KR102326937B1 - Thermoplastic resin composition having reduced squeak sound and molded article produced therefrom - Google Patents

Abstract

One aspect of the present invention provides a thermoplastic resin composition comprising: 10 to 35 wt% of a first graft copolymer resin in which an ethylene·α-olefin-based rubber polymer and a first monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer are graft polymerized; 10 to 35 wt% of a vinyl-based copolymer resin in which an aromatic vinyl monomer and a vinyl cyan monomer are polymerized in a weight ratio of 60 to 80 : 20 to 60; 30 to 75 wt% of a polycarbonate resin; 1 to 8 wt% of a slipping agent; and 1 to 5 wt% of a chain extender.

Description

Thermoplastic resin composition with reduced noise generation and molded article manufactured therefrom

The present invention relates to a thermoplastic resin composition having excellent noise reduction properties, and more particularly, to a thermoplastic resin composition that can significantly reduce friction noise generated during contact between different parts and can be applied without painting based on excellent light resistance. .

Among the thermoplastic resins, ABS (Acrylonitrile-Butadiene-Styrene) resin has excellent mechanical strength, formability, color realization and plating properties and is used in a wide range of fields such as automobiles, home appliances, and OA, but its use is limited due to limited heat resistance and impact resistance has been On the other hand, polycarbonate resin has excellent heat resistance and impact resistance, but its use is limited due to poor formability and low impact resistance at low temperatures. In order to solve these problems, a method of blending an ABS resin and a polycarbonate resin is widely used. In detail, PC-ABS (Polycarbonate-ABS) resin with excellent mechanical strength, moldability, impact resistance and heat resistance can be obtained, so it is used in various interior and exterior fields including automobile interior parts that require stability in the event of a collision. .

However, as the electric vehicle market, which is an eco-friendly vehicle, continues to expand with the development of technology and the strengthening of environmental regulations, the problem of noise (BSR, Buzz, Squeak, Rattle), which was largely undetectable by the engine noise of existing internal combustion locomotives, has emerged. have. This is because electric vehicles have become aware of noises that occur irregularly while driving as they have quieter driving performance compared to internal combustion engine vehicles. It refers to the noise generated in an environment where irregular contact between other parts such as etc. continues. Recently, as expectations for the emotional quality of automobiles increase, the demand for noise reduction is being strengthened.

As a solution to this problem, it is a method to reduce the vibration energy applied from the outside by reducing the surface friction force of the material used as interior and exterior materials of the vehicle, and to self-dissipate the vibration energy applied from the outside, that is, a dynamic load or dynamic fluctuation (vibration). ) was proposed to be annihilated by the damping factor existing inside the material system. As an example of such a method, there is a method of anti-friction coating that increases friction resistance while making the surface of the material slippery. There is a problem of a decrease in durability in

As another method, there is a method of increasing the friction resistance of the exterior through a thermoplastic resin blended with methyl phenyl silicone oil, alkyl-modified silicone oil, and amino-modified silicone oil. However, there is a problem in that the effect of reducing the appearance and noise generation is reduced due to the low molecular weight silicone oil, which is weak under the hydrolysis environment, and the light resistance is weak.

Therefore, as described above, it is necessary to develop a thermoplastic resin composition capable of reducing noise generation under environmental pollution, process simplification, and various environmental conditions.

SUMMARY OF THE INVENTION The present invention is to solve the problems of the prior art, and an object of the present invention is to provide a thermoplastic resin composition capable of reducing noise generation due to friction between materials while having excellent light resistance and heat resistance properties. Specifically, to provide a PC/alloy-based resin composition that self-dissipates vibration energy applied from the outside by a damping factor existing inside the material system.

One aspect of the present invention provides an ethylene/α-olefin-based rubber polymer and an aromatic vinyl monomer and a first monomer mixture comprising a vinyl cyan monomer in an amount of 10 to 35 wt%; Aromatic vinyl monomer and vinyl cyan monomer 60 to 80: 10 to 35% by weight of a vinyl-based copolymer resin polymerized in a weight ratio of 20 to 40; 30 to 75 wt% of polycarbonate resin; 1 to 8% by weight of a slip agent; and 1 to 5 wt% of a chain extender; provides a thermoplastic resin composition comprising.

In one embodiment, the first graft copolymer resin comprises 45 to 54 wt% of an ethylene/α-olefin-based rubber polymer, 45 to 54 wt% of a first monomer mixture in which an aromatic vinyl monomer and a vinyl cyan monomer are copolymerized, 0.1 to 4.0 wt% of the initiator and 0.1 to 5.0 wt% of the coupling agent may be graft polymerization.

In one embodiment, the first graft copolymer resin may be an ethylene/α-olefin-based rubber polymer in which an aromatic vinyl monomer and a vinyl cyan monomer are each polymerized in a weight ratio of 60 to 80: 20 to 40.

In one embodiment, the graft ratio of the first graft copolymer resin may be 10 to 20%.

In one embodiment, the ethylene/α-olefin rubber polymer is an ethylene/propylene copolymer, an ethylene/propylene/non-conjugated diene copolymer, an ethylene/1-butene copolymer, and an ethylene/1-butene/non-conjugated diene copolymer. It may be one selected from the group consisting of coalescing and mixtures of two or more thereof.

In one embodiment, the initiator is succinic acid peroxide, benzoyl peroxide, t-butyl peroxy laurate, 2,5-dimethyl-2,5-di(benzoyl peroxy)hexane, t-butyl peroxy acetate , di-t-butyl diperoxy phthalate, t-butyl peroxy maleic acid, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl peroxy-2-ethyl hexanoate, p-chlorobenzoyl peroxide , t-Butyl peroxy isobutylate, t-butyl peroxy isopropyl carbonate, t-butyl peroxy benzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl-peroxy) ) hexane, t-butyl cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane-3, alpha, alpha'-bis-t-butyl It may be one selected from the group consisting of peroxy-1,4-diisopropylbenzene and a mixture of two or more thereof.

In one embodiment, the initiator may be a mixture of a compound including one peroxide group and a compound including two or more peroxide groups in a weight ratio of 40-60: 40-60.

