KR101284654B1 - Environmentally Friendly Resin Composition - Google Patents
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- KR101284654B1 KR101284654B1 KR1020100028100A KR20100028100A KR101284654B1 KR 101284654 B1 KR101284654 B1 KR 101284654B1 KR 1020100028100 A KR1020100028100 A KR 1020100028100A KR 20100028100 A KR20100028100 A KR 20100028100A KR 101284654 B1 KR101284654 B1 KR 101284654B1
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Abstract
The present invention relates to an environment-friendly resin composition having excellent heat resistance and impact resistance, and relates to an affinity-hard resin composition comprising a polylactic acid resin and a polyethylene terephthalate resin as a base resin, and including an impact modifier and a chain extender.
Description
The present invention relates to an environment-friendly resin composition excellent in heat resistance and impact resistance. More specifically, the present invention not only can reduce environmental pollution load including environmentally friendly polylactic acid resin, polyethylene terephthalate and impact modifier, and chain extender, but also has excellent physical properties including heat resistance and impact resistance at the same time. Therefore, the present invention relates to an environment-friendly resin composition that can be usefully applied as a material for parts such as automobile interior and exterior materials and housings of electric and electronic devices.
Plastic materials (PP, ABS, etc.) that use fossil resources such as petroleum and coal have excellent physical properties, but they emit carbon dioxide during disposal, causing global warming due to the increase of carbon dioxide in the atmosphere. Therefore, in view of preventing global warming, it is desirable to reduce the amount of petrochemical materials derived from such petroleum and the like, and there is a need for development of environmentally friendly materials that can replace them.
On the other hand, even if the plant-derived resin produced by the photosynthesis reaction using carbon dioxide and water as the raw material is incinerated to generate carbon dioxide, the generated carbon dioxide corresponds to the carbon dioxide originally present in the atmosphere, thus increasing the amount of carbon dioxide in the atmosphere. I won't let you. When using carbon neutral material, the importance is emphasized from the viewpoint of preventing global warming by not increasing the total amount of carbon dioxide in the atmosphere.
Representative examples of such plant-derived resins include polylactic acid resins, which are obtained from corn or sugar cane and finally biodegradable (carbon neutral) into water and carbon dioxide, as well as excellent mechanical properties and melt molding. Therefore, it is used for various purposes in various fields. The polylactic acid resin has recently been attracting attention because it can be used in parts of automobiles or electronic products. In addition, it is advantageous from the viewpoint that stable supply is possible because the raw material is made from a permanent renewable plant, not a petroleum resource that is depleted due to limited reserves. In this regard, "biodegradable resins" are known as resins that can be degraded by the action of naturally occurring microorganisms such as bacteria and the like.
However, polylactic acid resin alone exhibits relatively hard and brittle properties as compared to other general-purpose polymer materials, and because of its low heat resistance, it is often difficult to be used for a member requiring high impact resistance and heat resistance, and the crystallization rate during molding processing. There is a disadvantage that the productivity is lowered because is slow.
In order to solve the problems caused by the application of the polylactic acid described above, a method of blending a polycarbonate resin or another heterogeneous polymer to a polylactic acid resin is known.
Japanese Patent No. 3279768 discloses a resin composition composed of an aromatic polycarbonate / polylactic acid alloy, having a pearl luster and excellent impact resistance and heat resistance. However, in the case of the above document, the thermal and mechanical properties are excellent, but the polylactic acid-based resin content is limited in that the carbon dioxide reduction effect is not large.
In the technique disclosed in Japanese Patent Application Laid-open No. 2004-272620, there is a disadvantage in that the carbon dioxide reduction effect is not large by limiting the amount of polylactic acid-based resin to 50 wt% or less in order to satisfy both heat resistance and impact resistance of the resin composition. .
In the case of most prior arts, including the above-mentioned literatures, when two or more polymers are blended, they are separated into their respective phases, which causes swelling during extrusion, which makes it difficult to pellet the strands. It may also cause the occurrence of flow marks or surface peeling.
As such, there is a continuous development of technology to solve the degradation of physical properties such as impact resistance and heat resistance of the polycarbonate and polylactic acid resin blend or alloy and to have more improved characteristics.
