Environment-friendly polyamide resin composition and article comprising same

Abstract

An environment-friendly polyamide resin composition of the present invention comprises: about 100 parts by weight of a base material; about 5-15 parts by weight of a poly(ether ester amide) block copolymer; and about 0.1-1 part by weight of talc, the base material comprising: about 5-25 wt% of a recycled polyamide resin; about 1-30 wt% of an aliphatic polyamide resin excluding polyamide 6 and polyamide 6.6; about 1-20 wt% of an aromatic polyamide resin; and about 40-80 wt% of a glass fiber. The environment-friendly polyamide resin composition is excellent in terms of eco-friendliness, adhesion to and disassemblability from a polyurethane adhesive, impact resistance, heat resistance, rigidity, and the like.

Description

Eco-friendly polyamide resin composition and molded article containing the same

[0001] The present invention relates to an environmentally friendly polyamide resin composition and a molded article comprising the same. More specifically, the present invention relates to an environmentally friendly polyamide resin composition having excellent environmental friendliness, adhesion to polyurethane adhesives, disintegration properties, impact resistance, heat resistance, rigidity, and the like, and a molded article comprising the same.

[0002]

[0003] Polyamide resins boast excellent processability and impact resistance, making them useful for housings of various products and for automotive interior and exterior materials. Furthermore, polyamide resins can be blended with inorganic fillers like glass fiber to further enhance mechanical properties like rigidity and heat resistance. In line with the trend toward thinner, lighter materials, their application in electronic device housings is increasing.

[0004] Meanwhile, in the assembly process for electrical / electronic products, automobiles, and other components, the bonding process is performed using adhesive tapes or glues. Compared to adhesive tapes, polyurethane adhesives, such as PUR (polyurethane reactive), offer a simpler process, increasing productivity, and also exhibit superior adhesive properties. They are particularly effective when the bonding area is small.

[0005] However, polyurethane adhesives have very poor adhesion to polyamide resins, so their use is limited.

[0006] Furthermore, with the gradual increase in plastic waste and environmental issues such as carbon reduction, interest in the eco-friendly product market that recycles plastic waste is growing. Many companies are developing technological processes to recycle waste plastic products into raw materials through methods such as pyrolysis. However, the heat energy consumed during this process is leading to increased energy investment in recycling systems. Consequently, there is a growing demand for methods that minimize this energy loss and maximize waste reuse, such as shredding waste and using it as raw material for resin processing.

[0007] However, in the case of resin, which is usually waste, there is a problem that mechanical properties and heat resistance deteriorate due to aging of the resin.

[0008] Therefore, there is a need to develop an environmentally friendly polyamide resin composition that is made by recycling plastic waste and has excellent adhesion and decomposition properties with polyurethane adhesives, impact resistance, heat resistance, and rigidity.

[0009] The background technology of the present invention is disclosed in U.S. Patent Publication No. US 2014 / 0179850, etc.

[0010]

[0011] The purpose of the present invention is to provide an environmentally friendly polyamide resin composition having excellent environmental friendliness, adhesion to polyurethane adhesives, disintegration properties, impact resistance, heat resistance, rigidity, etc.

[0012] Another object of the present invention is to provide a molded product formed from the above-mentioned eco-friendly polyamide resin composition.

[0013] The above and other objects of the present invention can all be achieved by the present invention described below.

[0014]

[0015] 1. One aspect of the present invention relates to an environmentally friendly polyamide resin composition. The environmentally friendly polyamide resin composition comprises: about 100 parts by weight of a base material comprising about 5 to about 25 wt% of a recycled polyamide resin, about 1 to about 30 wt% of an aliphatic polyamide resin excluding polyamide 6 and polyamide 6.6, about 1 to about 20 wt% of an aromatic polyamide resin, and about 40 to about 80 wt% of glass fiber; about 5 to about 15 parts by weight of a polyetheresteramide block copolymer; and about 0.1 to about 1 part by weight of talc; wherein the polyetheresteramide block copolymer is characterized in that it is a block copolymer of a reaction mixture comprising an aminocarboxylic acid having 6 or more carbon atoms, a lactam or diamine-dicarboxylate, polytetramethylene glycol, and a dicarboxylic acid having 4 to 20 carbon atoms.

[0016] 2. In the above 1 specific example, the recycled polyamide resin may include at least one of polyamide 6 derived from marine inflow waste and polyamide 6.6 derived from marine inflow waste.

[0017] 3. In the above 1 or 2 specific examples, the aliphatic polyamide resin may include at least one of polyamide 11, polyamide 12, polyamide 4.6, polyamide 6.10, polyamide 6.12, polyamide 10.10, and polyamide 10.12.

[0018] 4. In the above 1 to 3 specific examples, the aromatic polyamide resin may be a polymer of an aliphatic dicarboxylic acid and an aromatic diamine.

[0019] 5. In the above 1 to 4 specific examples, the glass fiber has a rectangular or oval cross-section, an aspect ratio of the cross-section (major axis of the cross-section / minor axis of the cross-section) of about 1.5 to about 10, and a minor axis of about 2 to about 10 ㎛.

[0020] 6. In the above 1 to 5 specific examples, the weight ratio of the glass fiber and the polyether esteramide block copolymer may be about 1:0.05 to about 1:0.3.

[0021] 7. In the above 1 to 6 specific examples, the weight ratio of the polyether esteramide block copolymer and the talc may be about 1:0.005 to about 1:0.08.