In one embodiment, the coupling agent is maleic anhydride, 2-methyl-maleic anhydride, 2,3-dimethyl-maleic anhydride, 2-ethyl-maleic anhydride, 2,3-diethyl-maleic anhydride , 2-Trifluoromethyl-maleic anhydride, 2,3-bis(trifluoromethyl)-maleic anhydride, 2-methyl-3-trifluoromethyl-maleic anhydride, citraconic anhydride, aconi It may be one selected from the group consisting of earth anhydride, itaconic anhydride, and a mixture of two or more thereof.

In an embodiment, the slip agent may be one selected from the group consisting of an organically modified siloxane compound, a long-chain fatty acid ester, a long-chain fatty acid amide, and a mixture of two or more thereof.

In one embodiment, the chain extender may be one selected from the group consisting of an anhydride monomer, an acrylate monomer, and a mixture thereof graft-polymerized on a copolymer of an aromatic vinyl monomer and a vinyl cyan monomer.

In one embodiment, the anhydride monomer is maleic anhydride, 2-methyl-maleic anhydride, 2,3-dimethyl-maleic anhydride, 2-ethyl-maleic anhydride, 2,3-diethyl-maleic anhydride , 2-Trifluoromethyl-maleic anhydride, 2,3-bis(trifluoromethyl)-maleic anhydride, 2-methyl-3-trifluoromethyl-maleic anhydride, citraconic anhydride, aconi It may be one selected from the group consisting of earth anhydride and itaconic anhydride, and a mixture of two or more thereof.

In one embodiment, the acrylate monomer is a group consisting of glycidyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, and a mixture of two or more thereof. It may be one selected from

In one embodiment, the thermoplastic resin composition is a second graft copolymer in which 35 to 45% by weight of a second monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer to 55 to 65% by weight of a diene-based rubbery polymer is graft polymerized. It may further include a copolymer resin.

In one embodiment, the second graft copolymer resin may be 1 to 15% by weight based on the total weight of the thermoplastic resin composition.

In addition, in order to achieve the above object, another aspect of the present invention provides a plastic molded article molded with the thermoplastic resin composition.

In one embodiment, the plastic molded body may have a material friction joint property of 3 or less, measured based on the VDA230-206 standard in at least one of low temperature, room temperature, high temperature, and hydrolysis.

In one embodiment, the impact strength of the plastic molded body may be ^{50 ~ 60kJ / m 2 .}

In one embodiment, the heat resistance (HDT) of the plastic molded body may be 105 ~ 115 ℃.

In one embodiment, light resistance of the plastic molded body ΔE may be 2 or less, and gray scale may be 3 or more.

The thermoplastic resin composition according to an aspect of the present invention includes an ethylene/α-olefin-based rubber polymer and a graft copolymer resin of an aromatic vinyl monomer and a vinyl cyan monomer, thereby generating a joint in a thermoplastic resin composition and a plastic molded article prepared therefrom The reduction properties, impact strength and light resistance can be significantly improved.

It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

Hereinafter, the present invention will be described. However, the present invention may be embodied in several different forms, and thus is not limited to the embodiments described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the specification, when a part is "connected" with another part, this includes not only the case where it is "directly connected" but also the case where it is "indirectly connected" with another member interposed therebetween. . In addition, when a part "includes" a certain component, this means that other components may be further provided without excluding other components unless otherwise stated.

Thermoplastic resin composition

The thermoplastic resin composition according to an aspect of the present invention is a first graft copolymer resin 10 to 35 in which a first monomer mixture including an ethylene/α-olefin-based rubber polymer and an aromatic vinyl monomer and a vinyl cyan monomer is graft-polymerized. weight%; Aromatic vinyl monomer and vinyl cyan monomer 60 to 80: 10 to 35% by weight of a vinyl-based copolymer resin polymerized in a weight ratio of 20 to 40; 30 to 75 wt% of polycarbonate resin; 1 to 8% by weight of a slip agent; and 1 to 5% by weight of a chain extender.

Hereinafter, the first graft copolymer resin, vinyl-based copolymer resin, polycarbonate resin, slip agent, chain extender and other additives constituting the thermoplastic resin composition will be described in detail.

(1) First graft copolymer resin

The thermoplastic resin composition comprises 10 to 35% by weight of the first graft copolymer resin, for example, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight. %, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, or 35% by weight may be included, but is not limited thereto. If the content of the first graft copolymer resin is less than 10% by weight, the noise reduction characteristics of the thermoplastic resin composition may be reduced, and if it is more than 35% by weight, the kneading property with other resins is reduced and mechanical properties such as surface properties this may be lowered.

The first graft copolymer resin is obtained by graft polymerization of a first monomer mixture to an ethylene/α-olefin-based rubber polymer, and known polymerization or extrusion such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and reaction extrusion. It may be polymerized by using the method or a combination of two or more of them, and it can be prepared by a reaction extrusion method with increased production process efficiency in order to effectively graft aromatic vinyl monomers and vinyl cyan monomers to ethylene/α-olefin-based rubbery polymers. However, the present invention is not limited thereto.

During graft polymerization, the first monomer mixture may be administered to the ethylene/α-olefin-based rubbery polymer together with a known initiator, coupling agent, etc., or may be continuously administered for a predetermined time if necessary.

The ethylene/α-olefin rubber polymer includes an ethylene/propylene copolymer, an ethylene/propylene/non-conjugated diene copolymer, an ethylene/1-butene copolymer, an ethylene/1-butene/non-conjugated diene copolymer, and two or more of them. It may be one selected from the group consisting of mixtures, but is not limited thereto.

The content of the ethylene/α-olefin-based rubbery polymer is 45 to 54% by weight, for example, 45% by weight, 46% by weight, 47% by weight, 48% by weight based on the total weight of the first graft copolymer resin composition. It may be weight %, 49 weight %, 50 weight %, 51 weight %, 52 weight %, 53 weight %, or 54 weight %, but is not limited thereto. When the content is less than 45% by weight based on the total weight of the first graft copolymer resin composition, the impact of the finally commercialized plastic molded article due to the low ratio of the rubbery polymer in the first graft copolymer resin in the thermoplastic resin composition The strength and noise reduction properties may be reduced, and if the ratio of the ethylene/α-olefin-based rubber polymer is more than 54% by weight, the viscosity increases and the grafting efficiency decreases during the graft reaction with a low ratio of the first monomer mixture. Excessive aggregation between particles occurs in the thermoplastic resin composition, resulting in a decrease in the dispersibility of the first graft copolymer resin, resulting in deterioration of moldability and heat resistance, and local deviations in the properties of reducing noise in the finally commercialized plastic molded article. may occur.

