Polyamide resin composition and article produced therefrom

Abstract

A polyamide resin composition of the present invention comprises: approximately 100 parts by weight of a base material comprising approximately 30-60 wt% of a copolymerized polyamide resin, which comprises a repeating unit derived from a cyclic aliphatic diamine and a repeating unit derived from an aliphatic dicarboxylic acid, approximately 10-40 wt% of a recycled polyamide resin recovered within 50 km from the coastline and approximately 20-40 wt% of glass fibers; approximately 1-10 parts by weight of a maleic anhydride-modified olefin-based elastomer; and approximately 5-15 parts by weight of a maleic anhydride-modified styrene-based elastomer. The polyamide resin composition has excellent eco-friendliness, impact resistance, flowability, appearance characteristics, a balance of these physical properties, and the like.

Description

Polyamide resin composition and molded article manufactured therefrom

[0001] The present invention relates to a polyamide resin composition and a molded article manufactured therefrom. More specifically, the present invention relates to a polyamide resin composition having excellent environmental friendliness, impact resistance, fluidity, appearance characteristics, and a balance of these physical properties, and a molded article manufactured therefrom.

[0002]

[0003] Polyamide resin boasts excellent processability, impact resistance, and mechanical properties, making it useful for housings for various electrical and electronic devices, as well as for interior and exterior automotive materials. Furthermore, with the trend toward thinner and lighter materials, polyamide resin is being blended with inorganic reinforcing agents like glass fiber to further enhance properties like rigidity and heat resistance, leading to its application in interior and exterior materials for electrical and electronic devices.

[0004] Wearable materials, for which demand is growing, require superior aesthetic properties in addition to mechanical properties such as impact resistance. Crystalline polyamide resins have limitations in achieving impact resistance, and their injection moldability is inferior to that of other long-chain polyamide resins. To address this issue, research has been conducted to improve impact resistance and injection moldability by introducing amorphous polyamide resins into crystalline polyamide resins.

[0005] Furthermore, with the passage of marine plastic reduction legislation, particularly in the US and Europe, global companies are increasingly demanding eco-friendly materials. Consequently, products using high levels of recycled raw materials are being developed. For example, in 2021, OBP (Ocean Bound Plastic) PET (recycled PET recovered within 50 km of the coastline) was used as a renewable raw material in a product.

[0006] However, since most recycled raw materials are processed multiple times and have unclear origins, even if they go through a washing process before being received, problems such as decomposition of thermoplastic resins caused by the recycled raw materials and deterioration of the properties of materials (thermoplastic resin compositions and molded products) may occur when recycled raw materials are used in high concentrations. In particular, OBP (Ocean Bound Plastic) materials contain a large amount of ionic components and foreign substances in the recycled plastic due to long-term exposure to seawater. Therefore, when applied in a high concentration of about 9 wt% or more of the total resin composition, there is a high possibility that the mechanical properties and appearance characteristics of the thermoplastic resin composition will deteriorate.

[0007] Therefore, there is a need to develop a polyamide resin composition that has excellent environmental friendliness, impact resistance, fluidity (injection properties), appearance characteristics, and a balance of these properties.

[0008] The background technology of the present invention is disclosed in Korean Patent Publication No. 10-2016-0038412, etc.

[0009]

[0010] The purpose of the present invention is to provide a polyamide resin composition having excellent environmental friendliness, impact resistance, fluidity, appearance characteristics, and balance of these physical properties.

[0011] Another object of the present invention is to provide a molded product formed from the polyamide resin composition.

[0012] The above and other objects of the present invention can all be achieved by the present invention described below.

[0013]

[0014] 1. One aspect of the present invention relates to a polyamide resin composition. The polyamide resin composition comprises about 100 parts by weight of a base material comprising about 30 to about 60 wt% of a copolymerized polyamide resin comprising a repeating unit derived from a cyclic aliphatic diamine and a repeating unit derived from an aliphatic dicarboxylic acid, about 10 to about 40 wt% of a recycled polyamide resin recovered within 50 km from a coastline, and about 20 to about 40 wt% of glass fiber; about 1 to about 10 parts by weight of a maleic anhydride-modified olefinic elastomer; and about 5 to about 15 parts by weight of a maleic anhydride-modified styrene-based elastomer.