[0022] 8. In the above 1 to 7 specific examples, the eco-friendly polyamide resin composition is applied with a polyurethane-based adhesive (HB Fuller, EH9777BS) of 0.018 g at a thickness of 1 mm at 110°C on a specimen measuring 50 mm × 50 mm × 4 mm, and glass measuring 25 mm × 25 mm × 0.7 mm is attached on the applied adhesive, and after curing for 72 hours under temperature conditions of 25°C and humidity conditions of 50%, a weight weighing 10 to 500 g is attached to the top of a drop test evaluation device and a specimen is fixed to the bottom, and then the weight is dropped from a height of 50 cm. The adhesive strength (potential energy) when the specimen is detached from the glass may be about 700 to about 990 mJ.

[0023] 9. In the above 1 to 8 specific examples, the eco-friendly polyamide resin composition may be formed by applying 0.018 g of a polyurethane-based adhesive (HB Fuller, EH9777BS) at 110°C to a thickness of 1 mm on a specimen measuring 50 mm × 50 mm × 4 mm, attaching glass measuring 25 mm × 25 mm × 0.7 mm on the applied adhesive, curing the adhesive for 72 hours under temperature conditions of 25°C and humidity conditions of 50%, heating the adhesive at 75°C for 15 minutes, and then using a UTM (Universal testing machine) device, fixing the specimen with the glass attached to the bottom of the device, fixing a weight having a diameter of 5 mm on the upper jig, and dropping the weight at a speed of 20 mm / min so that the glass and the specimen are detached, and when no adhesive remains on the specimen.

[0024] 10. In the above 1 to 9 specific examples, the environmentally friendly polyamide resin composition may have a notched Izod impact strength of about 12 to about 30 kgf·cm / cm of a 1 / 8" thick specimen measured according to ASTM D256.

[0025] 11. In the above 1 to 10 specific examples, the environmentally friendly polyamide resin composition may have a heat distortion temperature (HDT) of about 175 to about 195°C, measured under conditions of a load of 1.82 MPa and a heating rate of 120°C / hr, according to ASTM D648.

[0026] 12. In the above 1 to 11 specific examples, the eco-friendly polyamide resin composition has a flexural modulus of about 90,000 to about 180,000 kgf / cm of a 6.4 mm thick specimen measured at a speed of 2.8 mm / min according to ASTM D790. 2 It can be:

[0027] 13. Another aspect of the present invention relates to a molded article. The molded article is formed from an environmentally friendly polyamide resin composition according to any one of 1 to 12.

[0028] 14. Another aspect of the present invention relates to an electronic device housing. The electronic device housing comprises a glass frame; and a plastic member in contact with at least one surface of the glass frame; wherein the plastic member is formed from an environmentally friendly polyamide resin composition according to any one of 1 to 12.

[0029]

[0030] The present invention has the effect of providing an environmentally friendly polyamide resin composition having excellent environmental friendliness, adhesion to polyurethane adhesives, disintegration properties, impact resistance, heat resistance, rigidity, etc., and a molded article formed therefrom.

[0031]

[0032] FIG. 1 schematically illustrates a cross-section of an electronic device housing according to one specific example of the present invention.

[0033]

[0034] Hereinafter, the present invention will be described in detail as follows.

[0035] An environmentally friendly polyamide resin composition according to the present invention comprises (A) a recycled polyamide resin; (B) an aliphatic polyamide resin; (C) an aromatic polyamide resin; (D) glass fiber; (E) a polyether ester amide block copolymer; and (F) talc.

[0036] In this specification, “a to b” indicating a numerical range is defined as “≥a and ≤b”.

[0037]

[0038] (A) Recycled polyamide resin

[0039] A recycled polyamide resin according to one specific example of the present invention can be applied together with an aliphatic polyamide resin, an aromatic polyamide resin, glass fiber, a polyether ester amide block copolymer, talc, etc., thereby imparting environmental friendliness to the polyamide resin composition, while improving adhesion and disintegration properties with polyurethane adhesives, impact resistance, heat resistance, rigidity, etc.

[0040] In specific examples, the recycled polyamide resin may include polyamide 6 derived from marine inflow waste (waste polyamide), polyamide 6.6 derived from marine inflow waste, combinations thereof, and the like.

[0041] In a specific example, the recycled polyamide resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 100,000 g / mol, for example, about 20,000 to about 40,000 g / mol.

[0042] In a specific example, the recycled polyamide resin may be included in an amount of about 5 to about 25 wt%, for example, about 10 to about 20 wt%, based on 100 wt% of the total base material including the recycled polyamide resin, the aliphatic polyamide resin, the aromatic polyamide resin, and the glass fiber. If the content of the recycled polyamide resin is less than about 5 wt%, based on 100 wt% of the base material, there is a concern that the environmental friendliness of the eco-friendly polyamide resin composition may be reduced, and if it exceeds about 25 wt%, there is a concern that the decomposability and impact resistance of the eco-friendly polyamide resin composition with respect to the polyurethane adhesive may be reduced.

[0043]

[0044] (B) Aliphatic polyamide resin

[0045] An aliphatic polyamide resin according to one specific example of the present invention can be applied together with the recycled polyamide resin, aromatic polyamide resin, glass fiber, polyether ester amide block copolymer, talc, etc., to improve the eco-friendliness of the polyamide resin composition, adhesion and disintegration properties with polyurethane adhesive, impact resistance, heat resistance, rigidity, etc., and any conventional aliphatic polyamide resin other than polyamide 6 and polyamide 6.6 can be used.

