Environment-friendly polyamide resin composition and product comprising same

Abstract

The eco-friendly polyamide resin composition of the present invention comprises: about 100 parts by weight of a base material; about 5 to 15 parts by weight of a poly (ether ester amide) block copolymer; and about 0.1 to 1 part by weight of talc, the base material including: about 5 to 25 wt% of a recovered polyamide resin; about 1 to 30 wt% of an aliphatic polyamide resin other than polyamide 6 and polyamide 6.6; about 1 to 20 wt% of an aramid resin; and about 40 to 80 wt% of glass fibers. The environment-friendly polyamide resin composition is excellent in the aspects of environment friendliness, adhesion to a polyurethane adhesive, separability with the polyurethane adhesive, impact resistance, heat resistance, rigidity and the like.

Description

Technical Field

[0001] This invention relates to environmentally friendly polyamide resin compositions and molding articles comprising the same. More specifically, this invention relates to environmentally friendly polyamide resin compositions exhibiting superior properties in terms of environmental friendliness, adhesion and separability relative to polyurethane adhesives, impact resistance, heat resistance, and rigidity, as well as molding articles comprising the same. Background Technology

[0002] Polyamide resins possess excellent processing properties and impact resistance, making them advantageous for use in the housings of various products and in interior / exterior automotive materials. Polyamide resins can be blended with inorganic fillers such as glass fiber to improve heat resistance and mechanical properties, including rigidity. Furthermore, in line with the trend towards thinner and lighter designs, the application of polyamide resins has expanded to include the housings of electronic products.

[0003] In the assembly of components in electrical / electronic products and automobiles, bonding processes are performed using adhesive tapes or adhesives. Because bonding processes using PUR (reactive polyurethane) type polyurethane adhesives are simpler than those using adhesive tapes, PUR type polyurethane adhesives offer advantages in improving yield and ensuring good bond strength. In particular, PUR type polyurethane adhesives are highly efficient when the bonding area is narrow.

[0004] However, the use of polyurethane adhesives is limited due to their very poor adhesion strength to polyamide resins.

[0005] Furthermore, with the increasing volume of plastic waste and environmental concerns such as carbon reduction, there is growing market interest in environmentally friendly products derived from recycled plastic waste. In response, although many companies have developed technologies to convert waste plastic products into raw materials (such as through pyrolysis), these technologies require significant energy for the recycling system due to the high heat consumption during the process. Consequently, methods that minimize this energy consumption while maximizing waste reuse are needed, such as mechanical shredding to produce raw materials for resin processing.

[0006] However, due to aging, resins derived from waste generally exhibit deteriorated mechanical properties and heat resistance.

[0007] Therefore, there is a need to develop environmentally friendly polyamide resin compositions that are environmentally friendly by recycling plastic waste and have superior properties compared to polyurethane adhesives in terms of adhesion and separability, impact resistance, heat resistance, and rigidity.

[0008] The background technology of this invention is disclosed in U.S. Patent Publication No. 2014 / 0179850, etc. Summary of the Invention

[0009] [Technical Issues]

[0010] One object of the present invention is to provide an environmentally friendly polyamide resin composition that exhibits superior properties in terms of environmental friendliness, adhesion and separability relative to polyurethane adhesives, impact resistance, heat resistance and rigidity.

[0011] Another object of the present invention is to provide molded articles produced from environmentally friendly polyamide resin compositions.

[0012] The above and other objects of the present invention will become apparent from the detailed description of the present invention.

[0013] [Technical Solution]

[0014] 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 wt% to about 25 wt% of recycled polyamide resin, about 1 wt% to about 30 wt% of an aliphatic polyamide resin other than polyamide 6 and polyamide 6.6, about 1 wt% to about 20 wt% of an aromatic polyamide resin, and about 40 wt% to about 80 wt% of glass fiber; about 5 parts by weight to about 15 parts by weight of a poly(ether ester amide) block copolymer; and about 0.1 parts by weight to about 1 part by weight of talc, wherein the poly(ether ester amide) block copolymer is a block copolymer comprising a reaction mixture of an aminocarboxylic acid, a lactam or a diamine-dicarboxylic acid salt having 6 or more carbon atoms, polytetramethylene glycol, and a dicarboxylic acid having 4 to 20 carbon atoms.

[0015] 2. In embodiment 1, the recycled polyamide resin may include at least one of polyamide 6 derived from marine waste and polyamide 6.6 derived from marine waste.

[0016] 3. In embodiment 1 or 2, 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.

[0017] 4. In embodiments 1 to 3, the aromatic polyamide resin may be a polymer of aliphatic dicarboxylic acid and aromatic diamine.

[0018] 5. In embodiments 1 to 4, the glass fiber may have a rectangular or elliptical cross-section in the cross-sectional view, an aspect ratio (major axis / minor axis in the cross-section) of about 1.5 to about 10, and a minor axis of about 2 μm to about 10 μm.

[0019] 6. In embodiments 1 to 5, the glass fiber and the poly(ether ester amide) block copolymer may be present in a weight ratio of about 1:0.05 to about 1:0.3.