[0015] 2. In the above 1 specific example, the copolymerized polyamide resin may include at least one of polyamide MACM10, polyamide MACM12, polyamide MACM14, polyamide PACM10, polyamide PACM12, and polyamide PACM14.

[0016] 3. In the above 1 or 2 specific examples, the regenerated polyamide resin may include at least one of OBP (Ocean Bound Plastic) polyamide 6 and OBP polyamide 66.

[0017] 4. In the above 1 to 3 specific examples, the glass fiber may be a circular cross-section glass fiber with a cross-sectional diameter of about 5 to about 20 ㎛.

[0018] 5. In the above 1 to 4 specific examples, the maleic anhydride-modified olefin elastomer may include at least one of an ethylene-propylene copolymer graft-polymerized with maleic anhydride, an ethylene-1-butene copolymer graft-polymerized with maleic anhydride, an ethylene-1-octene copolymer graft-polymerized with maleic anhydride, and an ethylene-propylene-diene copolymer graft-polymerized with maleic anhydride.

[0019] 6. In the above 1 to 5 specific examples, the maleic anhydride-modified styrene-based elastomer may include at least one of a styrene-ethylene / butylene-styrene copolymer graft-polymerized with maleic anhydride, a styrene-ethylene-butylene copolymer graft-polymerized with maleic anhydride, a styrene-butadiene-styrene copolymer graft-polymerized with maleic anhydride, styrene-isobutylene-styrene and styrene-ethylene / butadiene-styrene graft-polymerized with maleic anhydride.

[0020] 7. In the above 1 to 6 specific examples, the weight ratio of the sum of the regenerated polyamide resin, the maleic anhydride-modified olefin-based elastomer, and the maleic anhydride-modified styrene-based elastomer may be about 1:0.1 to about 1:1.

[0021] 8. In the above 1 to 7 specific examples, the weight ratio of the maleic anhydride-modified olefin-based elastomer and the maleic anhydride-modified styrene-based elastomer may be about 1:1 to about 1:10.

[0022] 9. In the above 1 to 8 specific examples, the content of the regenerated polyamide resin may be about 10 wt% or more among 100 wt% of the total polyamide resin composition.

[0023] 10. In the above 1 to 9 specific examples, the polyamide resin composition may have a notched Izod impact strength of about 8 to about 20 kgf·cm / cm of a 1 / 8" thick specimen measured according to ASTM D256.

[0024] 11. In the above 1 to 10 specific examples, the polyamide resin composition may not cause cracks when a 1 kg weight or a 500 g weight is dropped 15 times from a height of 1 m onto an injection molded specimen having a thickness of 1 mm.

[0025] 12. In the above 1 to 11 specific examples, the polyamide resin composition may have a melt flow index (MI) of about 9 to about 30 g / 10 min, measured under conditions of 250°C and 5 kgf according to ASTM D1238.

[0026] 13. Another aspect of the present invention relates to a molded article. The molded article is characterized in that it is formed from a polyamide resin composition according to any one of 1 to 12.

[0027]

[0028] The present invention has the effect of providing a polyamide resin composition having excellent environmental friendliness, impact resistance, fluidity, appearance characteristics, and balance of physical properties thereof, and a molded article formed therefrom.

[0029]

[0030] Hereinafter, the present invention will be described in detail as follows.

[0031] The polyamide resin composition according to the present invention comprises (A) a copolymerized polyamide resin; (B) a regenerated polyamide resin; (C) glass fiber; (D) a maleic anhydride-modified olefin-based elastomer; and (E) a maleic anhydride-modified styrene-based elastomer.

[0032] In this specification, “a to b” indicating a numerical range is defined as “≥a and ≤b”.

[0033]

[0034] (A) Copolymer polyamide resin

[0035] According to one specific example of the present invention, a copolymer polyamide resin can be applied together with a regenerated polyamide resin, glass fiber, a maleic anhydride-modified olefin-based elastomer, a maleic anhydride-modified styrene-based elastomer, etc., to improve the eco-friendliness, impact resistance, fluidity, appearance characteristics, chemical resistance, and physical property balance of the polyamide resin composition. A copolymer polyamide resin including a repeating unit derived from a cyclic aliphatic diamine and a repeating unit derived from an aliphatic dicarboxylic acid can be used.