[0046] In specific examples, the aliphatic polyamide resin may include polyamide 11, polyamide 12, polyamide 4.6, polyamide 6.10, polyamide 6.12, polyamide 10.10, polyamide 10.12, combinations thereof, and the like. For example, polyamide 10.12 may be used.

[0047] In a specific example, the aliphatic polyamide resin is dissolved in a concentrated sulfuric acid solution (96%) at a concentration of 0.5 g / dL, and the relative viscosity [η] measured by an Ubbelohde viscometer at 25°C rel ] may be about 2 to about 3, for example, about 2.3 to about 2.8. In the above range, the processability, impact resistance, etc. of the eco-friendly polyamide resin composition may be excellent.

[0048] In a specific example, the aliphatic polyamide resin may be included in an amount of about 1 to about 30 wt%, for example, about 10 to about 25 wt%, based on 100 wt% of the base material (recycled polyamide resin, aliphatic polyamide resin, aromatic polyamide resin, and glass fiber). If the content of the aliphatic polyamide resin is less than about 1 wt%, based on 100 wt% of the base material, there is a concern that the impact resistance, etc. of the eco-friendly polyamide resin composition may be reduced, and if it exceeds about 30 wt%, there is a concern that the disintegration properties, heat resistance, rigidity, eco-friendliness, etc. of the eco-friendly polyamide resin composition with respect to the polyurethane adhesive may be reduced.

[0049] In a specific example, the weight ratio of the recycled polyamide resin and the aliphatic polyamide resin may be about 1:0.1 to about 1:4, for example, about 1:0.2 to about 1:3, and specifically about 1:0.2 to about 1:2.6. In this range, the eco-friendly polyamide resin composition may have better eco-friendliness, decomposability with polyurethane adhesive, impact resistance, heat resistance, rigidity, and the like.

[0050]

[0051] (C) Aromatic polyamide resin

[0052] An aromatic polyamide resin according to one specific example of the present invention can be applied together with the recycled polyamide resin, aliphatic polyamide resin, glass fiber, polyether ester amide block copolymer, talc, etc. to improve the eco-friendliness of the polyamide resin composition, adhesion and disintegration properties with polyurethane adhesive, impact resistance, heat resistance, rigidity, etc., and an aromatic polyamide resin used in a conventional polyamide resin composition can be used.

[0053] In a specific example, the aromatic polyamide resin may be a polymer of an aliphatic dicarboxylic acid and an aromatic diamine produced by reacting them according to a known polymerization method.

[0054] In this specification, the term dicarboxylic acid, etc. is used to mean dicarboxylic acid, its alkyl ester (lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester), acid anhydride thereof, etc., and reacts with diamine, etc. to form a repeating unit derived from dicarboxylic acid (dicarboxylic acid moiety). In addition, in this specification, the repeating unit derived from dicarboxylic acid and the repeating unit derived from diamine (diamine moiety) mean a residue remaining when a hydrogen atom (removed from an amine group), a hydroxyl group or an alkoxy group (removed from a carboxylic acid group) is removed when dicarboxylic acid and diamine undergo a polymerization reaction.

[0055] In a specific example, the aliphatic dicarboxylic acid may be a linear, branched or cyclic aliphatic dicarboxylic acid having 6 to 20 carbon atoms, such as adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, etc. Specifically, adipic acid, sebacic acid, etc. may be used.

[0056] In a specific example, the aromatic diamine may be at least one aromatic diamine having 6 to 30 carbon atoms. For example, phenylenediamine compounds such as m-phenylenediamine and p-phenylenediamine, xylenediamine compounds such as m-xylenediamine and p-xylenediamine, naphthalenediamine compounds, etc. may be used.

[0057] In a specific example, the aromatic polyamide resin may have a molar ratio (diamine / dicarboxylic acid) of repeating units derived from the dicarboxylic acid and repeating units derived from the diamine of about 0.95 to about 1.15, for example, about 1.00 to about 1.10. Within this range, a polyamide resin having a polymerization degree suitable for molding can be produced, and deterioration of physical properties due to unreacted monomers can be prevented.

[0058] In a specific example, the aromatic polyamide resin may have a glass transition temperature measured by differential scanning calorimetry (DSC) of about 30 to about 100°C, for example, about 40 to about 80°C. Within this range, the eco-friendly polyamide resin composition may have excellent heat resistance, rigidity, impact resistance, and the like.

[0059] In addition, the aromatic polyamide resin may have an intrinsic viscosity [η] of about 0.7 to about 1.2 dL / g, for example, about 0.8 to about 1.0 dL / g, measured at 25°C using an Ubbelohde viscometer after being dissolved in a concentrated sulfuric acid solution (98%) at a concentration of 0.5 g / dL. Within the above range, the eco-friendly polyamide resin composition may have excellent heat resistance, rigidity, impact resistance, etc.