[0020] 7. In embodiments 1 to 6, the poly(ether ester amide) block copolymer and talc may be present in a weight ratio of about 1:0.005 to about 1:0.08.

[0021] 8. In embodiments 1 to 7, according to the DuPont drop test, a drop hammer with a mass of 10g to 500g is dropped from a height of 50cm onto the sample using a drop tester. The sample with dimensions of 50mm × 50mm × 4mm is measured when it separates from a glass plate with dimensions of 25mm × 25mm × 0.7mm. The environmentally friendly polyamide resin composition can have an adhesive strength (potential energy) of about 700mJ to about 990mJ, wherein the drop hammer is fixed to the upper end of the drop tester and the sample is fixed to its lower end. 0.018g of polyurethane adhesive (EH9777BS, HB Fuller Ltd.) is applied to the sample at 110°C with a thickness of 1mm, and the glass plate is attached to the sample by the adhesive. The adhesive is then cured at 25°C and 50%RH for 72 hours.

[0022] 9. In embodiments 1 to 8, a drop hammer with a diameter of 5 mm is dropped onto the sample at a test speed of 20 mm / min using a universal testing machine (UTM). When the sample separates from a glass plate with dimensions of 25 mm × 25 mm × 0.7 mm, the environmentally friendly polyamide resin composition prevents adhesive residue from remaining on the sample with dimensions of 50 mm × 50 mm × 4 mm. The drop hammer is fixed to the upper clamp of the UTM and the glass plate is fixed to its lower end. 0.018 g of polyurethane adhesive (EH9777BS, HB Fuller Ltd.) is applied to the sample at 110°C with a thickness of 1 mm, and the glass plate is attached to the sample by the adhesive. The adhesive is then cured at 25°C and 50% RH for 72 hours and heated at 75°C for 15 min.

[0023] 10. In embodiments 1 to 9, the environmentally friendly polyamide resin composition can have a notched cantilever beam impact strength of about 12 kgf·cm / cm to about 30 kgf·cm / cm, as measured against a 1 / 8" thick sample according to ASTM D256.

[0024] 11. In embodiments 1 to 10, the environmentally friendly polyamide resin composition may have a heat distortion temperature (HDT) of about 175°C to about 195°C, as measured according to ASTM D648 at a heating rate of 120°C / hr under a load of 1.82 MPa.

[0025] 12. In embodiments 1 to 11, when a 6.4 mm thick sample was measured at a rate of 2.8 mm / min according to ASTM D790, the environmentally friendly polyamide resin composition could have approximately 90,000 kgf / cm².2 Approximately 180,000 kgf / cm 2 Flexural modulus.

[0026] 13. Another aspect of the invention relates to a molding article. The molding article is formed from an environmentally friendly polyamide resin composition according to any one of embodiments 1 to 12.

[0027] 14. A further aspect of the invention relates to an electronic device housing. The electronic device housing includes: a glass frame; and a plastic member adjacent to at least one surface of the glass frame, wherein the plastic member is formed of an environmentally friendly polyamide resin composition according to any one of embodiments 1 to 12.

[0028] [Beneficial Effects]

[0029] This invention provides an environmentally friendly polyamide resin composition that exhibits superior properties in terms of environmental friendliness, adhesion and separability relative to polyurethane adhesives, impact resistance, heat resistance, and rigidity, as well as molded articles produced therefrom. Attached Figure Description

[0030] Figure 1 This is a schematic cross-sectional view of an electronic device housing according to one embodiment of the present invention. Detailed Implementation

[0031] The embodiments of the present invention will be described in detail below.

[0032] The polyamide resin composition according to the present invention comprises: (A) recycled polyamide resin; (B) aliphatic polyamide resin; (C) aromatic polyamide resin; (D) glass fiber; (E) poly(ether ester amide) block copolymer; and (F) talc.

[0033] In this article, when used to represent a specific numerical range, "a to b" is defined as "≥a and ≤b".

[0034] (A) Recycled polyamide resin

[0035] According to one embodiment, the recycled polyamide resin can be used with aliphatic polyamide resins, aromatic polyamide resins, glass fibers, poly(ether ester amide) block copolymers, and talc, etc., to enhance the environmentally friendly polyamide resin composition in terms of adhesion and separability, impact resistance, heat resistance, and rigidity relative to polyurethane adhesives while imparting environmental friendliness to the polyamide resin composition.

[0036] In some embodiments, the recycled polyamide resin may include polyamide 6 derived from marine waste (waste polyamide), polyamide 6.6 derived from marine waste, and combinations thereof.

[0037] In some embodiments, the recovered polyamide resin may have a weight-average molecular weight (Mw) of about 10,000 g / mol to about 100,000 g / mol (e.g., about 20,000 g / mol to about 40,000 g / mol), as measured by gel permeation chromatography (GPC).

[0038] In some embodiments, based on a 100 wt% base material comprising recycled polyamide resin, aliphatic polyamide resin, aromatic polyamide resin, and glass fiber, the recycled polyamide resin may be present in an amount of about 5 wt% to about 25 wt% (e.g., about 10 wt% to about 20 wt%). If the content of recycled polyamide resin is less than about 5 wt% based on the 100 wt% base material, the environmentally friendly polyamide resin composition may suffer from degradation in environmental friendliness, etc., and if the content of recycled polyamide resin exceeds about 25 wt%, the environmentally friendly polyamide resin composition may suffer from degradation in separability from polyurethane adhesives and impact resistance, etc.