On the other hand, the first graft copolymer resin may be formed by graft polymerization of a first monomer mixture to an ethylene/α-olefin-based rubber polymer, and the first monomer mixture is a mixture of an aromatic vinyl monomer and a vinyl cyan monomer. may be, and the monovinyl monomer copolymerizable with them is 0.1 to 20% by weight, for example, 0.1% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7wt%, 8wt%, 9wt% 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt% Or it may be additionally mixed in an amount of 20% by weight, but is not limited thereto. The aromatic vinyl monomer and the vinyl cyan monomer may be mixed in a weight ratio of 60 to 80: 20 to 40, for example, a weight ratio of 60: 40, 65: 35, 70: 30, 75: 35 or 80: 20 by weight. It may be a mixture, but is not limited thereto.

As a non-limiting example of the present invention, the aromatic vinyl monomer may include styrene, alphamethylstyrene, alphaethylstyrene, vinyltoluene, parabromostyrene, parachlorostyrene, tert-butylstyrene, dimethylstyrene, and mixtures of two or more thereof. It may be one selected from the group consisting of.

As a non-limiting example of the present invention, the vinyl cyan monomer may be one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures of two or more thereof.

As a non-limiting example of the present invention, the mono vinyl monomer may be maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-phenylmaleimide, methylmethacrylate, or methylacrylate. , butyl acrylate, acrylic acid, maleic anhydride, and a mixture of two or more thereof may be one selected from the group consisting of.

On the other hand, the proportion of the vinyl cyan monomer may be 20 to 40% by weight based on the total weight of the first monomer mixture, for example, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight. , 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt% 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt% %, 38% by weight, 39% by weight or 40% by weight may be, but is not limited thereto, and if it is less than 20% by weight, the kneading property may be reduced, and the impact resistance of the finally manufactured plastic molded body may be significantly reduced. have. In addition, if the ratio of the vinyl cyan monomer is more than 40% by weight based on the total weight of the first monomer mixture, surface properties and kneadability with other resins may be reduced due to yellowing during high temperature molding of the thermoplastic resin composition.

The first graft copolymer resin may be prepared by reaction extrusion of 45 to 54% by weight of the ethylene/α-olefin-based rubbery polymer and 45 to 54% by weight of the first monomer mixture.

On the other hand, the graft ratio of the first graft copolymer resin derived from the following formula 1 may be 10 to 20%.

<Equation 1>

In Equation 1, G is the graft rate (%), M _g is the weight (g) of the monomer graft polymerized to the rubbery polymer (g), and W _c is the weight (g) of the rubbery polymer.

If the graft ratio of the first graft copolymer resin is less than 10% or more than 20%, the dispersion degree of the thermoplastic resin composition is lowered, and moldability and heat resistance characteristics may be lowered, and the damping effect to dissipate vibration energy is lowered. Noise reduction characteristics may be deteriorated.

The first graft copolymer resin may further include one initiator selected from the group consisting of inorganic peroxides, organic peroxides, and mixtures of two or more thereof, for example, the decomposition temperature for a half-life of 10 minutes may include an organic peroxide of 100 to 200 ℃, but is not limited thereto.

The initiator is succinic acid peroxide, benzoyl peroxide, t-butyl peroxy laurate, 2,5-dimethyl-2,5-di(benzoyl peroxy)hexane, t-butyl peroxy acetate, di-t-butyl Diperoxy phthalate, t-butyl peroxy maleic acid, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl peroxy-2-ethyl hexanoate, p-chlorobenzoyl peroxide, t-butyl peroxy Isobutylate, t-butyl peroxy isopropyl carbonate, t-butyl peroxy benzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl-peroxy)hexane, t-butyl Cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexane-3, alpha, alpha'-bis-t-butylperoxy-1,4 It may include one selected from the group consisting of -diisopropylbenzene and a mixture of two or more thereof, but is not limited thereto.

As an example of the initiator, a compound containing one peroxide group and a compound containing two or more peroxide groups may be mixed in a weight ratio of 40 to 60: 40 to 60, one of these examples is dicumyl peroxide and alpha , Alpha'-bis-t-butylperoxy-1,4-diisopropylbenzene may be mixed in a weight ratio of 40 to 60: 40 to 60, for example, 40: 60, 45: 55, 50 : 50, 55: 45 or 60: 40, but is not limited thereto.

In one embodiment, the content of the initiator may be 0.1 to 4.0% by weight or 0.5 to 2.0% by weight based on the total weight of the first graft copolymer resin composition, for example, 0.1% by weight, 0.5 It may be weight %, 1.0 weight %, 1.5 weight %, 2.0 weight %, 2.5 weight %, 3.0 weight %, 3.5 weight %, or 4.0 weight %, but is not limited thereto. If the content of the initiator is less than 0.1% by weight, the rate of the initiation reaction for radical generation is significantly reduced, and the graft rate is lowered when grafting the aromatic vinyl monomer and the vinyl cyan monomer to the ethylene/α-olefin-based rubber polymer, so that in the thermoplastic resin composition Excessive agglomeration between particles may reduce moldability and noise reduction characteristics, and if it exceeds 4.0% by weight, thermal stability is lowered due to the high content of initiator remaining in the first graft copolymer resin, The appearance of the thermoplastic resin composition may be discolored, or light resistance and heat resistance may be deteriorated.

Meanwhile, the first graft copolymer resin may include a coupling agent, and the coupling agent is maleic anhydride, 2-methyl-maleic anhydride, and 2,3-dimethyl-maleic anhydride which are unsaturated dicarboxylic acid anhydride monomers. Acid anhydride, 2-ethyl-maleic anhydride, 2,3-diethyl-maleic anhydride, 2-trifluoromethyl-maleic anhydride, 2,3-bis(trifluoromethyl)-maleic anhydride, 2 -Methyl-3-trifluoromethyl-maleic anhydride, citraconic anhydride, aconitoic anhydride, itaconic anhydride, and may be one selected from the group consisting of mixtures of two or more thereof, but is not limited thereto.