[0036] 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 to form a repeating unit derived from dicarboxylic acid (dicarboxylic acid moiety). In addition, in this specification, the dicarboxylic acid moiety 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.

[0037] In a specific example, the cyclic aliphatic diamine may be a cyclic aliphatic diamine having 6 to 30 carbon atoms. For example, bis(p-amino-3-methyl-cyclohexyl)methane (MACM), bis(p-amino-cyclohexyl)methane (PACM), etc. may be used.

[0038] In a specific example, the aliphatic dicarboxylic acid may be a linear aliphatic dicarboxylic acid having 6 to 20 carbon atoms. Examples include dodecanedioic acid, decanoic acid, tetradecanoic acid, and eicosanedioic acid. In addition, the aliphatic dicarboxylic acid may also be a cyclic aliphatic dicarboxylic acid. Examples include isophthalic acid and terephthalic acid.

[0039] In a specific example, the copolymerized polyamide resin may include at least one of polyamide MACM10, polyamide MACM12, polyamide MACM14, polyamide PACM10, polyamide PACM12, and polyamide PACM14.

[0040] In a specific example, the copolymerized polyamide resin can be manufactured according to a conventional polyamide manufacturing method, and for example, can be manufactured by polymerizing a monomer mixture including the aliphatic dicarboxylic acid and the cyclic aliphatic diamine. Here, the polymerization can be performed according to a conventional polymerization method, and for example, can be performed using a melt polymerization method, etc., and the polymerization temperature can be about 80 to about 300°C, for example, about 90 to about 280°C, and the polymerization pressure can be about 10 to about 40 kgf / cm. 2 It may include, but is not limited to.

[0041] In a specific example, the molar ratio (diamine / dicarboxylic acid) of the repeating unit derived from the cyclic aliphatic diamine and the repeating unit derived from the aliphatic dicarboxylic acid may be about 0.95 to about 1.15, for example, about 1 to about 1.1. Within this range, it is possible to produce a polymer having a degree of polymerization suitable for molding, and to prevent deterioration of physical properties due to unreacted monomers.

[0042] In a specific example, the copolymerized polyamide resin may have an intrinsic viscosity [η] of about 0.5 to about 2.5 dL / g, for example, about 0.5 to about 2 dL / g, measured using an Ubbelodhde viscometer at 25°C after being dissolved in a 98% sulfuric acid solution at a concentration of 0.5 g / dl. Within this range, the polyamide resin composition may have excellent fluidity (moldability), impact resistance, etc.

[0043] In a specific example, the copolymerized polyamide resin may be included in an amount of about 30 to about 60 wt%, for example, about 40 to about 55 wt%, specifically about 40 to about 50 wt%, based on 100 wt% of the total base material including the copolymerized polyamide resin, the recycled polyamide resin, and the glass fiber. When the content of the copolymerized polyamide resin is less than about 30 wt%, based on 100 wt% of the base material, the impact resistance, fluidity, appearance properties, etc. of the polyamide resin composition may be deteriorated, and when it exceeds about 60 wt%, there is a concern that the fluidity, appearance properties, etc. of the polyamide resin composition may be deteriorated.

[0044]

[0045] (B) Regenerated polyamide resin

[0046] According to one specific example of the present invention, a regenerated polyamide resin can be applied together with a copolymerized polyamide resin, glass fiber, a maleic anhydride-modified olefin-based elastomer, a maleic anhydride-modified styrene-based elastomer, etc., to improve the eco-friendliness, impact resistance, fluidity, appearance characteristics, and physical property balance of the polyamide resin composition, and a regenerated polyamide resin recovered within 50 km from the coastline can be used.

[0047] In a specific example, the regenerated polyamide resin may include at least one of OBP (Ocean Bound Plastic) polyamide 6 and OBP polyamide 66 as an environmentally friendly material.

[0048] In a specific example, the regenerated polyamide resin may have an intrinsic viscosity [η] measured according to ASTM D2857 of about 0.5 to about 4 dl / g, for example, about 1 to about 3 dl / g. Within this range, the polyamide resin composition may have excellent impact resistance, chemical resistance, and the like.