[0039] (B) Aliphatic polyamide resin

[0040] According to one embodiment, the aliphatic polyamide resin can be used with recycled polyamide resin, aromatic polyamide resin, glass fiber, poly(ether ester amide) block copolymer and talc, etc., to enhance the properties of the environmentally friendly polyamide resin composition in terms of environmental friendliness, adhesion and separability relative to polyurethane adhesives, impact resistance, heat resistance and rigidity, and can be a typical aliphatic polyamide resin other than polyamide 6 and polyamide 6.6.

[0041] In some embodiments, 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, and combinations thereof. For example, the aliphatic polyamide resin may be polyamide 10.12, etc.

[0042] In some embodiments, the aliphatic polyamide resin can have a relative viscosity [η] of about 2 to about 3 (e.g., about 2.3 to about 2.8) when the sample is measured using an Ubbelohde viscometer at 25°C. rel The sample was prepared by dissolving an aliphatic polyamide resin in a concentrated sulfuric acid solution (96%) to a concentration of 0.5 g / dL. Within this range, the environmentally friendly polyamide resin composition exhibits excellent processing properties and impact resistance, among other characteristics.

[0043] In some embodiments, based on 100 wt% of the base materials (recycled polyamide resin, aliphatic polyamide resin, aromatic polyamide resin, and glass fiber), the aliphatic polyamide resin may be present in an amount of about 1 wt% to about 30 wt% (e.g., about 10 wt% to about 25 wt%). If the content of the aliphatic polyamide resin is less than about 1 wt%, the environmentally friendly polyamide resin composition may suffer from degradation in impact resistance, etc., and if the content of the aliphatic polyamide resin exceeds about 30 wt%, the environmentally friendly polyamide resin composition may suffer from degradation in separability from the polyurethane adhesive, etc.

[0044] In some embodiments, the recycled polyamide resin and aliphatic polyamide resin may be present in a weight ratio of about 1:0.1 to about 1:4 (e.g., about 1:0.2 to about 1:3, specifically about 1:0.2 to about 1:2.6). Within this range, environmentally friendly polyamide resins exhibit superior properties in terms of environmental friendliness, separability from polyurethane adhesives, impact resistance, heat resistance, and rigidity.

[0045] (C) Aromatic polyamide resin

[0046] According to one embodiment, the aromatic polyamide resin can be used with recycled polyamide resin, aliphatic polyamide resin, glass fiber, poly(ether ester amide) block copolymer and talc, etc., to enhance the properties of the environmentally friendly polyamide resin composition in terms of environmental friendliness, adhesion and separability relative to polyurethane adhesives, impact resistance, heat resistance and rigidity, and can be used as an aromatic polyamide resin for typical polyamide resin compositions.

[0047] In some embodiments, the aromatic polyamide resin may be a polymer of aliphatic dicarboxylic acids and aromatic diamines, prepared by polymerization methods well known in the art.

[0048] In this document, the term "dicarboxylic acid," for example, is used to refer to compounds comprising dicarboxylic acids, their alkyl esters (C1 to C4 low-carbon alkyl esters, such as monomethyl esters, monoethyl esters, dimethyl esters, diethyl esters, or dibutyl esters, etc.), and their anhydrides, which can react with diamines to form repeating units derived from dicarboxylic acids (dicarboxylic acid moieties). Furthermore, repeating units derived from dicarboxylic acids and repeating units derived from diamines (diamine moieties) refer to residues from which hydrogen atoms (from the amino group) or hydroxyl or alkoxy groups are removed during the polymerization of dicarboxylic acids and diamines.

[0049] In some embodiments, the aliphatic dicarboxylic acid may be C6 to C6. 20 Straight-chain, branched, or cyclic aliphatic dicarboxylic acids, such as adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid. Specifically, aliphatic dicarboxylic acids can be adipic acid or sebacic acid.

[0050] In some embodiments, the aromatic diamine may be at least one type of C6 to C6. 30 Aromatic diamines. For example, aromatic diamines can be selected from phenylenediamine compounds (such as m-phenylenediamine and p-phenylenediamine), xylene diamine compounds (such as m-xylene diamine and p-xylene diamine), and naphthylenediamine compounds, etc.

[0051] In some embodiments, the molar ratio (diamine / dicarboxylic acid) of repeating units derived from dicarboxylic acids to repeating units derived from diamines in the aromatic polyamide resin can range from about 0.95 to about 1.15 (e.g., from about 1.00 to about 1.10). Within this range, the environmentally friendly polyamide resin composition can form a polyamide resin with a suitable degree of polymerization for molding and can prevent the deterioration of properties due to unreacted monomers.

[0052] In some embodiments, the aromatic polyamide resin can have a glass transition temperature of about 30°C to about 100°C (e.g., about 40°C to about 80°C), as measured by differential scanning calorimetry (DSC). Within this range, environmentally friendly polyamide resin compositions can exhibit excellent properties in terms of heat resistance, rigidity, and impact resistance.

