KR101746265B1 - Environment friendly thermoplastic resin composition having improved weldline and plastics comprising same - Google Patents

Abstract

The present invention relates to an environmentally friendly thermoplastic resin composition and a molded article including the environmentally friendly composition which are less harmful to the environment and improved in appearance characteristics and can increase the likelihood to consumers.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an environmentally friendly thermoplastic resin composition having improved appearance,

The present invention relates to an environmentally friendly thermoplastic resin composition including plant-derived biomass plastics, which is less harmful to the environment and has an improved appearance characteristic and can increase the likelihood to consumers, and a molded article comprising the same.

Polylactic acid (PLA) is one of the synthetic biodegradable resins and has recently been attracting much attention because it is a resin made from natural raw materials that can be regenerated. In terms of physical properties, strength and stiffness are excellent, Toughness, heat distortion temperature (HDT) and gas barrier properties are poor, so there are restrictions on the products or areas to which they are applied.

A polymer blend including a biodegradable resin such as polylactic acid is referred to as a bio-blend. Currently, a bio-blend is used as a packaging material, a drug delivery system, a bioabsorbable suture, a tissue implant, It is being developed for toys and the like.

For example, attempts have been made to replace ABS resins used in existing toys for children by using the above polylactic acid and an acrylonitrile-butadiene-styrene copolymer (ABS) alloy resin composition. However, And does not meet the desired weld line characteristics, and does not provide sufficient assemblability.

SUMMARY OF THE INVENTION [0006]

To provide an environmentally friendly thermoplastic resin composition having improved appearance characteristics and excellent assembling properties.

[0010] Another object of the present invention is to provide

And a molded article comprising the environmentally friendly thermoplastic resin composition.

According to an aspect of the present invention,

100 parts by weight of polylactic acid resin;

10 to 300 parts by weight of a graft copolymer obtained by grafting an aromatic vinyl compound and a cyan compound onto a conjugated diene rubbery copolymer;

30 to 300 parts by weight of a methyl methacrylate-styrene-acrylonitrile copolymer; And

And 10 to 150 parts by weight of a (meth) acrylic acid alkyl ester polymer.

According to another aspect of the present invention,

And a molded article comprising the environmentally friendly thermoplastic resin composition.

According to the present invention, there is provided an environmentally friendly thermoplastic resin composition which has improved appearance characteristics and can have improved assemblability, while at the same time reducing the generation of carbon dioxide compared to conventional ABS and containing environmentally friendly components, Such an eco-friendly or biomass resin composition can be usefully used for various molded articles such as toys and electronic products.

Fig. 1 shows an SEM image of the surface of the molded article obtained in Example 2. Fig.
Fig. 2 shows a SEM image of the surface of the molded article obtained in Comparative Example 2. Fig.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and the inventor can properly define the concept of the term to describe its invention in the best possible way And should be construed in accordance with the principles and meanings and concepts consistent with the technical idea of the present invention.

Hereinafter, the present invention will be described in detail.

An environmentally friendly thermoplastic resin composition having improved appearance characteristics according to one embodiment,

100 parts by weight of polylactic acid resin;

10 to 300 parts by weight of a graft copolymer obtained by grafting an aromatic vinyl compound and a cyan compound onto a conjugated diene rubbery copolymer;

30 to 300 parts by weight of a methyl methacrylate-styrene-acrylonitrile copolymer; And

And 10 to 150 parts by weight of a (meth) acrylic acid alkyl ester polymer.

Generally, when the resin flow in two or more directions in a process of injection or the like is diverged, a weld line which occurs after reaching a certain distance necessarily occurs, thereby deteriorating the appearance characteristics of the molded article. Therefore, it is preferable that the weld line is minimized to improve the appearance characteristics, and the environmentally friendly thermoplastic resin composition of the present invention has improved appearance properties due to improved compatibility between the respective components.

Hereinafter, each component constituting the resin composition will be described in more detail.