The content of the coupling agent may be 0.1 to 5.0% by weight or 0.5 to 2.5% by weight, for example, 0.1% by weight, 0.5% by weight, 1.0% by weight, 1.5% by weight, 2.0% by weight, 2.5% by weight, 3.0 It may be weight %, 3.5 weight %, 4.0 weight %, 4.5 weight % or 5.0 weight %, but is not limited thereto. If the content of the coupling agent is less than 0.1% by weight, local deviations may occur in impact resistance and noise reduction characteristics due to a decrease in compatibility of the first graft copolymer resin in the thermoplastic resin composition, and 5.0% by weight If it exceeds, the appearance of discoloration may occur due to deterioration of moldability and deterioration of thermal stability due to deterioration of flowability due to increase in viscosity of the thermoplastic resin.

(2) Vinyl-based copolymer resin

The thermoplastic resin composition comprises 10 to 35% by weight of the vinyl-based copolymer resin, for example, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt% %, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, or 35% by weight may include, but is not limited thereto. When the content of the vinyl-based copolymer resin is included in the above range, the impact resistance of the finally commercialized plastic molded body may be improved.

The vinyl-based copolymer resin is a copolymer of an aromatic vinyl monomer and a vinyl cyan monomer, and the aromatic vinyl monomer and the vinyl cyan monomer may be polymerized in a weight ratio of 60 to 80: 20 to 40, for example, 60: It may be polymerized in a weight ratio of 40, 65:35, 70:30, 75:35 or 80:20, but is not limited thereto.

If the content of the vinyl cyanide monomer is less than 20% by weight based on the total weight of the vinyl-based copolymer resin, the impact resistance of the finally manufactured plastic molded article may be significantly reduced, and if it exceeds 40% by weight, the high temperature of the thermoplastic resin composition During molding, surface properties may be deteriorated due to yellowing.

As a non-limiting example of the present invention, the aromatic vinyl monomer and the vinyl cyan monomer of the vinyl-based copolymer resin may include at least one of the materials exemplified as the vinyl monomer and the vinyl cyan monomer of the first graft polymer resin described above. and, for example, the vinyl-based copolymer resin may be a SAN resin in which styrene and acrylonitrile are copolymerized.

As a non-limiting example of the present invention, the weight average molecular weight of the vinyl-based copolymer resin may be 80,000 to 110,000, for example, 80,000, 90,000, 100,000 or 110,000. If the weight average molecular weight of the vinyl-based copolymer resin is less than 80,000, the impact resistance of the finally commercialized plastic molded article may be lowered, and if it exceeds 110,000, the flowability of the thermoplastic resin composition may be insufficient and the moldability may be reduced. .

(3) polycarbonate resin

The thermoplastic resin composition contains the polycarbonate resin in an amount of 30 to 75% by weight, for example, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight. %, 38% by weight, 39% by weight, 40% by weight, 41% by weight, 42% by weight, 43% by weight, 44% by weight, 45% by weight, 46% by weight, 47% by weight, 48% by weight, 49% by weight, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62% %, 63% by weight, 64% by weight, 65% by weight, 66% by weight, 67% by weight, 68% by weight, 69% by weight, 70% by weight 71% by weight, 72% by weight, 73% by weight, 74% by weight, or It may include 75% by weight, but is not limited thereto. If the content of the polycarbonate resin is less than 30% by weight, the moldability of the thermoplastic resin composition and the impact resistance of the finally manufactured plastic molded article may be reduced, and if it is more than 75% by weight, the first graft copolymer resin in the thermoplastic resin composition The content of is reduced and the noise reduction characteristic may be deteriorated.

The polycarbonate resin may be prepared by a method of reacting a diphenol-based compound with phosgene, halogen formate or diester carbonate, but is not limited thereto, and may be prepared using various known methods as needed. .

As a non-limiting example of the present invention, the polycarbonate resin is bisphenol-A-polycarbonate resin, tetramethyl-polycarbonate resin, bisphenol-Z-polycarbonate resin, tetrabromo-polycarbonate resin and tetraacrylo- It may be one selected from the group consisting of polycarbonate resins and mixtures of two or more thereof, and may have excellent compatibility and impact resistance including, for example, bisphenol-A-polycarbonate resins.

As a non-limiting example of the present invention, the weight average molecular weight of the polycarbonate resin may be 10,000 to 40,000, for example, 10,000, 20,000, 30,000 or 40,000. If the weight average molecular weight of the polycarbonate resin is less than 10,000, the impact resistance of the finally manufactured plastic molded body may be reduced, and if it exceeds 40,000, the dispersion and elongation of the thermoplastic resin composition may be reduced, and the resistance of the plastic molded body may be reduced. Impact resistance may be reduced.

As a non-limiting example of the present invention, the weight average molecular weight of the polycarbonate resin may be 15,000 to 35,000, for example, 15,000, 25,000 or 35,000. When the weight average molecular weight of the polycarbonate resin is within the above range, the impact resistance and heat resistance of the finally manufactured plastic molded body may be greatly improved.

(4) slip agent

The thermoplastic resin composition comprises 1 to 8 wt% of the slip agent, for example, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt% , 5% by weight, 5.5% by weight, 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, or may include 8% by weight, but is not limited thereto. If the content of the slip agent is less than 1% by weight, the effect of imparting frictional force to the surface may be weak, so that the noise reduction properties of the thermoplastic resin composition and the plastic molded body may be reduced, and if it is more than 8% by weight, the first graft copolymer Since the relative content of the resin and the vinyl-based copolymer resin is reduced, the impact resistance of the finally commercialized plastic molded article may be reduced, and the appearance quality of the thermoplastic resin composition may be deteriorated due to agglomeration between particles of the slip agent.