[0053] Furthermore, using an Ubbelohde viscometer at 25°C, the aromatic polyamide resin can have an intrinsic viscosity [η] of about 0.7 dL / g to about 1.2 dL / g (e.g., about 0.8 dL / g to about 1.0 dL / g), wherein the sample is prepared by dissolving the aromatic polyamide resin in a concentrated sulfuric acid solution (98%) to a concentration of up to 0.5 g / dL. Within this range, the environmentally friendly polyamide resin composition exhibits excellent properties in terms of heat resistance, rigidity, and impact resistance.

[0054] In some embodiments, based on 100 wt% of the base materials (recycled polyamide resin, aliphatic polyamide resin, aromatic polyamide resin, and glass fiber), the aromatic polyamide resin may be present in an amount of about 1 wt% to about 20 wt% (e.g., about 5 wt% to about 15 wt%). If the content of the aromatic polyamide resin is less than about 1 wt% based on 100 wt% of the base materials, the environmentally friendly polyamide resin composition may suffer from deterioration in its separability from the polyurethane adhesive, heat resistance, and rigidity, etc., and if the content of the aromatic polyamide resin exceeds about 20 wt%, the environmentally friendly polyamide resin composition may suffer from deterioration in its impact resistance, etc.

[0055] (D) Glass fiber

[0056] According to one embodiment, glass fiber can be used with recycled polyamide resins, aliphatic polyamide resins, aromatic polyamide resins, poly(ether ester amide) block copolymers, and talc to enhance the properties of environmentally friendly polyamide resin compositions in terms of environmental friendliness, adhesion and separability relative to polyurethane adhesives, impact resistance, heat resistance, and rigidity, and can be used as glass fiber for typical thermoplastic resin compositions.

[0057] In some implementations, the glass fiber may have a cross-section of various shapes (such as circular, elliptical, and rectangular shapes).

[0058] In some embodiments, the glass fiber may be a flat glass fiber with a rectangular or elliptical cross-section. Measured using a scanning electron microscope (SEM), the flat glass fiber may have a cross-sectional aspect ratio (major axis to minor axis in the cross-section) of about 1.5 to about 10 (e.g., about 2 to about 8), a minor axis of about 2 μm to about 10 μm (e.g., about 4 μm to about 8 μm), and a pre-processing length of about 1 mm to about 15 mm (e.g., about 2 mm to about 8 mm). Within this range, the environmentally friendly polyamide resin composition can achieve improvements in rigidity and processability, among other things.

[0059] In some implementations, glass fibers may be surface-treated using typical surfactants.

[0060] In some embodiments, based on 100 wt% of the base materials (recycled polyamide resin, aliphatic polyamide resin, aromatic polyamide resin, and glass fiber), the glass fiber may be present in an amount of about 40 wt% to about 80 wt% (e.g., about 50 wt% to about 70 wt%). If the glass fiber content is less than about 40 wt% based on 100 wt% of the base materials, the environmentally friendly polyamide resin composition may suffer from deterioration in adhesion to polyurethane adhesives, etc., and if the glass fiber content exceeds about 80 wt%, the environmentally friendly polyamide resin composition may suffer from deterioration in separability from polyurethane adhesives, etc.

[0061] (E) Poly(ether ester amide) block copolymer

[0062] According to one embodiment, the poly(ether ester amide) block copolymer can be used with recycled polyamide resins, aliphatic polyamide resins, aromatic polyamide resins, glass fibers, and talc to enhance the environmentally friendly polyamide resin composition in terms of environmental friendliness, adhesion and separability relative to polyurethane adhesives, impact resistance, heat resistance, and rigidity. The poly(ether ester amide) block copolymer can be a block copolymer comprising a reaction mixture of an aminocarboxylic acid, a lactam or a diamine-dicarboxylic acid salt having 6 or more carbon atoms, polytetramethylene glycol, and a dicarboxylic acid having 4 to 20 carbon atoms.

[0063] In some embodiments, salts of aminocarboxylic acids, lactams, or diamine-dicarboxylic acids having six or more carbon atoms may include, for example, aminocarboxylic acids such as ω-aminohexanoic acid, ω-aminoheptanoic acid, ω-aminooctanoic acid, ω-aminononanoic acid, ω-aminodecanoic acid, 1,1-aminoundecanoic acid, and 1,2-aminododecanoic acid; lactams such as caprolactam, heptanolactam, octanolactam, and lauryllactam; and salts of diamine-dicarboxylic acids such as salts of hexamethylenediamine-adipic acid and hexamethylenediamine-isophthalic acid. For example, salts of 1,2-aminododecanoic acid, caprolactam, or hexamethylenediamine-adipic acid may be used.

[0064] In some embodiments, dicarboxylic acids having 4 to 20 carbon atoms may include, for example, terephthalic acid, 1,4-cyclohexanoic acid, sebacic acid, adipic acid, and dodecanecarboxylic acid.