(a) polylactic acid

Generally, poly (lactic acid) resin is commercially available as a polyester resin produced by using lactic acid obtained by decomposing corn starch as a monomer. The polylactic acid resin may be a poly L-lactic acid (L-isomer), a poly-D-lactic acid (D-isomer) or a poly L, D-lactic acid (L, D-isomer). One or more of the above polylactic acid isomers can be selected and used in the thermoplastic resin composition. On the other hand, such a poly (lactic acid) resin preferably contains poly L-lactic acid in an amount of 90% by weight or more in consideration of heat resistance and processability. On the other hand, the weight average molecular weight of the poly (lactic acid) resin is not limited in its constitution, but it may be at least 10,000 or more in order to improve the impact strength and scratch resistance of the resin composition. Preferably, a poly (lactic acid) resin having a weight average molecular weight of 10,000 to 300,000 can be used.

(b) a graft copolymer obtained by grafting an aromatic vinyl compound and a cyan compound onto a conjugated diene rubbery copolymer

A method for producing a graft copolymer in which an aromatic vinyl compound and a cyan compound are grafted to a conjugated diene rubber-like copolymer contained in the thermoplastic resin composition according to the above embodiment is as follows.

First, the conjugated diene-based rubbery polymer may be prepared by preparing a small-diameter rubbery polymer having a relatively small average particle size, and then fusing it with an acid to prepare a large-diameter rubbery polymer having a relatively large average particle size. At this time, the particle diameter and the gel content of the conjugated diene-based rubbery polymer used have a great influence on the impact strength and workability of the resin.

In general, the smaller the particle diameter of the conjugated diene rubber polymer is, the lower the impact strength and processability are, and the larger the particle diameter is, the larger the impact strength is. When the gel content is smaller, the monomer is swollen much in the conjugated diene rubber polymer, The particle size is increased and the impact strength is improved. However, there is a problem that the content of the conjugated diene-based rubbery polymer is large and the graft rate decreases as the particle size increases. The graft ratio greatly affects the physical properties of the conjugated diene-based graft copolymer. If the grafting rate is lowered, there is a large amount of ungrafted conjugated diene-based rubbery polymer, which results in poor thermal stability.

Therefore, it is important to produce a conjugated diene-based rubbery polymer having an appropriate particle size and gel content, and it is important to ensure proper graft rate when grafting an aromatic vinyl compound and a vinyl cyanide compound to the conjugated diene-based rubbery polymer. In view of this, the conjugated diene-based rubbery polymer may have an average particle diameter of 2500 to 5000 Å. Specifically, the method for producing the graft copolymer (b) can be produced according to the method disclosed in Korean Patent Application No. 2006-0000898, which is a prior application of the present applicant, which is incorporated herein by reference.

The conjugated diene-based rubbery polymer is not limited in its constitution, but at least one selected from the group consisting of a butadiene rubber polymer, an isoprene rubber polymer, and a chloroisoprene rubber polymer can be used. When such a conjugated diene-based rubbery polymer is used, the graft ratio is high and the impact strength of the graft copolymer finally produced is excellent.

At this time, the type of the aromatic vinyl compound grafted to the conjugated diene rubber polymer is not limited, but at least one selected from the group consisting of styrene, alpha methyl styrene, and para methyl styrene can be used. The structure of the vinyl cyan compound grafted to the conjugated diene rubber polymer is not limited, but at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile can be used.

Most preferably, a resin obtained by grafting at least one of acrylonitrile and styrene onto a butadiene rubbery copolymer showing excellent physical properties such as impact resistance and heat resistance can be used.

The content of the aromatic vinyl compound and the vinyl cyan compound grafted to the conjugated diene rubber polymer is not limited. However, in order to increase the graft ratio and optimize the physical properties including the impact resistance of the finally produced graft copolymer, 30 to 60 parts by weight of an aromatic vinyl compound and 10 to 30 parts by weight of a vinyl cyan compound may be grafted to 100 parts by weight of the conjugated diene rubber polymer.