The slip agent is included in the thermoplastic resin composition, and when friction occurs due to contact between parts by vibration energy applied from the outside, the noise generation reduction effect can be significantly improved by the low friction force of the surface. The slip agent may include an organically modified siloxane compound, a long-chain fatty acid ester, a long-chain fatty acid amide, and a mixture of two or more thereof. For example, the slip agent is easily kneaded with other components included in the thermoplastic resin composition. One organic modified siloxane compound may be included, but is not limited thereto.

(5) chain extenders

The thermoplastic resin composition may contain 1 to 5% by weight of the chain extender, for example, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight %, or 5% by weight, but is not limited thereto. If the content of the chain extender is less than 1% by weight, the noise reduction property due to chain decomposition of the thermoplastic resin composition under high temperature and hydrolysis material friction joint evaluation environment may be significantly reduced, and if it exceeds 5% by weight, the thermoplastic resin composition Mechanical properties, including impact resistance, may be reduced due to a decrease in compatibility between the first graft copolymer, the vinyl-based copolymer, and the polycarbonate according to the increase in the viscosity resistance.

The chain extender may be one selected from the group consisting of an anhydride monomer, an acrylate monomer, and a mixture thereof to a copolymer of an aromatic vinyl monomer and a vinyl cyan monomer, but is not limited thereto.

The anhydride monomer is maleic anhydride; 2-methyl-maleic anhydride; 2,3-dimethyl-maleic anhydride; 2-ethyl-maleic anhydride; 2,3-diethyl-maleic anhydride; 2-trifluoromethyl-maleic anhydride; 2,3-bis(trifluoromethyl)-maleic anhydride; 2-methyl-3-trifluoromethyl-maleic anhydride, citraconic anhydride, aconitoic anhydride and itaconic anhydride and mixtures of two or more thereof.

The acrylate monomer may include glycidyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and 2-hydroxyethyl methacrylate, and a mixture of two or more thereof, but is limited thereto. it is not

In one non-limiting example of the present invention, the anhydride monomer may be maleic anhydride, and the acrylate monomer may be glycidyl methacrylate.

(6) Second graft copolymer resin

The thermoplastic resin composition comprises 1 to 15 wt% of the second graft copolymer resin, for example, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt% %, 4.5% by weight, 5% by weight, 5.5% by weight, 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, 8% by weight, 8.5% by weight, 9% by weight, 9.5% by weight, 10% by weight; 10.5% by weight, 11% by weight, 11.5% by weight, 12% by weight, 12.5% by weight, 13% by weight, 13.5% by weight, 14% by weight, 14.5% by weight or 15% by weight may be further included, but is limited thereto no. If the content of the second graft copolymer resin is less than 1% by weight, the effect according to the content may be insignificant, and if it exceeds 15% by weight, the plastic molded article finally manufactured as the content of the first graft copolymer is relatively decreased. of noise reduction properties and light resistance may be deteriorated.

The second graft copolymer resin may be one obtained by graft polymerization of 35 to 45% by weight of a second monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer to 55 to 65% by weight of a diene-based rubbery polymer, but is limited thereto it is not In one example, the second graft copolymer resin is obtained by graft polymerization of a second monomer mixture to a diene-based rubbery polymer, and known polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or two of them It may be polymerized by combining the above.

During graft polymerization, the monomer mixture may be administered to the diene-based rubbery polymer together with a known emulsifier, polymerization initiator, catalyst, etc., or may be continuously administered for a predetermined time if necessary. The graft copolymer resin first obtained by the graft polymerization is in the form of a latex, but when it is treated with an acid or a salt and coagulated and dried, it can be obtained in the form of a powdery solid.

As a non-limiting example of the present invention, the second graft copolymer resin may be prepared by emulsion polymerization to graft an aromatic vinyl monomer and a vinyl cyan monomer to a diene-based rubbery polymer.

As a non-limiting example of the present invention, the diene-based rubbery polymer may include butadiene-aromatic vinyl compound copolymers such as polybutadiene, butadiene-styrene copolymer, butadiene-vinyltoluene copolymer; butadiene-vinyl cyanide compound copolymers such as butadiene-acrylonitrile copolymer and butadiene-methacrylonitrile copolymer; Or it may be polyisoprene, and two or more of them may be mixed.

As a non-limiting example of the present invention, the second monomer mixture may be mixed in the same weight ratio as the first monomer mixture, for example, an aromatic vinyl monomer and a vinyl cyan monomer in a weight ratio of 60 to 80: 20 to 40. In addition, the aromatic vinyl monomer and the vinyl cyan monomer may be one or more of the materials exemplified above.

As a non-limiting example of the present invention, the aromatic vinyl monomer and the vinyl cyan monomer used in the first graft copolymer resin and the second graft copolymer resin may be the same material.

The second graft copolymer resin may have a graft ratio of 30 to 40% derived from Equation 1 above. If the graft ratio of the second graft copolymer resin is less than 30% or more than 40%, the dispersion degree of the thermoplastic resin composition may be lowered, thereby reducing moldability and impact resistance.

(7) other additives

The thermoplastic resin composition may further include other additives as necessary. The additives are intended to provide various additionally necessary functions to the thermoplastic resin composition, and commonly used stabilizers, lubricants, metal soaps, ultraviolet absorbers, plasticizers, colorants (pigments, dyes), glass fibers, fillers (silica, wood flour, etc.), a flame retardant, an anti-drip agent, an antibacterial agent, an antifungal agent, and one selected from the group consisting of a mixture of two or more thereof, but is not limited thereto.

In particular, the flame retardant may impart flame retardancy to the thermoplastic resin composition having poor heat resistance and combustion resistance, and may be divided into halogen-based flame retardants, inorganic flame retardants, phosphorus-based flame retardants, and melanin-based flame retardants according to components.

Halogen-based flame retardants can be divided into bromine-based flame retardants and chlorine-based flame retardants. Brominated flame retardants can provide excellent flame-retardant effects even in small amounts, but plastic cannot be recycled and toxic environmental pollutants such as dioxins can be emitted during combustion. .

The inorganic flame retardant may be, for example, aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc stannate, molybdate, guanidine, or zirconium. Aluminum hydroxide is non-toxic, low flammability, excellent electrical insulation, and inexpensive Mechanical properties and workability may be reduced.

