by weight or more measured according to ASTM D6866. While being certified as biomass plastic within the above range, there is an effect of excellent physical property balance. For example, it may be 25 to 60% by weight.

Manufacturing method of molded products using eco-friendly polyamide resin composition

Another aspect of the present invention relates to a method of manufacturing a molded article using an eco-friendly polyamide resin composition. In one embodiment, the method of manufacturing the molded article is (A) 20 to 60% by weight of a biopolyamide resin; (B) 20 to 60% by weight of a polyamide resin; (C) 1 to 19% by weight of a modified polyolefin copolymer; (D) 3-25% by weight of 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; and extruding after melt-kneading an eco-friendly polyamide resin composition containing; includes.

The melt-kneading may be performed at 240 to 280°C, for example, 240 to 260°C. When melt-kneading in the above range, a molded article having excellent impact strength and low temperature impact strength and excellent flexural modulus can be manufactured.

Molded product manufactured using eco-friendly polyamide resin composition

Another aspect of the present invention relates to a molded article manufactured using the eco-friendly polyamide resin composition.

In one embodiment, the molded article may have a bio-carbon (C14) content of 25% by weight or more measured according to ASTM D6866. While being certified as biomass plastic within the above range, there is an effect of excellent physical property balance. For example, it may be 25 to 60% by weight.

In one embodiment, the molded article may have a room temperature impact strength of 15 to 50 kgf·cm/cm, and a low temperature impact strength at -10° C. of 3 to 20 kgf·cm/cm according to ASTM D256. Within the above range, the impact strength and 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. For another example, it may be 20 to 35 kgf·cm/cm. For example, the low-temperature impact strength may be 3 to 20 kgf·cm/cm. For another example, it may be 4 to 18 kgf·cm/cm. For another example, it may be 5 to 16 kgf·cm/cm.

In one embodiment, the molded article may have a tensile strength of 210 to 600 kgf/cm ² and a tensile elongation of 35 to 150% according to ASTM D638. Within the above range, there is an effect of excellent mechanical property and property balance. 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%, for example 40 to 120%, and for another example, 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 the above range of flexural strength, mechanical properties and physical property balance are excellent, and in the above range of flexural modulus, excellent flexural modulus and impact strength and low-temperature impact strength are excellent. For example, the flexural strength of the molded article may be 400 to 650 kgf/cm ² . For another example, it 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 . For 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) of 120°C or higher according to ASTM D648. Within this range, there is an effect of excellent heat resistance and physical property balance. For example, it may be 125°C or higher. For another example, it may be 125 ~ 170 ℃.

In one embodiment, the molded article may have a color difference difference (ΔE*) of 2 or less before/after standing in an oven at 80°C for 300 hours. Within the above range, there is an effect of excellent appearance quality and physical property balance.

In one embodiment, the molded article may have a color difference difference (ΔE*) of 2 or less before/after exposure to ultraviolet rays according to SAE J 2412. Within this range, the appearance quality and physical property balance are excellent.

In one embodiment, the molded article may be a molded article for automobile interior materials. In one embodiment, the molded article may be a glove box, a cowl side cover, or a rear cover for an audio video navigation system (AVN).

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is presented as a preferred example of the present invention and cannot be construed as limiting the present invention in any sense.

Example And Comparative example

Components used in the following Examples and Comparative Examples are as follows.

(A) Biopolyamide resin: The biocarbon content measured according to ASTM D6866 is 100% by weight, the relative viscosity (20°C, 1g of the resin component in 100ml of 96% sulfuric acid) is 1.9 to 2.3, and the glass transition temperature: 55 ℃ and melting temperature: 200 ℃ biopolyamide 1010 resin was used.

(B) Polyamide resin: Polyamide 6 resin with a relative viscosity (20°C, 1 g of resin component in 100 ml of 96% sulfuric acid) is 2.3 to 2.6 dl/g, glass transition temperature: 55°C and melting temperature: 220°C I did.

(C) 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 in which glycidyl methacrylate was grafted to an ethylene-octene copolymer at a grafting ratio 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 according to ASTM D1238 (190° C., 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 μm was used.

(E) weather stabilizer

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

(E-2): A weight average molecular weight: 481 g/mol of a hindered amine-based weathering stabilizer (HALS-based), bis(2,2,6,6-tetramethyl-4-piperidyl-sebaciete (Bis( 2,2,6,6-tertamethyl-4-piperidyl)sebaceate), a weathering stabilizer was used.

(F) Heat-resistant stabilizer: Weight average molecular weight: 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (4,4'-Bis(α,α-dimathylbenzyl)diphenylamine) of 406 g/mol A stabilizer was 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., load 2.16 kg measurement standard) was used.

Example One

Mixing with a mixer by applying the ingredients and contents shown in Table 1 below, melt-kneading using a twin-screw extruder at 250°C, and extruding to prepare an eco-friendly polyamide resin composition pellet, which was again prepared using an injection molding machine I did.

Example 2~7

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

Comparative example 1~9

A specimen was prepared in the same manner as in Example 1, except for applying the components and contents shown in Table 2 below.

[Test Example]

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

* Impact strength (kgf·cm/cm): Notched Izod impact strength was measured according to ASTM D256, the thickness of the specimen was 6.4 mm, and the specimen was notched at room temperature (23° C.).

* Low-temperature impact strength (kgf·cm/cm): It was measured according to ASTM D256, the thickness of the specimen was 6.4mm, and it was measured at low temperature (-10 ℃) after notched in the specimen.

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

* Flexural strength (kgf/cm ² ): It was measured according to ASTM D790, the thickness of the specimen was 6.4mm, and the measurement speed was 30mm/min.