[0060] In a specific example, the aromatic polyamide resin may be included in an amount of about 1 to about 20 wt%, for example, about 5 to about 15 wt%, based on 100 wt% of the base material (recycled polyamide resin, aliphatic polyamide resin, aromatic polyamide resin, and glass fiber). When the content of the aromatic polyamide resin is less than about 1 wt%, based on 100 wt% of the base material, there is a concern that the decomposability, heat resistance, rigidity, etc. of the eco-friendly polyamide resin composition with respect to the polyurethane adhesive may be reduced, and when it exceeds about 20 wt%, there is a concern that the impact resistance, etc. of the eco-friendly polyamide resin composition may be reduced.

[0061]

[0062] (D) Glass fiber

[0063] According to one specific example of the present invention, glass fiber can be applied together with the recycled polyamide resin, aliphatic polyamide resin, aromatic polyamide resin, polyether ester amide block copolymer, talc, etc. to improve the eco-friendliness of the polyamide resin composition, adhesion and disintegration properties with polyurethane adhesive, impact resistance, heat resistance, rigidity, etc., and glass fiber used in a typical thermoplastic resin composition can be used.

[0064] In specific embodiments, the glass fiber may have a cross-section of various shapes, such as circular, oval, or rectangular.

[0065] In a specific example, the glass fiber may be a flat glass fiber having a rectangular or oval cross-section. The flat glass fiber may have an aspect ratio (major axis of the cross-section / minor axis of the cross-section) of about 1.5 to about 10, for example, about 2 to about 8, as measured using a Scanning Electron Microscope (SEM), a minor axis of the cross-section may be about 2 to about 10 μm, for example, about 4 to about 8 μm, and a length before processing may be about 1 to about 15 mm, for example, about 2 to about 8 mm. Within the above range, the rigidity, processability, etc. of the eco-friendly polyamide resin composition may be improved.

[0066] In a specific example, the glass fiber may be treated with a conventional surface treatment agent.

[0067] In a specific example, the glass fiber may be included in an amount of about 40 to about 80 wt%, for example, about 50 to about 70 wt%, based on 100 wt% of the base material (recycled polyamide resin, aliphatic polyamide resin, aromatic polyamide resin, and glass fiber). If the content of the glass fiber is less than about 40 wt%, based on 100 wt% of the base material, there is a concern that the adhesiveness of the eco-friendly polyamide resin composition with the polyurethane adhesive may be reduced, and if it exceeds about 80 wt%, there is a concern that the disintegration property of the eco-friendly polyamide resin composition with the polyurethane adhesive may be reduced.

[0068]

[0069] (E) Polyether esteramide block copolymer

[0070] A polyether esteramide block copolymer according to one specific example of the present invention can be applied together with the recycled polyamide resin, aliphatic polyamide resin, aromatic polyamide resin, glass fiber, talc, etc. to improve the eco-friendliness of the polyamide resin composition, adhesion and disintegration properties with polyurethane adhesive, impact resistance, heat resistance, rigidity, etc., and a block copolymer of a reaction mixture including an amino carboxylic acid, lactam, or diamine-dicarboxylate having 6 or more carbon atoms; polytetramethylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms can be used.

[0071] In specific examples, salts of aminocarboxylic acids, lactams or diamine-dicarboxylic acids having 6 or more carbon atoms may include aminocarboxylic acids such as ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminofalconic acid, ω-aminocaprinic acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid, etc.; lactams such as caprolactam, enantlactam, caprylactam, lauryllactam, etc.; and salts of diamines and dicarboxylic acids such as salts of hexamethylenediamine-adipic acid and salts of hexamethylenediamine-isophthalic acid, etc. For example, salts of 1,2-aminododecanoic acid, caprolactam, hexamethylenediamine-adipic acid, etc. can be used.

[0072] In specific examples, examples of the dicarboxylic acid having 4 to 20 carbon atoms include terephthalic acid, 1,4-cyclohexacarboxylic acid, sebacic acid, adipic acid, dodecanocarboxylic acid, etc.

[0073] In a specific example, the bond between the amino carboxylic acid, lactam or diamine-dicarboxylic acid salt having 6 or more carbon atoms and the polytetramethylene glycol may be an ester bond, the bond between the amino carboxylic acid, lactam or diamine-dicarboxylic acid salt having 6 or more carbon atoms and the dicarboxylic acid having 4 to 20 carbon atoms may be an amide bond, and the bond between the polytetramethylene glycol and the dicarboxylic acid having 4 to 20 carbon atoms may be an ester bond.

[0074] In a specific example, the polyether esteramide block copolymer can be produced by a known synthetic method, for example, it can be produced according to the synthetic method disclosed in Japanese Patent Publication No. 56-045419 and Japanese Patent Laid-Open No. 55-133424.

[0075] In a specific example, the polyether esteramide block copolymer may contain about 10 to about 95 wt% of a polyether-ester block. Within this range, the impact resistance, etc. of the eco-friendly polyamide resin composition may be excellent.

[0076] In a specific example, the polyether esteramide block copolymer may be included in an amount of about 5 to about 15 parts by weight, for example, about 6 to about 12 parts by weight, relative to about 100 parts by weight of the base material (recycled polyamide resin, aliphatic polyamide resin, aromatic polyamide resin, and glass fiber). If the content of the polyether esteramide block copolymer is less than about 5 parts by weight relative to about 100 parts by weight of the base material, there is a concern that the adhesiveness, impact resistance, etc. of the eco-friendly polyamide resin composition with the polyurethane adhesive may be reduced, and if it exceeds about 15 parts by weight, there is a concern that the disintegration property, heat resistance, rigidity, etc. of the eco-friendly polyamide resin composition with the polyurethane adhesive may be reduced.