[0049] In a specific example, the recycled polyamide resin may be included in an amount of about 10 to about 40 wt%, for example, about 15 to about 35 wt%, specifically about 20 to about 30 wt%, based on 100 wt% of the total base material. If the content of the recycled polyamide resin is less than about 10 wt%, based on 100 wt% of the base material, the environmental friendliness, fluidity, appearance characteristics, etc. of the polyamide resin composition may be deteriorated, and if it exceeds about 40 wt%, there is a concern that the impact resistance, fluidity, appearance characteristics, etc. of the polyamide resin composition may be deteriorated.

[0050]

[0051] (C) Glass fiber

[0052] According to one specific example of the present invention, glass fiber can be applied together with a copolymerized polyamide resin, a regenerated polyamide resin, a maleic anhydride-modified olefin-based elastomer, a maleic anhydride-modified styrene-based elastomer, etc., to improve the eco-friendliness, impact resistance, fluidity, appearance characteristics, chemical resistance, and physical property balance of the polyamide resin composition, and glass fibers used in conventional thermoplastic resin compositions can be used.

[0053] In a specific example, the glass fiber may be in the form of a fiber and may have a round type cross-section.

[0054] In a specific example, the glass fibers of the circular cross-section may have a cross-sectional diameter of about 5 to about 20 µm as measured using a Scanning Electron Microscope (SEM) and a length before processing of about 2 to about 20 mm. Within this range, the rigidity, moldability, appearance characteristics, etc. of the polyamide resin composition may be improved.

[0055] In a specific example, the glass fiber may be treated with a conventional surface treatment agent. The surface treatment agent may include, but is not limited to, a silane compound, a urethane compound, an epoxy compound, or the like.

[0056] In a specific example, the glass fiber may be included in an amount of about 20 to about 40 wt%, for example, about 25 to about 35 wt%, based on 100 wt% of the total base material. If the content of the glass fiber is less than about 20 wt%, based on 100 wt% of the base material, the impact resistance of the polyamide resin composition may be reduced, and if it exceeds about 40 wt%, there is a concern that the fluidity, appearance characteristics, etc. of the polyamide resin composition may be reduced.

[0057]

[0058] (D) Maleic anhydride-modified olefin elastomer

[0059] According to one specific example of the present invention, a maleic anhydride-modified olefin-based elastomer can be applied together with a copolymerized polyamide resin, a regenerated polyamide resin, glass fiber, and a maleic anhydride-modified styrene-based elastomer, thereby improving the eco-friendliness, impact resistance, fluidity, appearance characteristics, and physical property balance of a polyamide resin composition, and may be obtained by graft polymerizing maleic anhydride (MAH) onto an olefin-based rubber polymer.

[0060] In a specific example, the maleic anhydride-modified olefin elastomer may include at least one of an ethylene-propylene copolymer graft-polymerized with maleic anhydride, an ethylene-1-butene copolymer graft-polymerized with maleic anhydride, an ethylene-1-octene copolymer graft-polymerized with maleic anhydride, and an ethylene-propylene-diene copolymer graft-polymerized with maleic anhydride.

[0061] In a specific example, the maleic anhydride-modified olefin-based elastomer may have a maleic anhydride content of about 0.1 to about 3 wt%, for example, about 0.3 to about 1.5 wt%, based on 100 wt% of the total maleic anhydride-modified olefin-based elastomer. Within this range, the impact resistance, appearance properties, etc. of the polyamide resin composition may be excellent.

[0062] In a specific example, the maleic anhydride-modified rubber polymer may have a melt flow index of about 0.01 to about 40 g / 10 min, for example, about 0.1 to about 10 g / 10 min, measured under conditions of 190°C and 2.16 kgf according to ASTM D1238. Within this range, the impact resistance, fluidity, etc. of the polyamide resin composition may be excellent.

[0063] In a specific example, the maleic anhydride-modified olefin-based elastomer may be included in an amount of about 1 to about 10 parts by weight, for example, about 2 to about 8 parts by weight, based on about 100 parts by weight of the base material. If the amount of the maleic anhydride-modified olefin-based elastomer is less than about 1 part by weight based on about 100 parts by weight of the base material, there is a concern that the impact resistance, etc. of the polyamide resin composition may be reduced, and if it exceeds about 10 parts by weight, there is a concern that the fluidity, appearance characteristics, etc. of the polyamide resin composition may be reduced.