[0065] Specifically, the bond between a salt of an aminocarboxylic acid, lactam, or diamine-dicarboxylic acid having 6 or more carbon atoms and polytetramethylene glycol can be an ester bond; the bond between a salt of an aminocarboxylic acid, lactam, or diamine-dicarboxylic acid having 6 or more carbon atoms and a dicarboxylic acid having 4 to 20 carbon atoms can be an amide bond; and the bond between polytetramethylene glycol and a dicarboxylic acid having 4 to 20 carbon atoms can be an ester bond.

[0066] In some embodiments, the poly(ether ester amide) block copolymer can be prepared by methods well known in the art. For example, the poly(ether ester amide) block copolymer can be prepared by the methods disclosed in Japanese Patent Publication No. S56-045419 and Japanese Patent Publication No. S55-133424.

[0067] In some embodiments, the poly(ether ester amide) block copolymer may comprise about 10 wt% to about 95 wt% of polyether-ester blocks. Within this range, environmentally friendly polyamide resin compositions can exhibit excellent impact resistance, etc.

[0068] In some embodiments, the poly(ether ester amide) block copolymer may be present in an amount of about 5 parts by weight to about 15 parts by weight (e.g., about 6 parts by weight 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 poly(ether ester amide) block copolymer is less than about 5 parts by weight relative to about 100 parts by weight of the base resin, the environmentally friendly polyamide resin composition may suffer from deterioration in adhesion to polyurethane adhesives and impact resistance, etc., and if the content of the poly(ether ester amide) block copolymer exceeds about 15 parts by weight, the environmentally friendly polyamide resin composition may suffer from deterioration in separability from polyurethane adhesives, heat resistance, and rigidity, etc.

[0069] In some embodiments, glass fiber (D) and poly(ether ester amide) block copolymer (E) may be present in a weight ratio (D:E) of about 1:0.05 to about 1:0.3 (e.g., about 1:0.1 to about 1:0.2). Within this range, environmentally friendly polyamide resin compositions may exhibit better adhesion and separability, impact resistance, heat resistance, and rigidity compared to polyurethane adhesives.

[0070] (F) Talc

[0071] According to one embodiment, talc can be used with recycled polyamide resins, aliphatic polyamide resins, aromatic polyamide resins, glass fibers, and poly(ether ester amide) block copolymers to enhance the properties of environmentally friendly polyamide resin compositions in terms of environmental friendliness, adhesion and separability relative to polyurethane adhesives, impact resistance, heat resistance, and rigidity, and can be used as talc for typical thermoplastic resin compositions.

[0072] In some embodiments, talc may be a flake-type inorganic filler and may have an average particle size of about 0.5 μm to about 10 μm (e.g., about 1 μm to about 7 μm), as measured by a particle analyzer (MalvernMastersizer 3000). Within this range, environmentally friendly polyamide resin compositions may exhibit excellent adhesion and separability relative to polyurethane adhesives, as well as heat resistance, etc.

[0073] In some embodiments, talc may be present in an amount of about 0.1 parts by weight to about 1 part by weight (e.g., about 0.15 parts by weight to about 0.5 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 talc content is less than about 0.1 parts by weight relative to about 100 parts by weight of the base resin, the environmentally friendly polyamide resin composition may suffer from deterioration in adhesion to polyurethane adhesives, etc., and if the talc content exceeds about 1 part by weight, the environmentally friendly polyamide resin composition may suffer from deterioration in impact resistance, etc.

[0074] In some embodiments, the poly(ether ester amide) block copolymer (E) and talc (F) may be present in a weight ratio (E:F) of about 1:0.005 to about 1:0.08 (e.g., about 1:0.01 to about 1:0.07). Within this range, the environmentally friendly polyamide resin composition exhibits superior properties relative to polyurethane adhesives in terms of adhesion and separability, impact resistance, heat resistance, and rigidity.

[0075] The environmentally friendly polyamide resin composition according to the invention may further include typical additives as needed, provided that the additives do not inhibit the effects of the invention. Additives may include, but are not limited to, heat stabilizers, flame retardants, antioxidants, lubricants, release agents, nucleating agents, colorants, and mixtures thereof. The additives may be present in an amount of about 0.001 parts by weight to about 40 parts by weight (e.g., about 0.1 parts by weight to about 20 parts by weight) relative to about 100 parts by weight of the base material.

[0076] An environmentally friendly polyamide resin composition according to one embodiment can be prepared in granular form by mixing the aforementioned components and then melt-extruded in a typical twin-screw extruder at 240°C to 320°C (e.g., 250°C to 310°C).

[0077] In some embodiments, following the DuPont drop test, the environmentally friendly polyamide resin composition can have an adhesive strength (potential energy) of about 700 mJ to about 990 mJ (e.g., about 750 mJ to about 950 mJ) when a drop hammer with a mass of 10 g to 500 g is dropped onto the sample from a height of 50 cm using a drop tester, and the sample with dimensions of 50 mm × 50 mm × 4 mm separates from a glass plate with dimensions of 25 mm × 25 mm × 0.7 mm. The drop hammer is fixed to the upper end of the drop tester and the sample is fixed to its lower end. 0.018 g of polyurethane adhesive (EH9777BS, HB Fuller Ltd.) is applied to the sample at 110°C with a thickness of 1 mm, and the glass plate is attached to the sample by the adhesive. The adhesive is then cured at 25°C and 50% RH for 72 hours.