Meanwhile, in the thermoplastic resin composition according to the above-described embodiment of the present invention, the graft copolymer is contained in an amount of 10 to 300 parts by weight, or 30 to 150 parts by weight based on 100 parts by weight of poly (lactic acid) And for improving the workability in the injection and assembly processes. If the amount of the graft copolymer exceeds 300 parts by weight, scratch resistance and workability become poor. When the amount of the graft copolymer is less than 10 parts by weight, impact strength is lowered, It is not preferable.

(c) Methyl methacrylate-acrylonitrile-styrene copolymer

According to one embodiment, the methyl methacrylate-acrylonitrile-styrene copolymer used in the resin composition comprises i) 10 to 30 parts by weight of a styrene monomer, 60 to 80 parts by weight of a methyl methacrylate monomer, 5 to 20 parts by weight of a nitrile monomer and 25 to 35 parts by weight of a reaction medium to prepare a reaction mixture; Ii) adding an organic peroxide initiator having a bifunctional group to the reaction mixture of step i) in an amount of 0.005 to 0.05 part by weight based on 100 parts by weight of the reaction mixture; And iii) bulk polymerization of the mixture to which the initiator of step ii) has been added; . ≪ / RTI >

The bulk polymerization in the step iii) may be carried out at a temperature of 110 to 140 ° C for 2 to 4 hours and then at 120 to 160 ° C for 2 to 4 hours.

The styrene-based monomer may be at least one member selected from the group consisting of styrene,? -Methylstyrene, p-bromostyrene, p-methylstyrene, p-chlorostyrene and o-bromostyrene.

The reaction medium may be at least one member selected from the group consisting of ethylbenzene, toluene and xylene, and is preferably doluene.

When the styrene monomer is added in an amount of less than 10 parts by weight, there is a problem that the reactivity of the reaction product is high and workability and fluidity of the produced product deteriorate. When the amount exceeds 30 parts by weight, the refractive index increases and transparency decreases.

When the reaction medium is added in an amount of less than 25 parts by weight, the viscosity of the reactant may increase sharply. If the reaction medium is more than 35 parts by weight, the molecular weight and the production amount may be lowered.

When methyl methacrylate is added in an amount of less than 60 parts by weight, the refractive index increases and the transparency decreases. When the amount of the methyl methacrylate exceeds 80 parts by weight, the viscosity of the reactant increases sharply.

When the acrylonitrile monomer is added in an amount of less than 5 parts by weight, there is a problem that the chemical resistance is poor. When the acrylonitrile monomer is more than 20 parts by weight, heat discoloration occurs.

The organic peroxide initiator may be selected from the group consisting of 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and 1,1-bis (t-butylperoxy) cyclohexane, t-butylperoxy) 2-methylcyclohexane, and the like. It is preferable that 100 parts by weight of a reaction mixture composed of a styrene monomer, a methyl methacrylate monomer, an acrylonitrile monomer and a reaction medium is used Is added in an amount of from 0.005 to 0.05 part by weight. When the amount of the polymerization initiator is less than 0.005 part by weight, the production amount is low and the thermal discoloration occurs more frequently due to the difference in composition ratio in the polymer. So that the viscosity of the reactant rapidly increases.

The addition of the methyl methacrylate-acrylonitrile-styrenic copolymer to the thermoplastic composition not only improves the impact resistance but also acts as an auxiliary compatibilizer although it is not a compatibilizing agent, thereby slightly improving the compatibility of the resin composition, By eliminating the line, it improves the appearance quality. The methyl methacrylate-acrylonitrile-styrenic copolymer is preferably contained in an amount of 30 to 300 parts by weight, 50 to 150 parts by weight, or 70 to 130 parts by weight based on 100 parts by weight of the poly (lactic acid) When the amount is less than 30 parts by weight, there is a problem that the effect as a compatibilizing agent may be weak. When the amount is more than 300 parts by weight, there is a possibility of causing problems in physical properties and economical efficiency.