[0064]

[0065] (E) Maleic anhydride modified styrene elastomer

[0066] A maleic anhydride-modified styrene-based elastomer according to one specific example of the present invention can be applied together with a copolymerized polyamide resin, a regenerated polyamide resin, glass fiber, and a maleic anhydride-modified olefin-based elastomer, thereby improving the eco-friendliness, impact resistance, fluidity, appearance characteristics, chemical resistance, and physical property balance of a polyamide resin composition, and may be obtained by graft polymerizing maleic anhydride (MAH) onto a styrene-based rubber polymer.

[0067] In a specific example, the maleic anhydride-modified styrene-based elastomer may include at least one of a styrene-ethylene / butylene-styrene copolymer graft-polymerized with maleic anhydride, a styrene-ethylene-butylene copolymer graft-polymerized with maleic anhydride, a styrene-butadiene-styrene copolymer graft-polymerized with maleic anhydride, styrene-isobutylene-styrene and styrene-ethylene / butadiene-styrene graft-polymerized with maleic anhydride.

[0068] In a specific example, the maleic anhydride-modified styrene elastomer may have a maleic anhydride content of about 0.1 to about 3 wt%, for example, about 0.3 to about 1.5 wt%, based on 100 wt% of the total maleic anhydride-modified styrene elastomer. Within this range, the polyamide resin composition may have excellent impact resistance, appearance properties, etc.

[0069] In a specific example, the maleic anhydride-modified rubber polymer may have a melt flow index of about 0.01 to about 40 g / 10 min, for example, about 0.1 to about 10 g / 10 min, measured under conditions of 230°C and 2.16 kgf according to ISO 1133. Within this range, the polyamide resin composition may have excellent impact resistance, fluidity, etc.

[0070] In a specific example, the maleic anhydride-modified styrene elastomer may be included in an amount of about 5 to about 15 parts by weight, for example, about 7 to about 13 parts by weight, based on about 100 parts by weight of the base material. If the amount of the maleic anhydride-modified styrene elastomer is less than about 5 parts by weight based on about 100 parts by weight of the base material, there is a concern that the impact resistance, etc. of the polyamide resin composition may be reduced, and if it exceeds about 15 parts by weight, there is a concern that the impact resistance, appearance characteristics, etc. of the polyamide resin composition may be reduced.

[0071] In a specific example, the weight ratio of the regenerated polyamide resin and the sum of the maleic anhydride-modified olefin-based elastomer and the maleic anhydride-modified styrene-based elastomer (regenerated polyamide resin: (maleic anhydride-modified olefin-based elastomer + maleic anhydride-modified styrene-based elastomer)) may be from about 1:0.1 to about 1:1, for example, from about 1:0.5 to about 1:0.8. In this range, the impact resistance, chemical resistance, appearance characteristics, etc. of the polyamide resin composition may be more excellent.

[0072] In a specific example, the weight ratio of the maleic anhydride-modified olefin-based elastomer and the maleic anhydride-modified styrene-based elastomer (maleic anhydride-modified olefin-based elastomer: maleic anhydride-modified styrene-based elastomer) may be about 1:1 to about 1:10, for example, about 1:1 to about 1:8, specifically about 1:1.2 to about 1:6. In this range, the impact resistance, moldability, appearance characteristics, etc. of the polyamide resin composition may be more excellent.

[0073]

[0074] A polyamide resin composition according to one specific embodiment of the present invention may further include additives included in conventional polyamide resin compositions. Examples of the additives include, but are not limited to, flame retardants, anti-drip agents, antioxidants, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, 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 10 parts by weight, based on about 100 parts by weight of the base material.

[0075]

[0076] A 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 220 to about 300°C, for example, about 230 to about 280°C, using a conventional twin-screw extruder.

[0077] In a specific example, the polyamide resin composition may have a content of recycled polyamide resin of about 10 wt% or more, for example, about 15 wt% or more, based on 100 wt% of the total polyamide resin composition. Within this range, the environmental friendliness requirement of the polyamide resin composition can be satisfied.