The phosphorus-based flame retardant may be, for example, red, ammonium phosphate, ammonium polyphosphate, haloalkyl phosphate, and the like. The phosphorus-based flame retardant exhibits an excellent flame retardant effect in a solid phase reaction, and may be particularly effective for plastics containing a large amount of oxygen.

The melanin-based flame retardant may be, for example, melanin phosphate, melanin cyanurate, melanin phosphate, and the like. The melanin-based flame retardant does not generate toxic gas, and the amount of soot generated during combustion may reduce the risk of environmental pollution.

As described above, in the thermoplastic resin composition of the present invention, as plating properties such as conductivity, plating adhesion, and appearance are improved, a separate electroless plating process can be omitted during plating, so eco-friendliness and plating process efficiency are improved, and impact Because of its excellent strength, it can be used as a material suitable for interior and exterior materials of automobiles.

plastic molded body

The plastic molded body according to another aspect of the present invention may be manufactured by molding the above-described thermoplastic resin composition. The thermoplastic resin composition may be prepared including a first graft copolymer resin, a vinyl-based copolymer resin, a polycarbonate resin, a slip agent, and a chain extender, and a plastic molded body manufactured by molding the same is used for automobiles according to the purpose. It can be applied to various fields such as interior and exterior materials for ships, ships, and buildings.

In particular, in the plastic molded article made of the thermoplastic resin composition of the present invention, frictional force between materials is reduced and vibration energy applied from the outside is reduced and extinguished, thereby finally reducing noise generation.

Accordingly, the plastic molded body may have a material friction joint property of 3 or less grade measured based on the VDA230-206 standard in at least one of low temperature, room temperature, high temperature, and hydrolysis. The material friction joint properties can be assigned a grade of 1 to 10 depending on the degree of stick-slip measurement based on the VDA230-206 standard. When the grade is 3 or less, it can be determined that the noise does not occur, and it can be confirmed that the lower the grade, the better the noise reduction effect.

The material friction joint properties may be performed at -20 ~ 100 ℃, depending on the temperature range can be divided into low temperature, room temperature, high temperature and hydrolysis environment. Irrespective of the environmental classification, the evaluation of the material friction joint properties may be performed by pre-treating a plastic molded body, which is a specimen, at a relative humidity of 50% or less for 20 to 24 hours, and then performing the evaluation by a method suitable for each environmental condition. For example, a low temperature environment can be measured after 0.1 to 24 hours at -20 to 10 ° C, a room temperature environment for 0.1 to 24 hours at 10 to 30 ° C, and 0.1 to 24 hours in a high temperature environment at 30 to 100 ° C. The hydrolysis environment may be measured after 150-200 hours of residence at 30-100° C. and 70% or more relative humidity, but is not limited thereto.

On the other hand, the impact strength of the plastic molded body may be ^{50 ~ 60kJ / m 2 .} If the impact strength of the plastic molded body is 50 ^{kJ/m 2} or less, mechanical properties and lifespan may be reduced, and ^{if it exceeds 60 kJ/m 2 ,} workability may be reduced, but is not limited thereto. In addition, the heat resistance (HDT) of the plastic molded article may be 105 ~ 115 ℃, if it is less than 105 ℃, impact resistance and mechanical properties may be reduced, and if it exceeds 115 ℃, workability may be reduced, but is limited thereto no.

On the other hand, light resistance of the plastic molded body ΔE may be 2 or less, and gray scale may be 3 or more. The light resistance of the plastic molded body is ΔE of 2 or less, and the light stability is improved to improve the life-maintaining effect and surface properties, and may be gray scale grade 3 or higher, and if it is less than grade 3, surface discoloration, fading, etc. of the plastic molded body may deteriorate the surface properties, but is not limited thereto.

Hereinafter, embodiments of the present invention will be described in detail.

Example 1

(i) 48.5 wt% of an ethylene/α-olefin rubber polymer as the first graft copolymer resin, 48.6 wt% of a copolymer in which an aromatic vinyl monomer and a vinyl cyan monomer as the first monomer mixture are mixed in a weight ratio of 75:25; Dicumyl peroxide and alpha, alpha'-bis-t-butylperoxy-1,4-diisopropylbenzene in a 50:50 weight ratio of 0.9 wt% of an initiator and 2.0 wt% of a maleic anhydride coupling agent were reacted and extruded (Reactive Extrusion) was prepared. Reaction extrusion was performed using a twin-screw extruder with 32mm∮, L/D=48. After mixing an ethylene/α-olefin rubber polymer, a copolymer mixed with an aromatic vinyl monomer and a vinyl cyan monomer, and an initiator in a Henschel mixer for 3 minutes, Batch administration was carried out, and the coupling agent was continuously administered at the stop of the twin screw extruder through a metering feeder. The melt-kneading temperature of the twin-screw extruder was 180 degrees, and the first graft copolymer resin in the form of pellets was prepared by cutting.

25% by weight of the first graft copolymer resin having a graft ratio of 15% and a weight average molecular weight of 110,000; (ii) 15% by weight of a vinyl-based copolymer resin having a styrene content of 75% by weight, an acrylonitrile content of 25% by weight, a weight average molecular weight of 105,000, and a melt index of 40 (230° C., based on 3.8 kg); (iii) 56 wt% of a polycarbonate resin having a weight average molecular weight of 22,000; (iv) 2 wt% of an organic modified siloxane compound having an apparent specific gravity of 1.03 to 1.04 g/cm ^{3 as a} slip agent, (v) A copolymer in which an acrylate monomer is grafted onto a copolymer of an aromatic vinyl monomer and a vinyl cyan monomer as a chain extender 2% by weight is administered to a Henschel mixer and blended for 3 minutes, then melt-kneaded (cylinder set temperature 260° C.) using an extruder with 32 mm∮, L/D=40, and cut to prepare a thermoplastic resin composition in the form of pellets did.

Example 2

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that 20% by weight of the first graft copolymer resin and 61% by weight of the polycarbonate resin were administered.

Example 3

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that 20% by weight of the first graft copolymer resin, 10% by weight of the vinyl-based copolymer resin, and 66% by weight of the polycarbonate resin were administered. did.