On the other hand, polyethylene terephthalate is a container material for various beverages, and has been rapidly spread due to its convenience, and a large amount of polyethylene terephthalate waste is generated every day. Legal and administrative standards for recycling such polyethylene terephthalate waste have been prepared, and in the meantime, polyester fiber for clothes is manufactured using recycled polyethylene terephthalate, or it is made of polymer concrete and used as building materials. Has been proposed. However, there is a continuing need for recycling polyethylene terephthalate waste in a broader and higher value-added sector.
The present invention overcomes the limitations of conventionally known polylactic acid resin compositions and provides a resin composition excellent in impact resistance and heat resistance, and extrusion and injection processability.
In addition, the present invention is to provide a resin composition having a large environmental load reduction effect by recycling waste plastics, especially polyethylene terephthalate waste, which occupies a considerable amount of household waste.
To achieve these and other advantages and in accordance with the purpose of the present invention,
(a) 16 to 82 weight percent of polylactic acid resin;
(b) 15 wt% to 60 wt% polyethylene terephthalate resin;
(c) 2 wt% to 15 wt% of methyl methacrylate-butadiene-styrene type copolymer having a core-shell structure as an impact modifier;
(d) 0.3 wt% to 3.0 wt% of an epoxy group-containing acrylic ester resin as a chain extender; And
(e) 0.3 wt% to 3.0 wt% of the nucleating agent; And
(f) 0.3 to 3.0% by weight of the hydrolysis agent; an environmentally friendly resin composition is provided.
In addition, the present invention provides an eco-friendly resin composition characterized in that the epoxy group-containing acrylic ester resin is represented by the following formula (1).
[Formula 1]
In Formula 1, R1, R2, R3, R4, and R5 each independently represent a hydrogen atom or a methyl group, and R6 is an alkyl group. x, y, z respectively represent an average degree of polymerization as an integer of 1-20.
In addition, the present invention is characterized in that the weight average molecular weight of the polylactic acid resin is 50,000 to 400,000.
In another aspect, the present invention provides an environment-friendly resin composition, characterized in that the polyethylene terephthalate resin is recycled polyethylene terephthalate resin.
In addition, the present invention provides an environmentally friendly resin composition characterized in that the polyethylene terephthalate resin has a melting temperature of 240 ℃ to 280 ℃, an average intrinsic viscosity of 0.3 to 1.3 dl / g, and a moisture content of 0.1 to 0.4%.
In addition, the present invention is an environmentally friendly resin composition, wherein the methyl methacrylate-butadiene-styrene type copolymer is made of butadiene in the core, and the shell is made of (meth) acrylic acid ester, styrenevinyl, vinyl cyanide or a combination thereof. To provide.
According to another embodiment of the present invention, the carbodiimide-based compound is a carbodiimide of the monomer type represented by the following formula (2), a polymer type carbodiimide represented by the following formula (3), or a combination thereof It provides an environmentally friendly resin composition comprising:
[Formula 2]
In Formula 2, R 1 and R 2 each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 36 carbon atoms.
(3)
In Formula 3, R is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 36 carbon atoms, and n represents an average degree of polymerization as an integer of 2 to 30,000.
According to another embodiment of the present invention, 0.2 to 5 wt% of at least one additive selected from the group consisting of a thermal stabilizer, an antioxidant, a lubricant, a light stabilizer, a black master batch and a nucleating agent based on 100 parts by weight of the total resin composition It provides an eco-friendly resin composition characterized in that it further comprises within the sub range.
According to another embodiment of the present invention, a molded article prepared from the resin composition is provided.
The resin composition according to the present invention can reduce environmental load by using polylactic acid as part of the base resin. In particular, by using a polyethylene terephthalate resin available from recycled polyethylene terephthalate in order to improve the low carbon dioxide reduction effect that is a problem in the conventional polylactic acid resin blend has an advantage that can further improve the environmental friendliness.
Therefore, it is expected that the present invention can be widely applied to materials for components such as automobile parts and housings of electric and electronic devices.
The present invention can be all accomplished by the following description. It is to be understood that the preferred embodiments of the invention are described, but the invention is not necessarily limited thereto.