[0078] In a specific example, the polyamide resin composition may have a notched Izod impact strength of about 8 to about 20 kgf·cm / cm, for example, about 10 to about 15 kgf·cm / cm, of a 1 / 8" thick specimen measured according to ASTM D256.

[0079] In a specific example, the polyamide resin composition may not cause cracks when a 1 kg weight or a 500 g weight is dropped 15 times from a height of 1 m onto an injection molded specimen having a thickness of 1 mm.

[0080] In a specific example, the polyamide resin composition may have a melt-flow index (MI) of about 9 to about 30 g / 10 min, for example, about 10 to about 20 g / 10 min, measured under conditions of 250°C and 5 kgf according to ASTM D1238.

[0081]

[0082] A molded article according to the present invention is formed from the polyamide resin composition. The polyamide resin composition can be manufactured in the form of pellets, and the manufactured pellets can be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those skilled in the art to which the present invention pertains. The molded article is environmentally friendly due to the high content of recycled raw materials, and has excellent environmental friendliness, impact resistance, fluidity (injectionability), appearance characteristics, chemical resistance, and a balance of these physical properties, and is therefore useful as an electronic product housing, particularly, a smartwatch housing, a mobile phone housing, and the like.

[0083]

[0084] 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.

[0085]

[0086] Example

[0087] Below, the specifications of each component used in the examples and comparative examples are as follows.

[0088] (A) Copolymer polyamide resin

[0089] Polyamide MACM12 (Manufacturer: Shandong-Dongchen, Product Name: TM03) was used.

[0090] (B) Regenerated polyamide resin

[0091] Regenerated polyamide 6 (manufacturer: Jinjiang-Yonghong Regeneration Resource, product name: YH-005) recovered within 50 km from the coastline was used.

[0092] (C) Glass fiber

[0093] Circular cross-section glass fiber (Manufacturer: Nippon Electric Glass, Product name: ECS 03T-251H) was used.

[0094] (D) Maleic anhydride-modified olefin elastomer

[0095] An ethylene-propylene copolymer graft-polymerized with maleic anhydride (MAH-g-EP, manufacturer: Mitsui Chemical, product name: Tafmer MH7020) was used.

[0096] (E) Maleic anhydride modified styrene elastomer

[0097] A maleic anhydride graft polymerized styrene-ethylene / butylene-styrene copolymer (MAH-g-SEBS, manufacturer: Asahi Kasei, product name: Tuftec M1913) was used.

[0098]

[0099] Examples 1 to 10 and Comparative Examples 1 to 11

[0100] Each of the above components was added in the amounts shown in Tables 1, 2, 3, and 4 below, and then extruded at 250°C to produce pellets. The extrusion was performed using a twin-screw extruder with an L / D of 29 and a diameter of 45 mm. The produced pellets were dried at about 100°C for about 2 hours, and then injection-molded using a 6 oz injection molding machine (molding temperature: about 300°C, mold temperature: about 80°C) to produce specimens. The physical properties of the produced specimens were evaluated using the following methods, and the results are shown in Tables 1, 2, 3, and 4 below.

[0101]

[0102] Method of measuring physical properties

[0103] (1) 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.

[0104] (2) Impact resistance evaluation: 1 kg and 500 g weights were dropped 15 times from a height of 1 m on an injection molded specimen with a thickness of 1 mm, and the occurrence of cracks was checked.

[0105] (3) Melt flow index (unit: g / 10 min): Melt flow index (MI) was measured at 300℃ and 5 kgf according to ASTM D1238.

[0106] (4) Evaluation of appearance characteristics: Using a pin-point gate three-stage mold, a specimen with a thickness of 1 mm, a width of 50 mm, and a height of 200 mm was injected, and then the occurrence of color discoloration (gas marks and / or whitening) on ​​the surface of the injection specimen was visually confirmed.