Example 4

A thermoplastic resin composition was prepared in the same manner as in Example 2, except that the polycarbonate resin was administered at 59% by weight and the slip agent was administered at 4% by weight.

Example 5

A thermoplastic resin composition was prepared in the same manner as in Example 2, except that 59% by weight of the polycarbonate resin was administered and 4% by weight of the chain extender was administered.

Example 6

The first graft copolymer resin is administered at 10% by weight, and (vi) the second graft copolymer resin has a polybutadiene content of 59% by weight, a graft rate of 35%, and a weight average molecular weight of 150,000 copolymer 10 A thermoplastic resin composition was prepared in the same manner as in Example 2, except that the weight % was additionally administered.

Comparative Example 1

A thermoplastic resin composition was prepared in the same manner as in Example 2, except that the second graft copolymer resin was administered in an amount of 20% by weight and the first graft copolymer resin was not administered.

Comparative Example 2

A thermoplastic resin composition was prepared in the same manner as in Example 2, except that the polycarbonate resin was administered in an amount of 65% by weight, and the slip agent and the chain extender were not administered.

Comparative Example 3

A thermoplastic resin composition was prepared in the same manner as in Example 5, except that the polycarbonate resin was administered at 63% by weight and the chain extender was not administered.

Comparative Example 4

A thermoplastic resin composition was prepared in the same manner as in Example 5, except that 56% by weight of the polycarbonate resin was administered and 7% by weight of the chain extender was administered.

The components and their contents of the thermoplastic resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 are shown in Table 1 below.

Example
One Example
2 Example
3 Example
4 Example
5 Example
6 comparative example
One comparative example
2 comparative example
3 comparative example
4 (i) First graft copolymer resin 25 20 20 20 20 10 - 20 20 20 (ii) Vinyl-based copolymer resin 15 15 10 15 15 15 15 15 15 15 (iii) polycarbonate resin 56 61 66 59 59 61 61 65 63 56 (iv) Slip agent 2 2 2 4 2 2 2 - 2 2 (v) chain extenders 2 2 2 2 4 2 2 - - 7 (vi) the second graft copolymer resin - - - - - 10 20 - - -

(Unit:% by weight)

Experimental example

In order to evaluate the physical properties of the thermoplastic resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4, experiments were performed as follows.

In order to evaluate the material friction joint properties, using an injection molding machine (electric 250 ton, LS Industrial Systems), the predetermined shape and size (65.0x55.0x3.2mm ) of the fixed part specimen and the moving part specimen having the size (50.0x25.0x3.2mm), a plastic molded body was prepared.

According to the VDA230-206 standard, the material friction joint properties under a room temperature environment were evaluated under an atmosphere of 23°C and 50% relative humidity after 24 hours of pretreatment of the specimen at 23°C and 50% relative humidity.

According to the VDA230-206 standard, the material friction joint properties under a high temperature environment were evaluated under an atmosphere of 23 ° C., 50% relative humidity after 24 hours pretreatment of the specimen at 23 ° C., 50% relative humidity in the chamber, 80 ° C., 3 hours stay in the chamber.

According to the VDA230-206 standard, the material friction joint properties under a low-temperature environment were evaluated under an atmosphere of -10°C, 0.5 hour stay in the chamber after 24 hours pretreatment of the specimen at 23°C, 50% relative humidity, and 23°C, relative humidity 50%. .

According to the VDA230-206 standard, the material friction joint properties under the hydrolysis environment are pre-treated for 24 hours at 23°C and 50% relative humidity, then 70°C in the chamber, 75% relative humidity, 23°C, relative humidity 50 after staying for 168 hours. %, after additional pretreatment for 24 hours, it was evaluated under an atmosphere of 23 °C and 50% relative humidity.

For each specimen, the material friction joint properties were evaluated by the following method. In addition, impact strength, heat resistance (HDT) and light resistance specimens were additionally prepared for each thermoplastic resin composition under the same injection machine and processing conditions as described above, and each specimen was evaluated by the following method.

- Material friction joint property evaluation: Normal Force 40(N), Velocity 1(mm/s), Displacement 20(mm) were evaluated using SSP-04 equipment of Ziegler-Instruments GmbH. The evaluation results based on the VDA230-206 standard are divided into grades 1 to 10, and when the grade is 3 or less, it is judged that the noise does not occur, and the lower the grade, the better the effect of reducing the noise generation characteristic.

- Impact strength (kJ/m ² ): Izod impact strength was evaluated according to ISO 180.

- Heat resistance (HDT, 1.8 MPa, ℃): measured according to ISO 75-2.

- Light resistance: were evaluated under Xenon Arc Lamp-, black panel temperature = 89 ± 3 ℃, relative humidity = 50 ± 5%, irradiation intensity = 66W / m ² at 300-400nm, total dose = 84MJ / m ² condition, △ E and Gray scale were measured. ΔE was calculated and evaluated from Equation 2 below.

<Equation 2>

ΔE =

The evaluation results for the material friction joint property evaluation, impact strength, heat resistance, and light resistance are shown in Table 2 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 material friction
joint evaluation room temperature One One One One One 2 4 4 2 One High temperature One 2 2 2 One 3 6 7 5 3 low temperature One One One One One 2 5 4 3 2 hydrolysis 2 2 2 2 One 3 7 8 7 3 impact strength
(kJ/m ² ) 60 54 57 56 56 55 53 57 55 47 Heat resistance (HDT, 1.8 MPa, ℃) 106 108 109 107 108 108 107 109 108 108 light fastness △E 1.0 0.8 0.8 1.0 0.8 1.4 1.8 1.2 1.3 1.7 gray scale 4-5 4-5 4-5 4-5 4-5 4 3-4 4 4 3-4

Referring to Table 2, the thermoplastic resin compositions of Examples 1 to 6 including the first graft copolymer resin showed improved noise reduction properties, and in particular, did not include the first graft copolymer resin. It can be seen that, compared to the thermoplastic resin composition of Comparative Example 1, it satisfies grade 3 or less in the evaluation of material friction joints under normal temperature, high temperature, and low temperature hydrolysis environment. In addition, it can be seen that the light resistance of the thermoplastic resin composition of Comparative Example 1 including only the second graft copolymer resin alone is excellent. The thermoplastic resin composition of Examples 1 to 6, including a copolymer in which an acrylate monomer is grafted to a copolymer of an organic modified siloxane compound as a slip agent and an aromatic vinyl monomer and a vinyl cyan monomer as a chain extender, is a slip agent and a chain extender. As compared to the thermoplastic resin composition of Comparative Example 2 which does not include, it can be seen that the noise generation reduction characteristics are improved in the material friction joint evaluation.