[0077] In a specific example, the weight ratio (D:E) of the glass fiber and the polyether ester amide block copolymer may be from about 1:0.05 to about 1:0.3, for example from about 1:0.1 to about 1:0.2. Within this range, the adhesiveness and decomposition properties, impact resistance, heat resistance, rigidity, etc. of the eco-friendly polyamide resin composition with respect to polyurethane adhesive may be better.

[0078]

[0079] (F) Talk

[0080] According to one specific example of the present invention, talc can be applied together with the recycled polyamide resin, aliphatic polyamide resin, aromatic polyamide resin, glass fiber, and polyether esteramide block copolymer, etc., to improve the eco-friendliness of the polyamide resin composition, adhesion and disintegration properties with polyurethane adhesive, impact resistance, heat resistance, rigidity, etc., and talc used in a typical thermoplastic resin composition can be used.

[0081] In a specific example, the talc is a plate-shaped inorganic filler, and may have an average particle size of about 0.5 to about 10 μm, for example, about 1 to about 7 μm, as measured by a particle size measuring device (Malvern mastersizer 3000). Within this range, the eco-friendly polyamide resin composition may have excellent adhesiveness and disintegration properties with a polyurethane adhesive, as well as heat resistance.

[0082] In a specific example, the talc may be included in an amount of about 0.1 to about 1 part by weight, for example, about 0.15 to about 0.5 part by weight, relative to about 100 parts by weight of the base material (recycled polyamide resin, aliphatic polyamide resin, aromatic polyamide resin, and glass fiber). If the content of the talc is less than about 0.1 part by weight relative to about 100 parts by weight of the base material, there is a concern that the bonding properties of the eco-friendly polyamide resin composition with a polyurethane adhesive may be reduced, and if it exceeds about 1 part by weight, there is a concern that the impact resistance of the eco-friendly polyamide resin composition may be reduced.

[0083] In a specific example, the weight ratio (D:E) of the polyether esteramide block copolymer and the talc may be from about 1:0.005 to about 1:0.08, for example from about 1:0.01 to about 1:0.07. Within this range, the eco-friendly polyamide resin composition may have better adhesiveness and disintegration properties with polyurethane adhesive, impact resistance, heat resistance, rigidity, and the like.

[0084]

[0085] An eco-friendly polyamide resin composition according to one embodiment of the present invention may further include conventional additives as needed, within a range that does not impair the effects of the present invention. Such additives include, but are not limited to, heat stabilizers, flame retardants, antioxidants, lubricants, release agents, nucleating agents, colorants, and mixtures thereof. When the additives are used, the content thereof may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 20 parts by weight, based on about 100 parts by weight of the base material.

[0086]

[0087] An eco-friendly polyamide resin composition according to one specific example of the present invention may be in the form of pellets obtained by mixing the above components and melt-extruding them at about 240 to about 320°C, for example, about 250 to about 310°C, using a conventional twin-screw extruder.

[0088] In a specific example, the eco-friendly polyamide resin composition is applied with a polyurethane adhesive (HB Fuller, EH9777BS) of 0.018 g at 110°C in a thickness of 1 mm on a specimen measuring 50 mm × 50 mm × 4 mm, and glass measuring 25 mm × 25 mm × 0.7 mm is attached on the applied adhesive, and cured for 72 hours under temperature conditions of 25°C and humidity conditions of 50%, and then a weight weighing 10 to 500 g is attached to the top of a drop test evaluation device using the Dupont drop test method and a specimen is fixed to the bottom, and the weight is dropped from a height of 50 cm. When the specimen is detached from the glass, the adhesive strength (potential energy) may be about 700 to about 990 mJ, for example, about 750 to about 950 mJ.

[0089] In a specific example, the eco-friendly polyamide resin composition may be prepared by applying 0.018 g of a polyurethane-based adhesive (HB Fuller, EH9777BS) at 110°C to a thickness of 1 mm on a specimen measuring 50 mm × 50 mm × 4 mm, attaching glass measuring 25 mm × 25 mm × 0.7 mm on the applied adhesive, curing the adhesive for 72 hours under temperature conditions of 25°C and humidity conditions of 50%, heating the adhesive at 75°C for 15 minutes, and then using a UTM (Universal testing machine) device, fixing the specimen with the glass attached to the bottom of the device, fixing a weight having a diameter of 5 mm on the upper jig, and dropping the weight at a speed of 20 mm / min so that the glass and the specimen are detached, and when no adhesive remains on the specimen.

[0090] In a specific example, the eco-friendly polyamide resin composition may have a notched Izod impact strength of about 12 to about 30 kgf·cm / cm, for example, about 14 to about 25 kgf·cm / cm, of a 1 / 8" thick specimen measured according to ASTM D256.

[0091] In a specific example, the eco-friendly polyamide resin composition may have a heat distortion temperature (HDT) of about 175 to about 195°C, for example, about 177 to about 193°C, measured under conditions of a load of 1.82 MPa and a heating rate of 120°C / hr according to ASTM D648.

[0092] In a specific example, the eco-friendly polyamide resin composition has a flexural modulus of about 90,000 to about 180,000 kgf / cm of a 6.4 mm thick specimen measured at a speed of 2.8 mm / min according to ASTM D790. 2 , for example, about 100,000 to about 170,000 kgf / cm 2 It could be.