(d) a (meth) acrylic acid alkyl ester polymer

The (meth) acrylic acid alkyl ester polymer is preferably at least one polymer selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl ethacrylate, and ethyl ethacrylate, , And more preferably, methyl methacrylate may be used to improve impact resistance and processability. By adding such a (meth) acrylic acid alkyl ester polymer to the thermoplastic resin composition, it is possible to improve not only the appearance quality but also the overall mechanical properties by improving the compatibility of the resin composition.

The (meth) acrylic acid alkyl ester polymer is a compatibilizer which is compatible with acrylonitrile-butadiene copolymer, methyl methacrylate-acrylonitrile-styrene copolymer, poly (lactic acid) and (Meth) acrylic acid alkyl ester polymer to lower the interfacial tension to facilitate mixing and dispersion.

The amount of the alkyl (meth) acrylate polymer used is 10 to 150 parts by weight, or 10 to 70 parts by weight, based on 100 parts by weight of the poly (lactic acid) contained in the thermoplastic resin composition according to the above- It is desirable to optimize the properties and improve the appearance characteristics.

(e)

The composition may further include a lubricant for reducing friction and promoting sliding, and the constitution is not limited as long as it is usually added to the thermoplastic resin composition, but preferably N, N-ethylene bisstearamide, oxidized polyethylene wax , And magnesium stearate may be used. The amount of the lubricant added is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin contained in the thermoplastic resin composition.

Such a lubricant can improve the assemblability when used especially in the field of block toys and the like.

 (f)

The resin composition may further include a releasing agent and may be added to facilitate release from the mold during molding of the resin and to maintain the morphology of the molded resin well. Especially, it is possible to improve the assemblability in the field of block toys and the like.

In general, any releasing agent used in the thermoplastic resin composition can be selected without limitation of its constitution. Specifically, at least one siloxane-based copolymer such as dimethylpolysiloxane, diphenylpolysiloxane, and methylphenylpolysiloxane may be used, and these may be used in combination with an acrylonitrile-butadiene-styrene copolymer. In this case in a weight ratio of about 1: 0.1 to 10.

The release agent may be used in an amount of 1 to 30 parts by weight, or 3 to 20 parts by weight based on 100 parts by weight of the thermoplastic resin.

(g) Additive

Meanwhile, the thermoplastic resin composition according to the above-described embodiment may contain additives conventionally used in the resin composition, if necessary. Specifically, the additive selected from the group consisting of a flame retardant, an impact modifier, a flame retardant additive, a plasticizer, a heat stabilizer, a dripping inhibitor, an antioxidant, a compatibilizer, a light stabilizer, a pigment, a dye, an inorganic additive, an antistatic agent, a UV stabilizer and an anti- And may further include one or more species.

The antioxidant among the above additives is not particularly limited as long as it is usually added to the thermoplastic resin composition, but preferably a phenolic antioxidant can be used. Examples of phenolic antioxidants include bis- (3,3-bis- (4'-hydroxy-3'-tetrabutylphenol) butanoic acid) -glycol ester, tetrakismeethylene 3- (3,5- (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2 , 4,6- (1H, 3H, 5H) trione, and 1,3,5-tris- (3,5-di-t- butyl-4-hydroxybenzyl) -2,4,6- (1H, 3H, 5H) -thione may be used, but the present invention is not limited to these examples. And IR1076, which is a commonly used phenolic antioxidant, can be preferably used. The amount of the IR1076 to be used may be 0.1 to 3 parts by weight based on 100 parts by weight of the thermoplastic resin.

The antistatic agent among the above additives may be used without limitation in the constitution as long as it is usually added to the thermoplastic resin composition. Specifically, at least one selected from anionic surfactants, nonionic surfactants, and mixtures thereof can be used. The amount of the antistatic agent may be 0.1 to 20 parts by weight based on 100 parts by weight of the thermoplastic resin.