(a) Polylactic acid Suzy
In the present invention, the polylactic acid resin, which is one of the components constituting the base resin, is generally 2-hydroxy lactate (lactic acid) or a thermoplastic polyester of lactide (L- and D-lactic acid as a raw material, or a mixture thereof, Any of lactide, a dimer of lactic acid, is possible) and has a repeating unit of-[O-CH (CH 3 ) -CO]-. The alpha carbon of the monomer has optical activity (L-form). In this connection, it is preferable to use a resin having high optical purity of the lactic acid component. Specifically, it is preferable that L-type (ie, poly-L-lactic acid) is included in the total lactic acid component of about 80% or more, and includes about 95% or more More preferred. The higher the optical purity of 95% or more, the better the compatibility, the faster the crystallization rate and excellent mechanical properties can be obtained.
The molecular weight of the polylactic acid resin is not particularly limited as long as it can be molded, but is preferably about 50,000 to 400,000, more preferably 100,000 to 350,000 based on the weight average molecular weight (Mw). If the weight average molecular weight is less than 50,000, the mechanical properties may be lowered, while if the weight average molecular weight is more than 400,000, there may be a problem that the fluidity is lowered.
The melting point of the polylactic acid resin is also not particularly limited, but is preferably about 145 ° C or higher. In particular, since the melting point tends to be higher with higher optical purity, it is preferable to use a resin having high optical purity when a high temperature is required during processing.
The content of the resin composition thickening polylactic acid resin according to the present invention is preferably in the range of about 16 to 82% by weight, more preferably about 30 to 70% by weight, based on the weight of the base resin. When the polylactic acid resin content is less than 16% by weight, the effect of reducing the environmental load is small, whereas when it exceeds 82% by weight, impact resistance and heat resistance are lowered, so that the intended physical property level cannot be achieved.
(b) Polyethylene terephthalate Suzy
In the present invention, a fresh polyethylene terephthalate or recycled polyethylene terephthalate may be used as the polyethylene terephthalate resin. One of the advantages of the present invention is that it is possible to improve the physical properties of the resin composition by using polyethylene terephthalate waste, which has been required to recycle the existing. That is, the polyethylene terephthalate resin contained in the resin composition of the present invention can use the recycled polyethylene terephthalate resin without particular limitation because the recycled polyethylene terephthalate resin has substantially the same composition. Therefore, in the present invention, the polyethylene terephthalate resin can use both recycled polyethylene terephthalate including newly synthesized polyethylene terephthalate, and it will be particularly advantageous to use recycled polyethylene terephthalate from the viewpoint of economics and environmental protection. Such recycled polyethylene terephthalate may have a form in which a waste polyethylene terephthalate bottle is first washed and pulverized flakes are pelletized through an extrusion process.
In the present invention, the polyethylene terephthalate component not only improves the thermal and mechanical properties of the resin composition, but also improves the recyclability of the waste polyethylene terephthalate as described above, thereby reducing the environmental load and reducing the cost.
In addition, in the composition according to the present invention, the polyethylene terephthalate resin provides a reactive end group capable of reacting with the chain extender, thereby synergistically acting in increasing the molecular weight and improving heat resistance and mechanical strength. The polyethylene terephthalate resin preferably has a melting temperature of about 240 to 280 ° C., more preferably about 255 to 265 ° C., and an average intrinsic viscosity of about 0.3 to 1.3 dl / g, more preferably about 0.45. To 1.0 dl / g, and a moisture content is preferably about 0.1 to 0.4%, more preferably about 0.15 to 0.25%.
According to the invention, the content of polyethylene terephthalate resin is in the range of about 15 to 60% by weight, more preferably about 30 to 50% by weight, based on the weight of the resin. If the content of the polyethylene terephthalate resin is less than 15% by weight, the heat resistance is lowered. If the content exceeds 60% by weight, the workability is lowered, and thus, the intended physical properties cannot be achieved.
Therefore, since the cycle time (cycle time) may be increased during injection molding, it is necessary to adjust the range described above.