[0093]

[0094] A molded product according to the present invention is formed from the above-mentioned eco-friendly polyamide resin composition.

[0095] In a specific example, the molded product may be a plastic member of an electronic device housing including a glass frame and a plastic member in contact with at least one surface of the glass frame.

[0096] FIG. 1 schematically illustrates a cross-section of an electronic device housing according to one embodiment of the present invention. The sizes of components constituting the invention in the drawing are exaggerated for clarity of the specification and are not limited thereto. As illustrated in FIG. 1, an electronic device housing according to one embodiment of the present invention includes a glass frame (10); and at least one plastic member (20) in contact with at least one surface of the glass frame (10), wherein the plastic member is characterized in that it is formed from the eco-friendly polyamide resin composition.

[0097] In a specific example, the shape of the glass frame (10) and the plastic member (20) is not limited to the drawing and may have various shapes. However, the glass frame (10) and the plastic member (20) have a structure in which at least one surface is in contact with each other. The contact structure can be implemented by bonding using a polyurethane adhesive.

[0098] In a specific example, a product applicable to a typical electronic device housing can be used as the glass frame (10), and is readily available commercially.

[0099] In a specific example, the plastic member (20) may be formed from the eco-friendly polyamide resin composition through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Specifically, the plastic member (20) may be a plastic member of an electronic device housing, an internal material of an electrical or electronic device, etc.

[0100]

[0101] Hereinafter, the present invention will be described in more detail through examples; however, these examples are for the purpose of explanation only and should not be construed as limiting the present invention.

[0102]

[0103] Example

[0104] The specifications of each component used in the following examples and comparative examples are as follows.

[0105] (A) Recycled polyamide resin

[0106] Polyamide 6 derived from marine waste (Manufacturer: Jinjiang-Yonghong Regeneration Resource, Product Name: YH-005) was used.

[0107] (B) Aliphatic polyamide resin

[0108] Polyamide 10.12 (Manufacturer: Shandong Guangyin New Materials, Product Name: B150) was used.

[0109] (C) Aromatic polyamide resin

[0110] Polyamide MXD10 (Manufacturer: Mitsubishi Gas Chemical, Product Name: LEXTER8000) was used.

[0111] (D) Glass fiber

[0112] Flat glass fiber (manufacturer: NITTOBO, product name: CSG 3PA-820) was used.

[0113] (E) Polyether esteramide block copolymer

[0114] (E1) Polyamide 12-polytetramethylene oxide block copolymer (manufacturer: Evonik, product name: Vestamid E62-S3) was used.

[0115] (E2) Polyamide 6-polyethylene oxide block copolymer (PA6-b-PEO, manufacturer: Sanyo chemical, product name: Pelestat 1251) was used.

[0116] (F) Talk

[0117] Talc (Manufacturer: KOCH, Product Name: KCM-6300C) was used.

[0118]

[0119] Examples 1 to 12 and Comparative Examples 1 to 10

[0120] Each of the above components was added in the amounts shown in Tables 1, 2, 3, and 4 below, and then extruded at about 260°C to produce pellets. The extrusion was performed using a twin-screw extruder with an L / D of 44 and a diameter of 45 mm. The manufactured pellets were dried at about 80°C for about 4 hours or more, and then injection-molded using a 6 oz injection molding machine (molding temperature: about 280°C, mold temperature: about 80°C) to produce specimens. The physical properties of the manufactured specimens were evaluated using the following methods, and the results are shown in Tables 1, 2, 3, and 4 below.

[0121]

[0122] Physical property evaluation method

[0123] (1) Adhesive strength (potential energy, unit: mJ): 0.018 g of polyurethane adhesive (HB Fuller, EH9777BS) was applied to a 1 mm thickness on a 50 mm × 50 mm × 4 mm sized specimen at 110℃, and a 25 mm × 25 mm × 0.7 mm sized glass was attached on the applied adhesive, and after curing for 72 hours under temperature conditions of 25℃ and humidity conditions of 50%, a weight weighing 10 to 500 g was attached to the top of the drop evaluation device using the DuPont drop test method, and the specimen was fixed to the bottom, and the weight was dropped from a height of 50 cm to measure the adhesive strength (potential energy) when the specimen was detached from the glass.

[0124] (Positional energy (Ep) = Mass (Weight of weight at release) × 9.8 (Acceleration due to gravity) × 50 (Height of weight at release))

[0125] (2) Demountability evaluation: 0.018 g of polyurethane adhesive (HB Fuller, EH9777BS) was applied to a 50 mm × 50 mm × 4 mm specimen at 110℃ with a thickness of 1 mm, and a 25 mm × 25 mm × 0.7 mm glass was attached to the applied adhesive, and then cured for 72 hours under temperature conditions of 25℃ and humidity of 50%, and then heated at 75℃ for 15 minutes, and then, using a UTM (Universal testing machine), the specimen with the glass attached was fixed to the bottom of the machine, a weight with a diameter of 5 mm was fixed to the upper jig, and the weight was dropped at a speed of 20 mm / min to check whether there was any adhesive remaining on the specimen when the glass and specimen were detached. (OK: no adhesive remaining, NG: adhesive remaining)

[0126] (3) Notched Izod impact strength (unit: kgf·cm / cm): The notched Izod impact strength of a 1 / 8" thick specimen was measured according to ASTM D256.