The ultraviolet stabilizer among the additives may be added to the thermoplastic resin composition. Specifically, TINUVIN 326, which is an ultraviolet absorber, can be used. The amount of the UV absorbing agent to be used may be 0.05 to 3 parts by weight, more preferably 0.2 to 1 part by weight based on 100 parts by weight of the thermoplastic resin.

On the other hand, the environmentally friendly thermoplastic resin composition according to the above-described embodiment has excellent mechanical properties, excellent workability, and can exhibit improved appearance characteristics.

In addition, when the above-mentioned lubricant and release agent are selectively included, the assemblability can be improved, which can be an advantageous advantage in the case of repeating insertion and withdrawal in the same field as a toy for assembly. That is, if the assemblability is poor, it becomes difficult due to the friction between the parts, so that it is difficult to insert or remove the assemblies. However, when the assemblability is improved, such symptoms can be further mitigated.

According to one aspect, the composite material containing the thermoplastic resin composition is not particularly limited, but it is preferable to mix the mixture of (a) to (d) and (e) A kneader and a mixing roll, and kneading the mixture at a temperature of about 100 to 500 ° C or 200 to 400 ° C.

The order of mixing the raw materials is not particularly limited, and the resin composition, and if necessary, the lubricant, the releasing agent, the additives, and the like are preliminarily blended and then melt-kneaded with a single screw or a twin-screw extruder at a temperature not lower than the melting point of the thermoplastic resin A method of removing the solvent after mixing in a solution, and the like are used. Of these, from the viewpoint of productivity, a method of homogeneously melt-kneading with a single-screw or twin-screw extruder is preferred. In particular, a method of uniformly melt-kneading at a melting point or higher of the thermoplastic resin using a twin screw extruder is preferably used.

A composite material having a shape such as pellets can be produced through the above extrusion method.

The composite material according to one embodiment can be molded by any known method such as injection molding, blow molding, press molding, and spinning, and can be processed into various molded articles. As the molded article, it can be used as an injection molded article, an extrusion molded article, a blow molded article, a film, a sheet, a fiber and the like.

Particularly, the composite material of the present invention can be processed into a molded product such as a block toy for assembly, taking advantage of its excellent appearance and excellent assembling property.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. , And it is natural that such variations and modifications fall within the scope of the appended claims.

<Component>

In the following Examples and Comparative Examples, the following components were used.

 (a) polylactic acid resin

PLA 4032D (Nature Works) was used as the poly lactic acid resin.

The polylactic acid resin used had a mass average molecular weight (Mw 200,000), a polydispersity of 1.74, a glass transition temperature (Tg) of 55 占 폚 and a melting temperature (Tm) of 165 占 폚.

 (b) a graft copolymer obtained by grafting an aromatic vinyl compound and a cyan compound onto a conjugated diene rubbery copolymer

ABS DP (product name: DP270, manufactured by LG Chemical Co., Ltd.), which was prepared by grafting an aromatic vinyl compound and a vinyl cyan compound onto a conjugated diene rubber polymer, was emulsion polymerized and used without purification.

The conjugated diene-based rubbery polymer having an average particle diameter of 3000 Å was used.

(c-1) methyl methacrylate-acrylonitrile-styrene copolymer (SAN-MMA)

20 parts by weight of a styrene-based monomer, 70 parts by weight of a methyl methacrylate monomer, 10 parts by weight of an acrylonitrile monomer and 30 parts by weight of toluene were mixed in a reactor, and 1,1-bis (t-butylperoxy) And 0.01 part by weight of hexane were added and polymerization was carried out at a temperature of 120 ° C for 3 hours and then further polymerization was carried out at a temperature of 140 ° C for 3 hours.

The melt index was measured according to ASTM D1238 at a temperature of 220 캜 under a load of 5 kg for 10 minutes, and the weight (g) was 10 g / 10 min.