(C) Methyl methacrylate Butadiene-styrene MBS ) Type copolymer
In the present invention, a methyl methacrylate-butadiene-styrene copolymer type having a core-shell structure (hereinafter, referred to as an MBS type copolymer), which is widely known in the art as an impact modifier of a resin composition. ) Resin is used.
In a preferred embodiment of the MBS type copolymer, the core is made of butadiene rubber, and the shell is preferably made of one or two or more of (meth) acrylic acid esters, styrenevinyl and vinyl cyanide. Examples of the meta (acrylic acid) ester in the components constituting the shell include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate and t-butyl (meth) acrylate. N-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxy (meth) acrylate Propyl, etc., and examples of styrene vinyl include styrene, alpha-methylstyrene, vinyltoluene, o-ethylstyrene, and the like, and examples of vinyl cyanide include acrylonitrile, methacrylonitrile, and ethacrylonitrile.
In the present invention, the MBS type impact modifier acts as an impact modifier in the base resin (polylactic acid resin / polyethylene terephthalate resin) to improve impact resistance. The content of the MBS type copolymer is in the range of 2 wt% to 15 wt%, preferably 3 to 13 wt% of the base resin. At this time, if less than 2 parts by weight, the impact strength is insufficient to obtain the desired physical properties, while if it exceeds 15 parts by weight it is necessary to control the above range because the fluidity is lowered may cause difficulties in processing.
(d) epoxy group-containing Acrylic Ester resin
According to the present invention, an oligomer resin containing various functional groups may be used as the chain extender, and an acrylic oligomer resin containing an epoxy group represented by the following general formula (3) may be used. More specifically, a styrene-acrylic ester resin containing an epoxy group or an acrylic ester resin containing no styrene is a resin having a molecular weight of 3,000 or less and an average number of functional groups of 4 or more and a polydispersity index (PDI) of 3 or more.
[Formula 1]
Wherein R1, R2, R3, R4 and R5 each contain a hydrogen atom or a methyl group, and R6 is an alkyl group. x, y, z respectively represent an average degree of polymerization as an integer of 1-20.
The chain extender component may react with a polylactic acid resin and a carboxyl group at the end of polyethylene terephthalate and an epoxy group of a chain extender to form a branched chain through chain extension, thereby improving melt strength and improving compatibility. By contributing, the mechanical, thermal and general properties are improved.
According to the present invention, the acrylic ester resin containing the epoxy group is preferably contained in an amount of about 0.3 to 3 parts by weight, more preferably about 0.5 to 2 parts by weight. When the content of the chain extender is too small, it does not affect the expected improvement of physical properties according to the addition, while in the case of too high, it is preferable to control the above-mentioned range because the fluidity is difficult to injection injection due to the increase in molecular weight.
(e) Nucleating agent
Inorganic nucleating agents can be used as nucleating agents, and typically talc of fine particles can be used. More specifically, talc having an average particle size (d50 (μm)) of 1.0 to 5.0 μm may be used, and more preferably, talc of d50 (μm) of 2.0 to 4.0 is suitable.
In the present invention, talc, an inorganic nucleating agent, is contained in an amount of about 0.3 wt% to 3.0 wt%, preferably about 0.5 wt% to 2.5 wt%. If less than 0.3% by weight, the nucleus effect is not expressed and the cooling time is increased during injection molding, and post-deformation may occur during extraction, whereas if it exceeds 3.0% by weight, the mechanical stiffness is increased to reduce the elongation. In order to cause defects such as pinholes on the surface of the injection molded product, it is necessary to adjust the above range.
(f) Hydrolysis agent
According to the present invention, a carbodiimide-based compound may be used as the hydrolysis agent, and typically carbodiimide of the monomer type represented by the following formula (2) and carbodiimide of the polymer type represented by the following formula (3) It is possible to use, preferably a mixture of the monomer type and polymer type.
[Formula 2]
In the above formula, R 1 and R 2 are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 36 carbon atoms. Specific examples of the compound according to Chemical Formula 2 include bis- (2,6-diisopropyl-phenyl) -carbodiimide.
(3)
In the above formula, R is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 36 carbon atoms, and n represents an average degree of polymerization as an integer of 2 to 30,000.