[0127] (4) Heat deflection temperature (unit: ℃): According to ASTM D648, the heat deflection temperature (HDT) of the specimen was measured under the conditions of a load of 1.82 MPa and a heating rate of 120℃ / hr.

[0128] (5) Flexural modulus (unit: kgf / cm) 2 ): According to ASTM D790, the flexural modulus of 6.4 mm thick specimens was measured at a speed of 2.8 mm / min.

[0129]

[0130] Example 123456 (A) (% by weight) 101114201017.5 (B) (% by weight) 222118122522.5 (C) (% by weight) 8888510 (D) (% by weight) 606060606050 (E1) (parts by weight) 999999 (E2) (parts by weight)------ (F) (parts by weight) 0.20.20.20.20.20.2 Adhesive strength 850850900950850850 Disintegration evaluation OKOKOKOKOKOKOK Notched Izod impact strength 18.0 17.5 16.0 14.0 19.0 15.7 Heat deflection temperature 183 182 185 190 181 178 Flexural Elasticity modulus 138,000 135,000 140,000 155,000 135,000 125,000

[0131] * Weight parts: Weight parts per 100 weight parts of basic materials (A+B+C+D)

[0132]

[0133] Example 789101112(A) (Wt%)10.51514141414(B) (Wt%)13.52018181818(C) (Wt%)688888(D) (Wt%)705760606060(E1) (Wt%)9961299(E2) (Wt%)------(F) (Wt%)0.20.20.20.20.150.5Adhesive strength800850750950850850Disintegration evaluationOKOKOKOKOKOKOKNotched Izod impact strength20.016.915.318.717.116.4Heat deflection temperature191181188178185185Flexibility Elasticity modulus 165,000 140,000 155,000 135,000 158,000 153,000

[0134] * Weight parts: Weight parts per 100 weight parts of basic materials (A+B+C+D)

[0135]

[0136] Comparative Example 12345 (A) (Wt%) 414.53022.755.25 (B) (Wt%) 35.50.5229.256.75 (C) (Wt%) 0.5258133 (D) (Wt%) 6060603585 (E1) (Wt%) 99999 (E2) (Wt%)-----(F) (Wt%) 0.20.20.20.20.20.2 Adhesive Strength 6708401,1006801,050 Disintegration Evaluation OKOKNGOKNG Notched Izod Impact Strength 19.411.08,513.218.8 Heat Deflection Temperature 174180194175199 Flexural Modulus 85,000135,000150,00090,000180,000

[0137] * Weight parts: Weight parts per 100 weight parts of basic materials (A+B+C+D)

[0138]

[0139] Comparative Example 678910(A) (Wt%) 1414141414(B) (Wt%) 1818181818(C) (Wt%) 88888(D) (Wt%) 6060606060(E1) (Wt%) 120-99(E2) (Wt%) --9--(F) (Wt%) 0.20.20.20.012Adhesive Strength 3001,2001,050650850Disintegration Evaluation OKNGNGOKOKNotched Izod Impact Strength 10.022.516.519.59.5Heat Deflection Temperature 189168181171184Flexural Modulus 150,00080,000135,000140,000125,000

[0140] * Weight parts: Weight parts per 100 weight parts of basic materials (A+B+C+D)

[0141]

[0142] From the above results, it can be seen that the eco-friendly polyamide resin composition according to the present invention is eco-friendly by using a recycled polyamide resin in a certain amount or more (5 wt% or more of the total 100 wt% of the base material), and has excellent adhesion (adhesive strength) and disintegration properties with polyurethane adhesive, impact resistance (notched Izod impact strength), heat resistance (heat distortion temperature), and rigidity (flexural modulus).

[0143] On the other hand, in the case of Comparative Example 1, where a small amount of recycled polyamide resin and aromatic polyamide resin were applied, and an excessive amount of aliphatic polyamide resin was applied, it was found that the eco-friendliness, adhesion to polyurethane adhesive, heat resistance, rigidity, etc. were reduced, and in the case of Comparative Example 2, where an excessive amount of aromatic polyamide resin was applied, and a small amount of aliphatic polyamide resin was applied, it was found that impact resistance, etc. were reduced, and in the case of Comparative Example 3, where an excessive amount of recycled polyamide resin was applied, it was found that the disassembly property with polyurethane adhesive, impact resistance, etc. were reduced. In the case of Comparative Example 4, where a small amount of glass fiber was applied, it was found that the adhesion to polyurethane adhesive, etc. were reduced, and in the case of Comparative Example 5, where an excessive amount of glass fiber was applied, it was found that the disassembly property with polyurethane adhesive, etc. were reduced. In the case of Comparative Example 6, where a small amount of polyether esteramide block copolymer was applied, it was found that the adhesiveness with polyurethane adhesive, impact resistance, etc. were reduced, and in the case of Comparative Example 7, where an excessive amount of polyether esteramide block copolymer was applied, it was found that the disassembly property, heat resistance, rigidity, etc. with polyurethane adhesive were reduced, and in the case of Comparative Example 8, where a polyamide 6-polyethylene oxide block copolymer (E2) was applied instead of the polyether esteramide block copolymer of the present invention, it was found that the disassembly property with polyurethane adhesive, etc. were reduced. In addition, in the case of Comparative Example 9, where a small amount of talc was applied, it was found that the adhesiveness with polyurethane adhesive, etc. were reduced, and in the case of Comparative Example 10, where an excessive amount of talc was applied, it was found that the impact resistance, etc. were reduced.