[0107]

[0108] Example 12345 (A) (% by weight) 50464048.543.5 (B) (% by weight) 20243026.521.5 (C) (% by weight) 3030302535 (D) (parts by weight) 55555 (E) (parts by weight) 1010101010 Eco-friendly material content (% by weight) 17.420.926.12318.7 Notched Izod impact strength (kgf·cm / cm) 1413111014 Crack occurrence No occurrence No occurrence No occurrence No occurrence Melt flow index (g / 10 min) 1013152010 Color difference No occurrence No occurrence No occurrence No occurrence No occurrence

[0109] * Weight parts: Weight parts per 100 weight parts of basic materials (A+B+C)

[0110]

[0111] Example 678910(A) (% by weight) 4646464646(B) (% by weight) 2424242424(C) (% by weight) 3030303030(D) (parts by weight) 28552(E) (parts by weight) 101071313Content of eco-friendly material (% by weight) 21.420.321.420.320.9Notched Izod impact strength (kgf·cm / cm) 1014121312Crack occurrenceNo occurrenceNo occurrenceNo occurrenceNo occurrenceNo occurrenceMelt flow index (g / 10 min) 1412131318Color discolorationNo occurrenceNo occurrenceNo occurrenceNo occurrenceNo occurrence

[0112] * Weight parts: Weight parts per 100 weight parts of basic materials (A+B+C)

[0113]

[0114] Comparative Example 12345 (A) (Wt%) 25655653.535 (B) (Wt%) 4551431.520 (C) (Wt%) 3030301545 (D) (Parts by weight) 55555 (E) (Parts by weight) 1010101010 Eco-friendly material content (Wt%) 39.14.3 12.22 7.4 17.4 Notched Izod impact strength (kgf·cm / cm) 81717815 Crack occurrence No occurrence No occurrence No occurrence Melt flow index (g / 10 min) 35211203 Color difference occurrence No occurrence No occurrence No occurrence No occurrence

[0115] * Weight parts: Weight parts per 100 weight parts of basic materials (A+B+C)

[0116]

[0117] Comparative Example 67891011(A) (Wt%) 464646464646(B) (Wt%) 242424242424(C) (Wt%) 303030303030(D) (Wt%) 0.51555150(E) (Wt%) 1010120015Eco-friendly material content (Wt%) 21.719.222.619.220.920.9Notched Izod impact strength (kgf·cm / cm) 6209111312Crack occurrenceNon-occurrenceNon-occurrenceNon-occurrenceNon-occurrenceNon-occurrenceNon-occurrenceNon-occurrenceNon-occurrenceNon-occurrenceNon-occurrenceNon-occurrenceNon-occurrenceNon-occurrence

[0118] * Weight parts: Weight parts per 100 weight parts of basic materials (A+B+C)

[0119]

[0120] From the above results, it can be seen that the polyamide resin composition of the present invention is environmentally friendly by applying a certain amount or more of recycled raw material, and has excellent impact resistance (notched Izod impact strength, occurrence of cracks), fluidity (melt flow index), appearance characteristics (occurrence of color discoloration), and balance of these physical properties.

[0121] On the other hand, in the case of Comparative Example 1, where a small amount of copolymerized polyamide resin was applied and an excessive amount of recycled polyamide resin was applied, it was found that impact resistance, fluidity, and appearance characteristics were deteriorated, and in the case of Comparative Example 2, where an excessive amount of copolymerized polyamide resin was applied and a small amount of recycled polyamide resin was applied, the content of recycled raw materials was too small (4.3 wt% of the total polyamide resin composition, the content of recycled polyamide resin was 100 wt%) to meet the environmentally friendly requirements, and it was found that fluidity, appearance characteristics, and the like were deteriorated, and in the case of Comparative Example 3, where a small amount of recycled polyamide resin was applied, it was found that the environmental friendliness was relatively lowered compared to the examples, and the appearance characteristics, etc. were deteriorated. In the case of Comparative Example 4, where a small amount of glass fiber was applied, it was found that impact resistance, etc. were deteriorated, and in the case of Comparative Example 5, where an excessive amount of glass fiber was applied, it was found that fluidity, appearance characteristics, etc. were deteriorated. In the case of Comparative Example 6, where a small amount of maleic anhydride-modified olefin elastomer was applied, it can be seen that impact resistance, etc. were reduced, and in the case of Comparative Example 7, where an excessive amount of maleic anhydride-modified olefin elastomer was applied, it can be seen that fluidity, appearance characteristics, etc. were reduced. In the case of Comparative Example 8, where a small amount of maleic anhydride-modified styrene elastomer was applied, it can be seen that impact resistance, etc. were reduced, and in the case of Comparative Example 9, where an excessive amount of maleic anhydride-modified styrene elastomer was applied, it can be seen that impact resistance, appearance characteristics, etc. were reduced.