[0078] In some embodiments, an environmentally friendly polyamide resin composition prevents adhesive residue on a 50mm × 50mm × 4mm sample when the sample is separated from a glass plate with dimensions of 25mm × 25mm × 0.7mm by using a universal testing machine (UTM) to drop a 5mm diameter drop hammer onto the sample at a test speed of 20mm / min. The drop hammer is fixed to the upper clamp of the UTM and the glass plate is fixed to its lower end. 0.018g of polyurethane adhesive (EH9777BS, HB Fuller Ltd.) is applied to the sample at 110°C with a thickness of 1mm, and the glass plate is attached to the sample by the adhesive. The adhesive is then cured at 25°C and 50%RH for 72 hours and heated at 75°C for 15 minutes.

[0079] In some embodiments, the environmentally friendly polyamide resin composition can have a notched cantilever beam impact strength of about 12 kgf·cm / cm to about 30 kgf·cm / cm (e.g., about 14 kgf·cm / cm to about 25 kgf·cm / cm) when measured against a 1 / 8" thick sample according to ASTM D256.

[0080] In some embodiments, the environmentally friendly polyamide resin composition may have a heat distortion temperature (HDT) of about 175°C to about 195°C (e.g., about 177°C to about 193°C) as measured by ASTM D648 at a heating rate of 120°C / hr under a load of 1.82 MPa.

[0081] In some embodiments, measured at a rate of 2.8 mm / min on a 6.4 mm thick sample according to ASTM D790, the environmentally friendly polyamide resin composition can have approximately 90,000 kgf / cm². 2 Approximately 180,000 kgf / cm 2 (For example, approximately 100,000 kgf / cm²) 2 Approximately 170,000 kgf / cm 2 ) flexural modulus.

[0082] The molded articles according to the present invention are produced from an environmentally friendly polyamide resin composition.

[0083] Specifically, the molded article may be an electronic device housing, which includes a glass frame and a plastic component adjacent to at least one surface of the glass frame.

[0084] Figure 1 This is a schematic cross-sectional view of an electronic device housing according to one embodiment. Although the length, thickness, or width of the components constituting the invention may be enlarged in the drawings for clarity, it should be understood that the invention is not limited thereto. Reference Figure 1 The electronic device housing according to an embodiment includes a glass frame 10 and a plastic component 20 adjacent to at least one surface of the glass frame 10, wherein the plastic component is formed of an environmentally friendly polyamide resin composition.

[0085] In some embodiments, the glass frame 10 and the plastic component 20 may have various shapes, not limited to those shown in the figures. Here, the glass frame 10 may be adjacent to at least one surface of the plastic component 20. Adjacent structures can be achieved by bonding using polyurethane adhesive.

[0086] In some implementations, the glass frame 10 may be selected from any product suitable for typical electronic device housings or a commercially available product.

[0087] In some embodiments, the plastic component 20 may be formed from an environmentally friendly polyamide resin composition by various molding methods (such as injection molding, extrusion molding, vacuum molding, and casting). Specifically, the plastic component 20 may be an internal material for electrical / electronic devices, etc. Detailed Implementation

[0088] The invention will now be described in more detail with reference to some embodiments. It should be understood that these embodiments are provided for illustrative purposes only and are in no way intended to limit the invention.

[0089] Example

[0090] Details of the components used in the examples and comparative examples are as follows.

[0091] (A) Recycled polyamide resin

[0092] Polyamide 6 derived from marine waste (manufacturer: Jinjiang Yonghong Renewable Resources, product name: YH-005).

[0093] (B) Aliphatic polyamide resin

[0094] Polyamide 10.12 (manufacturer: Shandong Guangyin New Material Co., Ltd., product name: B150) was used.

[0095] (C) Aromatic polyamide resin

[0096] Polyamide MXD10 (manufacturer: Mitsubishi Gas Chemical Co., Ltd., product name: LEXTER8000) was used.

[0097] (D) Glass fiber

[0098] Flat glass fiber (manufacturer: Nittobo Ltd., product name: CSG 3PA-820).

[0099] (E) Poly(ether ester amide) block copolymer

[0100] Use (E1) polyamide 12-polytetramethylene ether block copolymer (manufacturer: Evonik, product name: Vestamid E62-S3).

[0101] (E2) polyamide 6-polyethylene oxide block copolymer (PA6-b-PEO, manufacturer: Sanyo Chemical Co., Ltd., product name: Pelestat 1251).

[0102] (F) Talc

[0103] Use talc (manufacturer: KOCH, product name: KCM-6300C).

[0104] Examples 1 to 12 and Comparative Examples 1 to 10

[0105] The aforementioned components were mixed in the amounts listed in Tables 1 through 4, and then extruded at 260°C to prepare a polyamide resin composition in granular form. Here, extrusion was performed using a twin-bar extruder (L / D: 44, diameter: 45 mm). The prepared granules were dried at 80°C for 4 hours or longer, and then injection molded using a 6-ounce injection molding machine (molding temperature: 280°C, die temperature: 80°C) to prepare samples. The prepared samples were subjected to the following property evaluations. The results are shown in Tables 1, 2, 3, and 4.