Specific examples of the compound according to Chemical Formula 3 include poly [(2,4,6-triisopropyl-phenyl) -carbodiimide].
Monomer type carbodiimide is excellent in reactivity and reacts rapidly with carboxyl groups at the end of polyester to reduce the number of end groups, while carbodiimide of polymer type exhibits long-term hydrolysis characteristics, thereby maintaining the physical properties of the composition. It plays a role.
According to a preferred aspect of the present invention, when used in the form of a mixture of the monomer type and the polymer type carbodiimide-based compound, the composition ratio of the monomer type and the polymer type is based on weight, preferably about 90:10 to about 10: 90, more preferably about 50:50.
In addition, it is preferable to use monocarbodiimide and / or poly carbodiimide prepared in the form of granules to facilitate processing. In the present invention, the carbodiimide-based compound is contained in an amount of about 0.3 wt% to 3.0 wt%, preferably about 0.5 wt% to 2.5 wt%. If less than 0.3% by weight, the hydrolysis characteristics are not expressed, whereas if more than 3% by weight may cause a decrease in mechanical properties, it is necessary to adjust the above range.
(g) Other additives
According to the present invention, in addition to the above-described components, various additives commonly used in the art such as heat stabilizers, antioxidants, lubricants, light stabilizers, black master batches, nucleating agents and the like within the scope of not impairing the characteristics of the present invention alone. Or in combination up to about 5 parts by weight, preferably within the range of about 0.2 to 5 parts by weight, based on 100 parts by weight of the total resin composition described above, depending on the purpose of use and use.
According to a preferred embodiment of the present invention, the components constituting the composition can be obtained through a melt kneading process known in the art, for which ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single screw extruder, 2 A screw screw extruder, a corneader, a multi screw screw extruder, etc. can be used.
The resin composition described above can not only exhibit the excellent mechanical properties of polycarbonate and the environmentally friendly and excellent flow characteristics of the polylactic acid resin, but also can obtain a molded article with improved hydrolysis resistance and impact resistance. In particular, it is preferable in terms of environmental friendliness, since it is possible to further expand the applicability of waste polyethylene terephthalate, which has been continuously studied for its utilization. Therefore, it may be widely used in various fields such as various OA devices, information and communication devices, automobile interior and exterior materials, building members, and home telephone equipment.
The present invention can be more clearly understood by the following examples, which are only intended to illustrate the present invention and are not intended to limit the scope of the invention.
The components used in the following Examples and Comparative Examples are as follows.
1) Polylactic Acid Resin: 4032D (NatureWorks)
2) PET resin: recycled polyethylene terephthalate chip (Samyang)
3) Impact modifier: PARALOID EXL2602 (Rohm and Haas)
4) Chain Extender: ADR 4368S (BASF)
5) Nucleating agent: MICEL-TONE 5000S (HAYASHI KASEI)
6) Hydrolysis Agent: Stabilizer G500 (RASCHIG)
Examples 1 to 11
A polylactic acid resin having a weight average molecular weight of 200,000, a melting temperature of 255 to 265 ° C., an average intrinsic viscosity of 0.65 dl / g, and a moisture content of about 0.2% was prepared by mixing the remaining polyethylene terephthalate resin and the remaining ingredients in the composition of Table 1 below.
The components constituting the resin composition shown in Table 1 are uniformly mixed and dispersed in a Henschel mixer, and then the extrusion temperature is about 200 to 245 using a coaxial twin screw extruder of L / D = 40 and Φ = 25 (mm). The resin composition was prepared by extrusion under conditions of 200 ° C. and screw rotation speed.
Comparative Examples 1 to 6
A resin composition was prepared in the same manner as in Example 1, except that the composition ratio was changed as described in Table 2 below.
[Experimental Example]
Physical property measurement experiment
After fixing the pelletized resin compositions prepared in Examples 1 to 11 and Comparative Examples 1 to 6 at a cylinder temperature of about 220 to 260 ° C. and a mold temperature of 40 ° C., the specimens were injection molded, and the properties of each of the molded specimens were It was measured by the method. The experimental results are shown in Table 5 below.
Physical properties were evaluated by the following measuring method.