[0144]

[0145] The present invention has been described with reference to exemplary embodiments. Those skilled in the art will appreciate that the present invention can be implemented in modified forms without departing from its essential characteristics. Therefore, the disclosed embodiments should be considered illustrative rather than limiting. The scope of the present invention is set forth in the claims, not the foregoing description, and all differences within the scope equivalent thereto should be construed as being encompassed by the present invention.

Claims

1. About 100 parts by weight of a base material comprising about 5 to about 25 wt% of a recycled polyamide resin, about 1 to about 30 wt% of an aliphatic polyamide resin excluding polyamide 6 and polyamide 6.6, about 1 to about 20 wt% of an aromatic polyamide resin, and about 40 to about 80 wt% of glass fiber; About 5 to about 15 parts by weight of a polyether esteramide block copolymer; and Contains about 0.1 to about 1 part by weight of talc; An environmentally friendly polyamide resin composition characterized in that the polyether esteramide block copolymer is a block copolymer of a reaction mixture containing an amino carboxylic acid having 6 or more carbon atoms, a lactam or diamine-dicarboxylate, polytetramethylene glycol, and a dicarboxylic acid having 4 to 20 carbon atoms.

2. An eco-friendly polyamide resin composition according to claim 1, characterized in that the recycled polyamide resin comprises at least one of polyamide 6 derived from marine inflow waste and polyamide 6.6 derived from marine inflow waste.

3. An environmentally friendly polyamide resin composition according to claim 1 or 2, characterized in that the aliphatic polyamide resin comprises at least one of polyamide 11, polyamide 12, polyamide 4.6, polyamide 6.10, polyamide 6.12, polyamide 10.10, and polyamide 10.

12.

4. An environmentally friendly polyamide resin composition according to any one of claims 1 to 3, wherein the aromatic polyamide resin is a polymer of an aliphatic dicarboxylic acid and an aromatic diamine.

5. An environmentally friendly polyamide resin composition according to any one of claims 1 to 4, wherein the glass fiber has a rectangular or elliptical cross-section, an aspect ratio of the cross-section (major axis of the cross-section / minor axis of the cross-section) of about 1.5 to about 10, and a minor axis of about 2 to about 10 ㎛.

6. An environmentally friendly polyamide resin composition according to any one of claims 1 to 5, wherein the weight ratio of the glass fiber and the polyether esteramide block copolymer is about 1:0.05 to 1:0.

3.

7. An environmentally friendly polyamide resin composition according to any one of claims 1 to 6, wherein the weight ratio of the polyether esteramide block copolymer and the talc is about 1:0.005 to about 1:0.

08.

8. In any one of claims 1 to 7, the eco-friendly polyamide resin composition is characterized in that the adhesive strength (potential energy) when the specimen is detached from the glass is about 700 to about 990 mJ, as measured by applying 0.018 g of a polyurethane-based adhesive (HB Fuller, EH9777BS) at 110°C to a thickness of 1 mm on a specimen measuring 50 mm × 50 mm × 4 mm, attaching glass measuring 25 mm × 25 mm × 0.7 mm on the applied adhesive, and curing it for 72 hours under temperature conditions of 25°C and humidity conditions of 50%, and then attaching a weight weighing 10 to 500 g to the top of a drop test evaluation device and fixing the specimen to the bottom, and then dropping the weight from a height of 50 cm.

9. In any one of claims 1 to 8, the eco-friendly polyamide resin composition is characterized in that, when a 0.018 g polyurethane-based adhesive (HB Fuller, EH9777BS) is applied to a 50 mm × 50 mm × 4 mm sized specimen at 110°C with a thickness of 1 mm, a 25 mm × 25 mm × 0.7 mm sized glass is attached to the applied adhesive, the adhesive is cured for 72 hours under temperature conditions of 25°C and humidity conditions of 50%, and the glass is heated at 75°C for 15 minutes, and then, using a UTM (Universal testing machine) device, the specimen with the glass attached is fixed to the bottom of the device, a weight having a diameter of 5 mm is fixed to the upper jig, and the weight is dropped at a speed of 20 mm / min so that the glass and the specimen are detached, no adhesive remains on the specimen.

10. An environmentally friendly polyamide resin composition according to any one of claims 1 to 9, characterized in that the environmentally friendly polyamide resin composition has a notched Izod impact strength of about 12 to about 30 kgf·cm / cm of a 1 / 8" thick specimen measured according to ASTM D256.

11. An environmentally friendly polyamide resin composition according to any one of claims 1 to 10, characterized in that the environmentally friendly polyamide resin composition has a heat distortion temperature (HDT) of about 175 to about 195°C, measured under conditions of a load of 1.82 MPa and a heating rate of 120°C / hr according to ASTM D648.

12. In any one of claims 1 to 11, the eco-friendly polyamide resin composition has a flexural modulus of about 90,000 to about 180,000 kgf / cm of a 6.4 mm thick specimen measured at a speed of 2.8 mm / min according to ASTM D790. 2 An environmentally friendly polyamide resin composition characterized by:

13. A molded product characterized by being formed from an eco-friendly polyamide resin composition according to any one of claims 1 to 12.

14. Glass frame; and A plastic member that contacts at least one surface of the glass frame; An electronic device housing, characterized in that the plastic member is formed from an eco-friendly polyamide resin composition according to any one of claims 1 to 12.

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