[0106] Feature evaluation

[0107] (1) Adhesive strength (potential energy, unit: mJ): According to the DuPont drop test, the adhesive strength (potential energy) was measured when a sample with a mass of 10g to 500g was dropped from a height of 50 cm onto the sample using a drop tester, and the sample with dimensions of 50mm×50mm×4mm was separated from a glass plate with dimensions of 25mm×25mm×0.7mm, wherein the drop hammer was fixed to the upper end of the drop tester and the sample was fixed to its lower end, wherein 0.018g of polyurethane adhesive (EH9777BS, HB Fuller Ltd.) was applied to the sample at 110°C with a thickness of 1mm, and the glass plate was attached to the adhesive on the sample, and then the adhesive was cured at 25°C and 50%RH for 72 hours.

[0108] Potential energy (Ep) = mass (mass of the falling hammer at separation) × 9.8 (acceleration due to gravity) × 50 (height of the weight at separation)

[0109] (2) Separability Assessment: A drop hammer with a diameter of 5 mm was dropped onto the sample using a universal testing machine (UTM) at a test speed of 20 mm / min. The presence of residual adhesive on the sample (50 mm × 50 mm × 4 mm) was examined as the sample separated from the glass plate (25 mm × 25 mm × 0.7 mm). The drop hammer was fixed to the upper clamp of the UTM, and the glass plate was fixed to its lower end. 0.018 g of polyurethane adhesive (EH9777BS, HB Fuller Ltd.) was applied to the sample at 110°C with a thickness of 1 mm, and the glass plate was attached to the adhesive on the sample. The adhesive was then cured at 25°C and 50% RH for 72 hours, followed by heating at 75°C for 15 min. (OK: No adhesive residue, NG: Residual adhesive)

[0110] (3) Cut cantilever beam impact resistance (unit: kgf·cm / cm): The cut cantilever beam impact strength was measured on a 1 / 8" thick sample according to ASTM D256.

[0111] (4) Heat distortion temperature (HDT) (unit: °C): HDT was measured according to ASTM D648 at a heating rate of 120 °C / hr under a load of 1.82 MPa.

[0112] (5) Flexural modulus (unit: kgf / cm) 2 ): The flexural modulus was measured on a 6.4 mm thick sample at a rate of 2.8 mm / min according to ASTM D790.

[0113] Table 1

[0114]

[0115] *Parts by weight: Parts by weight relative to 100 parts by weight of the base material (A+B+C+D)

[0116] Table 2

[0117]

[0118] *Parts by weight: Parts by weight relative to 100 parts by weight of the base material (A+B+C+D)

[0119] Table 3

[0120]

[0121] *Parts by weight: Parts by weight relative to 100 parts by weight of the base material (A+B+C+D)

[0122] Table 4

[0123]

[0124] *Parts by weight: Parts by weight relative to 100 parts by weight of the base material (A+B+C+D)

[0125] As can be seen from the results, the environmentally friendly polyamide resin composition according to the present invention ensures environmental friendliness by using a specific amount or more of recycled polyamide resin (5 wt% or more based on 100 wt% base material) and exhibits superior properties in terms of adhesion (bonding strength) and separability, impact resistance (cut cantilever beam impact strength), heat resistance (HDT) and rigidity (flexural modulus) relative to polyurethane adhesives.

[0126] Conversely, it is evident that the polyamide resin composition of Comparative Example 1, prepared using insufficient amounts of recycled polyamide resin and aromatic polyamide resin and excessive amounts of aliphatic polyamide resin, suffers from deterioration in environmental friendliness, adhesion to polyurethane adhesives, heat resistance, and rigidity; the polyamide resin composition of Comparative Example 2, prepared using excessive amounts of aromatic polyamide resin and insufficient amounts of aliphatic polyamide resin, suffers from deterioration in impact resistance; and the polyamide resin composition of Comparative Example 3, prepared using excessive amounts of recycled polyamide resin, suffers from deterioration in separability from polyurethane adhesives and impact resistance. It is evident that the polyamide resin composition of Comparative Example 4, prepared using insufficient amounts of glass fiber, suffers from deterioration in adhesion to polyurethane adhesives; and the polyamide resin composition of Comparative Example 5, prepared using excessive amounts of glass fiber, suffers from deterioration in separability from polyurethane adhesives. It is evident that the polyamide resin composition of Comparative Example 6, prepared using an insufficient amount of poly(ether ester amide) block copolymer, suffers from deterioration in adhesion to polyurethane adhesives and impact resistance; the polyamide resin composition of Comparative Example 7, prepared using an excessive amount of poly(ether ester amide) block copolymer, suffers from deterioration in separability from polyurethane adhesives, heat resistance, and rigidity; and the polyamide resin composition of Comparative Example 8, prepared using polyamide 6-polyethylene oxide block copolymer (E2) instead of the poly(ether ester amide) block copolymer according to the present invention, suffers from deterioration in separability from polyurethane adhesives. Furthermore, it is evident that the polyamide resin composition of Comparative Example 9, prepared using an insufficient amount of talc, suffers from deterioration in adhesion to polyurethane adhesives; and the polyamide resin composition of Comparative Example 10, including an excessive amount of talc, suffers from deterioration in impact resistance.