(c-2) styrene-acrylonitrile copolymer (SAN)

The styrene-acrylonitrile copolymer was a SAN-based resin in which styrene and acrylonitrile were copolymerized, and SAN (product name: 81HF, LG Chemical Co., Ltd.), which was produced through continuous bulk polymerization using a catalyst, was used without purification.

The styrene-acrylonitrile copolymer contains 20% by weight of acrylonitrile and 80% by weight of styrene, the melt index according to ASTM D1238 is 30 g (g) measured at a temperature of 220 캜 under a load of 10 kg for 10 minutes under a load of 10 kg / 10 minutes was used.

(d) a (meth) acrylic acid alkyl ester polymer (PMMA)

(Product name: IH830) manufactured by LG MMA as a (meth) acrylic acid alkyl ester polymer was used as it was without purification.

The (meth) acrylic acid alkyl ester polymer used had a melt index according to ASTM D1238 of 10 g / 10 min as a weight (g) measured at 230 DEG C under a load of 3.8 kg for 10 minutes.

(e)

N, N-ethylene bistostearamide was used as the lubricant as the amide-based lubricant.

(f)

The release agent contains 50% by weight of dimethylpolysiloxane and 50% by weight of acrylonitrile-butadiene-styrene copolymer as a siloxane-based copolymer. The melt index is measured in accordance with ASTM D1238 at a temperature of 220 캜 under a load of 10 kg for 10 minutes (g) of 14 g / 10 min.

Examples 1 to 4

The above components were uniformly mixed in a mixer as shown in Table 1, and then a polylactic acid resin composition in the form of a pellet was prepared using a twin-screw extruder and injection-molded to prepare a specimen for evaluation of physical properties.

Comparative Examples 1 to 3

The above components were uniformly mixed in the mixer as shown in Table 1, and then a polylactic acid resin composition in the form of a pellet was prepared using a twin-screw extruder and injection molded to prepare a specimen for evaluation of physical properties.

division
Example (parts by weight)
Comparative Example (parts by weight)
One 2 3 4 One 2 3 (a) polylactic acid 30 30 40 30 30 30 30 (b) Graft
Copolymer 20 30 20 30 30 30 30 (c-1) SAN-MMA 37 27 27 32 - - - (c-2) SAN 40 30 27 (d) PMMA 10 10 10 5 - 10 10 (e) 2 2 2 2 - - - (f) One One One One - - One

Experimental Example

The properties of the resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 2 below.

Melt index: The melt index was evaluated by the ASTM D1238 test method under the conditions of 200 占 폚 and a load of 5 kg.

Tensile Strength (TS): Evaluated according to ASTM D638 test method at a speed of 5 cm / min.

Flexural modulus: Evaluated according to ASTM D790 test method at a speed of 1.5 cm / min.

Izod Impact Strength: Evaluated on 1/8 inch notched specimens by ASTM D256 test method.

Assemblability: To evaluate the assemblability of the block product in the toy, two blocks were inserted and subtracted using UTM to measure the frictional force generated. The larger the value, the stiffer it means that it is inserted and difficult to remove.

Weldline: The molded article was visually evaluated. The evaluation criteria are as follows.

◎: Excellent

○: Excellent

△: Normal

X: Poor

XX: Very bad

division Example (parts by weight) Comparative Example (parts by weight) One 2 3 4 One 2 3 Melt Index
(g / 10 min) 12 8 9 9 13 13 7 The tensile strength
(kgf / cm ² ) 450 420 440 430 475 470 460 Flexural modulus
(kgf / cm ² ) 23500 20500 23000 21500 28000 27000 26000 Impact strength
(kg · cm / cm) 40 45 45 50 15 20 25 Assembly (N · m) 13 15 15 14 35 35 15 Weldline ◎ ◎ ○ ○ XX X X

As shown in Table 2, the resin compositions of Examples 1 to 4 exhibited substantially similar mechanical properties such as melt index, tensile strength and flexural modulus as compared with Comparative Examples 1 to 3, and the appearance properties were improved . Especially, it can be seen that the assemblability is excellent.