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

* Heat deflection temperature (℃): It was measured according to ASTM D648, the thickness of the specimen was 6.4mm, and it was measured under 4.6kgf stress.

* Light resistance: In accordance with the regulations of SAE J 2412, after irradiation under 700 KJ/m2 (340 nm) with Xenon Arc, the color difference value before/after irradiation is measured (L*a*b*) using a spectrophotometer. The difference ΔE* was calculated.

* Heat aging resistance: After the specimen was left in an oven set at 80 °C for 300 hours, the color difference value before and after (L*a*b*) was measured using a spectrophotometer, and the difference, △E*, was calculated. .

As shown in Tables 3 and 4, Examples 1 to 7 according to the present invention have excellent impact strength, particularly low-temperature impact strength, and flexural modulus, which are difficult to be compatible with each other, as well as heat deflection temperature, tensile strength, and tensile elongation. It was confirmed that this was excellent, and in particular, it was excellent in light resistance and heat aging resistance, so that the appearance had a beautiful effect 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 very poor impact strength and low temperature impact strength, and did not contain a modified olefin copolymer or contained a small amount of 0.5% by weight. In Comparative Examples 6 and 7, it was found that mechanical properties such as impact strength, low temperature impact strength, tensile strength and tensile elongation were severely deteriorated.

In addition, Comparative Example 8 containing a modified olefin copolymer at 20% by weight showed a particularly great decrease in tensile strength, flexural strength, flexural modulus, and heat deflection temperature, and Comparative Example 3 containing an inorganic filler at 30% by weight was impacted. It was found that the strength, low-temperature impact strength, and tensile elongation were lowered.

In addition, in the case of Comparative Examples 1 to 3 and 6 to 9 in which the heat-resistant stabilizer and the weathering stabilizer were not included, it was confirmed that light resistance and heat aging resistance were deteriorated, and a comparative example including a HALS-based weathering stabilizer rather than a benzotriazole-based weathering stabilizer 9 shows that the heat aging resistance is deteriorated.

Simple modifications or changes of the present invention can be easily implemented by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (20)

(A) 20 to 60% by weight of a biopolyamide resin;
(B) 20 to 60% by weight of a polyamide resin;
(C) 1 to 19% by weight of a modified polyolefin copolymer;
(D) 3-25% by weight of 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; Including,
The modified polyolefin copolymer (C) includes an ethylene-carbon number 3 or more alpha-olefin copolymer grafted with maleic anhydride,
The weathering stabilizer (E) is an eco-friendly polyamide resin composition comprising a benzotriazole-based weathering stabilizer having a weight average molecular weight of 300 to 1000 g/mol, a melting temperature of 120 to 150°C, and a specific gravity of 1 to 1.7 .
The method of claim 1, wherein the biopolyamide resin (A) has a biocarbon 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, and a melting temperature Eco-friendly polyamide resin composition comprising a polyamide 1010 resin of 180 ~ 220 ℃.
The method of claim 1, wherein the polyamide resin (B) contains 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. Eco-friendly polyamide resin composition, characterized in that.
delete The eco-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° C., 2.16 kg measurement standard).
The eco-friendly polyamide resin composition according to claim 1, wherein the inorganic filler (D) contains at least one of talc, olastonite, kaolin, barium sulfate, potassium carbonate, and silica.
delete The method of claim 1, wherein the heat-resistant stabilizer (F) comprises a diphenyl amine-based heat-resistant 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. Eco-friendly polyamide resin composition.
The eco-friendly polyamide resin composition of claim 1, further comprising more than 0 and 10% by weight or less of (G) ionomer copolymer based on the total weight of the eco-friendly polyamide resin composition.
The method of claim 9, wherein the ionomer copolymer (G) comprises an ethylene methacrylic acid copolymer neutralized with a metal ion,
The ionomer copolymer is an eco-friendly polyamide resin composition, characterized in that the melt index is 0.5 ~ 3g / 10min (ASTM D1238, 190 ℃, 2.16kg measurement standard).
The eco-friendly polyamide of claim 1, wherein the biopolyamide resin (A), polyamide resin (B), and modified polyolefin copolymer (C) are included in a weight ratio of 1:0.5 to 2.5:0.1 to 1 Resin composition.
(A) 20 to 60% by weight of a biopolyamide resin; (B) 20 to 60% by weight of a polyamide resin; (C) 1 to 19% by weight of a modified polyolefin copolymer; (D) 3-25% by weight of 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; and extruding an eco-friendly polyamide resin composition comprising melt-kneading and then extruding; and
The modified polyolefin copolymer (C) includes an ethylene-carbon number 3 or more alpha-olefin copolymer grafted with maleic anhydride,
The weathering stabilizer (E) has a weight average molecular weight of 300 to 1000 g/mol, a melting temperature of 120° C. or more, and a benzotriazole-based weathering stabilizer having a specific gravity of 1 to 1.7.
A molded article comprising the eco-friendly polyamide resin composition of any one of claims 1 to 3, 5, 6, and 8 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 according to ASTM D256, and an impact strength at -10°C of 3 to 20 kgf·cm/cm. .
The molded article of claim 13, wherein the molded article has a tensile strength of 210 to 600 kgf/cm ² and a tensile elongation of 35 to 150% according to ASTM D638.
The molded article according to claim 13, wherein the molded article has 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.
The molded article according to claim 13, wherein the molded article has a color difference difference (ΔE*) of 2 or less before and after standing in an oven at 80° C. for 300 hours.
14. The molded article according to claim 13, wherein the molded article has a color difference value difference (ΔE*) before/after exposure to ultraviolet rays according to the provisions of SAE J 2412 of 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.
The molded article according to claim 13, wherein the molded article is a glove box, a cowl side cover, or a rear cover for an audio video navigation system (AVN).