In addition, the thermoplastic resin compositions of Examples 1 to 6, which simultaneously contain a slip agent and a chain extender, are compared with the thermoplastic resin composition of Comparative Example 3, which includes an organic modified siloxane compound as a slip agent alone, under high temperature and hydrolysis environment. It was confirmed that the noise reduction characteristics were improved.

In addition, the thermoplastic resin compositions of Examples 1 to 6 containing 5% by weight or less of the chain extender have improved impact strength than the thermoplastic resin composition of Comparative Example 4 containing more than 5% by weight of the chain extender, and dispersibility It was confirmed that light resistance was improved as this was excellent.

The description of the present invention described above is for illustration, and those of ordinary skill in the art to which the present invention pertains can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a dispersed form, and likewise components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention.

Claims (19)

45-54 wt% of an ethylene/α-olefin-based rubbery polymer, 45-54 wt% of a first monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer, 0.1-4.0 wt% of an initiator, and 0.1-5.0 wt% of a coupling agent 10 to 35% by weight of the first graft copolymer resin polymerized;
Aromatic vinyl monomer and vinyl cyan monomer 60 to 80: 10 to 35% by weight of a vinyl-based copolymer resin polymerized in a weight ratio of 20 to 40;
30 to 75 wt% of polycarbonate resin;
1 to 8% by weight of an organically modified siloxane compound; and
A thermoplastic resin composition comprising 1 to 5% by weight of a chain extender. delete According to claim 1,
The first graft copolymer resin is a thermoplastic resin composition in which an aromatic vinyl monomer and a vinyl cyan monomer are each polymerized in a weight ratio of 60 to 80: 20 to 40 in an ethylene/α-olefin-based rubber polymer. According to claim 1,
A thermoplastic resin composition having a graft ratio of 10 to 20% of the first graft copolymer resin. According to claim 1,
The ethylene/α-olefin rubber polymer includes an ethylene/propylene copolymer, an ethylene/propylene/non-conjugated diene copolymer, an ethylene/1-butene copolymer, an ethylene/1-butene/non-conjugated diene copolymer, and at least two of them. A thermoplastic resin composition which is one selected from the group consisting of mixtures. According to claim 1,
The initiator is succinic acid peroxide, benzoyl peroxide, t-butyl peroxy laurate, 2,5-dimethyl-2,5-di(benzoyl peroxy)hexane, t-butyl peroxy acetate, di-t-butyl Diperoxy phthalate, t-butyl peroxy maleic acid, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl peroxy-2-ethyl hexanoate, p-chlorobenzoyl peroxide, t-butyl peroxy Isobutylate, t-butyl peroxy isopropyl carbonate, t-butyl peroxy benzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl-peroxy)hexane, t-butyl Cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexane-3, alpha,alpha'-bis-t-butylperoxy-1,4 -Diisopropylbenzene and a thermoplastic resin composition which is one selected from the group consisting of mixtures of two or more thereof. 7. The method of claim 6,
The initiator is a thermoplastic resin composition in which a compound containing one peroxide group and a compound containing two or more peroxide groups are mixed in a weight ratio of 40 to 60: 40 to 60. According to claim 1,
The coupling agent is maleic anhydride, 2-methyl-maleic anhydride, 2,3-dimethyl-maleic anhydride, 2-ethyl-maleic anhydride, 2,3-diethyl-maleic anhydride, 2-trifluoro Methyl-maleic anhydride, 2,3-bis(trifluoromethyl)-maleic anhydride, 2-methyl-3-trifluoromethyl-maleic anhydride, citraconic anhydride, aconitoic anhydride, itaconic anhydride and a thermoplastic resin composition selected from the group consisting of mixtures of two or more thereof. delete According to claim 1,
The chain extender is a thermoplastic resin composition in which one selected from the group consisting of an anhydride monomer, an acrylate monomer, and a mixture of two or more thereof is graft polymerized to a copolymer of an aromatic vinyl monomer and a vinyl cyan monomer. 11. The method of claim 10,
The anhydride monomer is maleic anhydride, 2-methyl-maleic anhydride, 2,3-dimethyl-maleic anhydride, 2-ethyl-maleic anhydride, 2,3-diethyl-maleic anhydride, 2-trifluoro Methyl-maleic anhydride, 2,3-bis(trifluoromethyl)-maleic anhydride, 2-methyl-3-trifluoromethyl-maleic anhydride, citraconic anhydride, aconitoic anhydride and itaconic anhydride and a thermoplastic resin composition selected from the group consisting of mixtures of two or more thereof. 11. The method of claim 10,
The acrylate monomer is one selected from the group consisting of glycidyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, and a mixture of two or more thereof. composition. According to claim 1,
The thermoplastic resin composition further comprises a second graft copolymer resin in which 35 to 45% by weight of a second monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer to 55 to 65% by weight of the diene-based rubbery polymer is graft polymerized. Thermoplastic resin composition. 14. The method of claim 13,
The content of the second graft copolymer resin is 1 to 15% by weight based on the total weight of the thermoplastic resin composition. A plastic molded article molded with the thermoplastic resin composition of any one of claims 1, 3 to 8, and 10 to 14. 16. The method of claim 15,
The plastic molded body has a material friction joint property of 3 or less grade measured according to the VDA230-206 standard in at least one of low temperature, room temperature, high temperature and hydrolysis. 16. The method of claim 15,
The impact strength of the plastic molded body is 50-60 kJ/m ² A plastic molded body. 16. The method of claim 15,
The heat resistance (HDT) of the plastic molded body is 105 ~ 115 ℃ plastic molded body. 16. The method of claim 15,
The light resistance of the plastic molded body is ΔE is 2 or less, and the gray scale is 3 or higher.