Fig. 1 is an SEM photograph of the specimen obtained in Example 2, and Fig. 2 is an SEM photograph of the specimen obtained in Comparative Example 2. Fig. Comparing the morphologies of Example 2 and Comparative Example 2, it can be seen that the appearance characteristics of Example 2 are superior to those of Comparative Example 2, and thus the compatibility of the resin composition of Example 2 is superior to Comparative Example 2 have.

Claims (22)

100 parts by weight of polylactic acid resin;
10 to 300 parts by weight of a graft copolymer obtained by grafting an aromatic vinyl compound and a cyan compound onto a conjugated diene rubber polymer;
30 to 300 parts by weight of a methyl methacrylate-acrylonitrile-styrene copolymer;
10 to 150 parts by weight of a (meth) acrylic acid alkyl ester polymer;
0.1 to 10 parts by weight of an amide-based lubricant; And
1 to 30 parts by weight of a mixture of a dimethylpolysiloxane and an acrylonitrile-butadiene-styrene copolymer as a releasing agent
Wherein the thermoplastic resin composition is a thermoplastic resin composition,
Wherein the (meth) acrylic acid alkyl ester polymer is contained in a weight ratio of 30: 5 to 30:10 relative to the polylactic acid resin. The method according to claim 1,
Wherein the polylactic acid is at least one of poly L-lactic acid (L-isomer), poly-D-lactic acid (D-isomer) and poly L, D-lactic acid (L, D-isomer). The method according to claim 1,
Wherein the polylactic acid comprises at least 90% by weight of poly L-lactic acid. The method according to claim 1,
Wherein the polylactic acid has a weight average molecular weight of 10,000 to 300,000. The method according to claim 1,
Wherein the conjugated diene-based rubbery polymer has an average particle diameter of 2500 to 5000 Å. The method according to claim 1,
Wherein the conjugated diene-based rubbery polymer is at least one of a butadiene rubber polymer, an isoprene rubber polymer, and a chloroisoprene rubber polymer. The method according to claim 1,
Wherein the aromatic vinyl compound is at least one of styrene, alphamethylstyrene, and para-methylstyrene. The method according to claim 1,
Wherein the cyan compound is at least one of acrylonitrile, methacrylonitrile, and ethacrylonitrile. The method according to claim 1,
The graft copolymer in which the aromatic vinyl compound and the cyan compound are grafted to the conjugated diene rubbery copolymer is obtained by blending 30 to 60 parts by weight of the aromatic vinyl compound and 10 to 30 parts by weight of the cyan compound in 100 parts by weight of the conjugated diene rubber polymer Lt; RTI ID = 0.0 &gt; thermoplastic &lt; / RTI &gt; resin composition. The method according to claim 1,
Wherein the methyl methacrylate-acrylonitrile-styrenic copolymer comprises 10 to 30 parts by weight of a styrene-based monomer, 60 to 80 parts by weight of a methyl methacrylate monomer, and 5 to 20 parts by weight of an acrylonitrile monomer And a thermoplastic resin composition. 11. The method of claim 10,
Wherein the styrene-based monomer is at least one of styrene,? -Methylstyrene, p-bromostyrene, p-methylstyrene, p-chlorostyrene and o-bromostyrene. The method according to claim 1,
Wherein the alkyl (meth) acrylate polymer is a compatibilizer. The method according to claim 1,
Wherein the methyl methacrylate-acrylonitrile-styrene copolymer is an auxiliary compatibilizer. The method according to claim 1,
Wherein the alkyl (meth) acrylate polymer is at least one polymer selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl ethacrylate, and ethyl ethacrylate. Resin composition. delete The method according to claim 1,
Wherein the lubricant is N, N-ethylene bisstearamide. delete delete delete delete A molded article obtained by processing the thermoplastic resin composition according to claim 1. 22. The method of claim 21,
Wherein the processing step is an extrusion step or an injection step.

Images