-Flow index: ASTM D1238 (250 ℃, 5.0kg)
-Tensile Strength and Elongation: ASTM D638 (cross head speed: 50 mm / min)
-Flexural strength and modulus: ASTM D790 (cross head speed: 10 mm / min)
-Impact Strength: ASTM D256 (1/8 inch, Notched Izod, Room Temperature)
-Heat Deflection Temperature: ASTM D648 (4.6 kg f / cm 2 )
-Hydrolysis test: After measuring for 60 days in a thermo-hygrostat and maintaining 90% RH of humidity, measured and evaluated the physical properties before and after the test.
-Extrusion processability: Relative comparison according to the degree of swelling of the strand during extrusion (see Table 3).
-Injection processability: The cooling time required to obtain a normal injection molding during injection
Relative comparison. (See Table 4)
Temperature (℃)
(kg f · cm / cm)
(kg f / cm 2)
(%)
(kg f / cm 2)
(kg f / cm 2)
(g / 10 min)
* Property retention rate (%) = ((property after hydrolysis test) / (property before hydrolysis test)) X100
As shown in Table 5, the physical properties before and after the constant temperature and humidity test of the resin composition specimens prepared according to Examples 1 to 11 were relatively superior to the physical properties of the specimens prepared according to Comparative Examples 1 to 6, All reference values were satisfied. Therefore, it was found that the resin composition of the present invention reduces the environmental load and can be applied to materials for components such as automobile parts and housings of electric and electronic devices.
All simple modifications and variations of the present invention fall within the scope of the present invention, and the specific scope of the present invention will be apparent from the appended claims.
Claims (9)
(b) 15 wt% to 60 wt% polyethylene terephthalate resin;
(c) 2% to 15% by weight of methyl methacrylate-butadiene-styrene type copolymer having a core-shell structure as an impact modifier;
(d) 0.3 wt% to 3.0 wt% of an epoxy group-containing acrylic ester resin as a chain extender;
(e) 0.3 to 3.0 weight percent talc as nucleating agent; And
(f) 0.3 to 3.0% by weight of a hydrolysis agent, a carbodiimide of a monomer type represented by the following formula (2), a carbodiimide of a polymer type represented by the following formula (3), or a combination thereof;
Eco-friendly resin composition:
(2)
In Formula 2, R 1 and R 2 each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 36 carbon atoms,
(3)
In Formula 3, R is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 36 carbon atoms, and n represents an average degree of polymerization as an integer of 2 to 30,000.
[Formula 1]
In Formula 1, R1, R2, R3, R4, and R5 each independently represent a hydrogen atom or a methyl group, and R6 is an alkyl group. x, y, z respectively represent an average degree of polymerization as an integer of 1-20.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080000594A (en) * | 2005-04-26 | 2008-01-02 | 유니티카 가부시끼가이샤 | Biodegradable resin composition, and molded body and production method thereof |
| KR100900251B1 (en) | 2007-07-19 | 2009-05-29 | 정지수 | Polymer composition of polylactic acid, foam sheet using the same, manufacturing method thereof and use of foam-molding product thereby |
| KR20090084372A (en) * | 2008-02-01 | 2009-08-05 | 주식회사 엘지화학 | Biodegradable polylactic acid resin composition having high thermal stability and impact strength, and preparation method thereof |
| KR20100079986A (en) * | 2008-12-31 | 2010-07-08 | 주식회사 삼양사 | Environmentally friendly resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080000594A (en) * | 2005-04-26 | 2008-01-02 | 유니티카 가부시끼가이샤 | Biodegradable resin composition, and molded body and production method thereof |
| KR100900251B1 (en) | 2007-07-19 | 2009-05-29 | 정지수 | Polymer composition of polylactic acid, foam sheet using the same, manufacturing method thereof and use of foam-molding product thereby |
| KR20090084372A (en) * | 2008-02-01 | 2009-08-05 | 주식회사 엘지화학 | Biodegradable polylactic acid resin composition having high thermal stability and impact strength, and preparation method thereof |
| KR20100079986A (en) * | 2008-12-31 | 2010-07-08 | 주식회사 삼양사 | Environmentally friendly resin composition |
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