[0127] Although some exemplary embodiments have been described herein, those skilled in the art will understand that these embodiments are given by way of illustration only, and various modifications, variations, and changes can be made without departing from the spirit and scope of the invention. Therefore, the embodiments should not be construed as limiting the scope of the invention, but rather as illustrative. The scope of the invention should be interpreted as covering all modifications or variations derived from the claims and their equivalents.

Claims

1. An environmentally friendly polyamide resin composition, comprising: The base material comprises about 100 parts by weight of recycled polyamide resin, about 5 wt% to about 25 wt% of aliphatic polyamide resin other than polyamide 6 and polyamide 6.6, about 1 wt% to about 20 wt% of aromatic polyamide resin and about 40 wt% to about 80 wt% of glass fiber. About 5 parts by weight to about 15 parts by weight of a poly(ether ester amide) block copolymer; and From about 0.1 parts by weight to about 1 part by weight of talc, The poly(ether ester amide) block copolymer is a block copolymer comprising a reaction mixture of an aminocarboxylic acid, a lactam or a diamine-dicarboxylic acid salt having 6 or more carbon atoms, polytetramethylene glycol and a dicarboxylic acid having 4 to 20 carbon atoms.

2. The environmentally friendly polyamide resin composition according to claim 1, wherein the recycled polyamide resin comprises at least one of polyamide 6 derived from marine waste and polyamide 6.6 derived from marine waste.

3. The environmentally friendly polyamide resin composition according to claim 1 or 2, wherein the aliphatic polyamide resin includes 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. The environmentally friendly polyamide resin composition according to any one of claims 1 to 3, wherein the aromatic polyamide resin is a polymer of aliphatic dicarboxylic acid and aromatic diamine.

5. The 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 in a cross-sectional view, an aspect ratio (major axis / minor axis in the cross-section) of about 1.5 to about 10, and a minor axis of about 2 μm to about 10 μm.

6. The environmentally friendly polyamide resin composition according to any one of claims 1 to 5, wherein the glass fiber and the poly(ether ester amide) block copolymer are present in a weight ratio of about 1:0.05 to about 1:0.

3.

7. The environmentally friendly polyamide resin composition according to any one of claims 1 to 6, wherein the poly(ether ester amide) block copolymer and the talc are present in a weight ratio of about 1:0.005 to about 1:0.

08.

8. The environmentally friendly polyamide resin composition according to any one of claims 1 to 7, wherein, according to the DuPont drop test, a drop hammer having a mass of 10 g to 500 g is dropped onto the sample from a height of 50 cm using a drop tester, and the sample having dimensions of 50 mm × 50 mm × 4 mm is separated from a glass plate having dimensions of 25 mm × 25 mm × 0.7 mm, the environmentally friendly polyamide resin composition has an adhesive strength (potential energy) of about 700 mJ to about 990 mJ, wherein the drop hammer is fixed to the upper end of the drop tester and the sample is fixed to its lower end, wherein 0.018 g of a polyurethane adhesive (EH9777BS, HB Fuller Ltd.) is applied to the sample at 110°C with a thickness of 1 mm, and the glass plate is attached to the sample via the adhesive, and the adhesive is subsequently cured at 25°C and 50% RH for 72 hours.

9. The environmentally friendly polyamide resin composition according to any one of claims 1 to 8, wherein a drop hammer with a diameter of 5 mm is dropped onto the sample at a test speed of 20 mm / min using a universal testing machine (UTM), and when the sample separates from a glass plate having dimensions of 25 mm × 25 mm × 0.7 mm, the environmentally friendly polyamide resin composition prevents the adhesive from remaining on the sample having dimensions of 50 mm × 50 mm × 4 mm, wherein the drop hammer is fixed to the upper clamp of the UTM and the glass plate is fixed to its lower end, wherein 0.018 g of a polyurethane adhesive (EH9777BS, HB Fuller Ltd.) is applied to the sample at 110°C with a thickness of 1 mm, and the glass plate is attached to the sample by the adhesive, and then the adhesive is cured at 25°C and 50% RH for 72 hours and heated at 75°C for 15 min.

10. The environmentally friendly polyamide resin composition according to any one of claims 1 to 9, wherein the environmentally friendly polyamide resin composition has a notched cantilever beam impact strength of about 12 kgf·cm / cm to about 30 kgf·cm / cm as measured according to ASTM D256 for a 1 / 8" thick sample.

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

12. The environmentally friendly polyamide resin composition according to any one of claims 1 to 11, wherein the environmentally friendly polyamide resin composition has a content of about 90,000 kgf / cm² when measured at a rate of 2.8 mm / min on a 6.4 mm thick sample according to ASTM D790. 2 Approximately 180,000 kgf / cm 2 Flexural modulus.

13. A molded article formed from an environmentally friendly polyamide resin composition according to any one of claims 1 to 12.

14. An electronic device housing, comprising: Glass frame; and A plastic component, adjacent to at least one surface of the glass frame. The plastic component is formed from an environmentally friendly polyamide resin composition according to any one of claims 1 to 12.

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