[0122] In addition, in the case of Comparative Example 10, where an excessive amount of maleic anhydride-modified olefin-based elastomer was applied and no maleic anhydride-modified styrene-based elastomer was applied, it can be seen that the fluidity, appearance characteristics, etc. were deteriorated, and in the case of Comparative Example 10, where no maleic anhydride-modified olefin-based elastomer was applied, it can be seen that the impact resistance, etc. were deteriorated.

[0123]

[0124] 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 30 to about 60 wt% of a copolymerized polyamide resin comprising a repeating unit derived from a cyclic aliphatic diamine and a repeating unit derived from an aliphatic dicarboxylic acid, about 10 to about 40 wt% of a regenerated polyamide resin recovered within 50 km from the coastline, and about 20 to about 40 wt% of glass fiber; About 1 to about 10 parts by weight of a maleic anhydride modified olefin elastomer; and A polyamide resin composition comprising about 5 to about 15 parts by weight of a maleic anhydride modified styrene elastomer.

2. A polyamide resin composition according to claim 1, characterized in that the copolymerized polyamide resin comprises at least one of polyamide MACM10, polyamide MACM12, polyamide MACM14, polyamide PACM10, polyamide PACM12, and polyamide PACM14.

3. A polyamide resin composition according to claim 1 or 2, characterized in that the regenerated polyamide resin comprises at least one of OBP (Ocean Bound Plastic) polyamide 6 and OBP polyamide 66.

4. A polyamide resin composition according to any one of claims 1 to 3, wherein the glass fiber is a circular glass fiber having a cross-sectional diameter of about 5 to about 20 ㎛.

5. A polyamide resin composition according to any one of claims 1 to 4, wherein the maleic anhydride-modified olefin elastomer comprises at least one of an ethylene-propylene copolymer graft-polymerized with maleic anhydride, an ethylene-1-butene copolymer graft-polymerized with maleic anhydride, an ethylene-1-octene copolymer graft-polymerized with maleic anhydride, and an ethylene-propylene-diene copolymer graft-polymerized with maleic anhydride.

6. A polyamide resin composition according to any one of claims 1 to 5, wherein the maleic anhydride-modified styrene-based elastomer comprises at least one of a styrene-ethylene / butylene-styrene copolymer graft-polymerized with maleic anhydride, a styrene-ethylene-butylene copolymer graft-polymerized with maleic anhydride, a styrene-butadiene-styrene copolymer graft-polymerized with maleic anhydride, styrene-isobutylene-styrene and styrene-ethylene / butadiene-styrene graft-polymerized with maleic anhydride.

7. A polyamide resin composition according to any one of claims 1 to 6, characterized in that the weight ratio of the sum of the regenerated polyamide resin, the maleic anhydride-modified olefin-based elastomer, and the maleic anhydride-modified styrene-based elastomer is about 1:0.1 to about 1:

1.

8. A polyamide resin composition according to any one of claims 1 to 7, characterized in that the weight ratio of the maleic anhydride-modified olefin-based elastomer and the maleic anhydride-modified styrene-based elastomer is about 1:1 to about 1:

10.

9. A polyamide resin composition according to any one of claims 1 to 8, characterized in that the content of the regenerated polyamide resin is about 10 wt% or more among 100 wt% of the total polyamide resin composition.

10. A polyamide resin composition according to any one of claims 1 to 9, characterized in that the polyamide resin composition has a notched Izod impact strength of about 8 to about 20 kgf·cm / cm of a 1 / 8" thick specimen measured according to ASTM D256.

11. A polyamide resin composition according to any one of claims 1 to 10, characterized in that no cracks occur when a 1 kg weight or a 500 g weight is dropped 15 times from a height of 1 m onto an injection molded specimen having a thickness of 1 mm.

12. A polyamide resin composition according to any one of claims 1 to 11, characterized in that the polyamide resin composition has a melt-flow index (MI) of about 9 to about 30 g / 10 min, measured under conditions of 250°C and 5 kgf according to ASTM D1238.

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