The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0132194, filed on October 31, 2018 and Korean Patent Application No. 10-2019-0133947, filed on October 25, 2019, and the corresponding Korean patent All content disclosed in the literature of the application is incorporated as a part of this specification.
[3]
[Technical field]
[4]
The present invention relates to a thermoplastic resin composition, and to a thermoplastic resin composition having excellent heat resistance, chemical resistance and appearance properties.
[5]
background
[6]
In general, an acrylic graft copolymer obtained by graft polymerization of an aromatic vinyl monomer and a vinyl cyanide monomer to an acrylic rubber polymer has excellent weather resistance and aging resistance. The thermoplastic resin composition containing such an acrylic graft copolymer is used in various fields such as automobiles, ships, leisure products, building materials, horticulture, and the like, and its usage is rapidly increasing.
[7]
On the other hand, as users' demands for emotional quality increase, research is being conducted to realize a luxurious appearance, excellent colorability, and weather resistance by finishing substrates such as PVC and iron plates with a thermoplastic resin composition.
[8]
The decorative sheet containing the acrylic graft copolymer has excellent processing stability compared to conventional PVC or PP, and does not contain heavy metal components, so it is attracting attention as an eco-friendly material. However, there are problems that press marks are generated during storage or that the dimensions of the sheet are deformed (stretched or reduced) during processing. In addition, when an adhesive is used for adhesion to the substrate, there is also a problem of melting due to poor chemical resistance.
[9]
Therefore, there is a need to develop a thermoplastic resin composition having improved appearance quality and chemical resistance.
[10]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[11]
It is an object of the present invention to provide a thermoplastic resin composition having improved heat resistance, chemical resistance and appearance characteristics while maintaining basic physical properties such as processability, hardness, and mechanical properties.
[12]
means of solving the problem
[13]
In order to solve the above problems, the present invention provides a graft copolymer comprising a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, a styrene-based monomer unit, and a vinyl cyan-based monomer unit; C 1 To C 3 A first styrenic copolymer including an alkyl-substituted styrenic monomer unit and a vinyl cyan-based monomer unit; and a second styrenic copolymer including an unsubstituted styrene-based monomer unit and a vinyl cyan-based monomer unit.
[14]
Effects of the Invention
[15]
The thermoplastic resin composition according to the present invention can implement excellent processability, hardness, colorability, mechanical properties, heat resistance, chemical resistance and appearance properties. In detail, the thermoplastic resin composition according to the present invention can implement excellent heat resistance and appearance characteristics by using the first styrenic copolymer including a C 1 to C 3 alkyl styrene-based monomer unit and a vinyl cyan-based monomer unit. . In addition, by using the second styrenic copolymer including an unsubstituted styrene-based monomer unit and a vinyl cyan-based monomer unit together, excellent chemical resistance may be realized.
[16]
Modes for carrying out the invention
[17]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[18]
The terms or words used in the present specification and claims are not to be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[19]
[20]
In the present invention, the weight average molecular weight of the shell of the graft copolymer may mean the weight average molecular weight of the copolymer including the styrene-based monomer unit and the vinyl cyan-based monomer unit grafted to the core.
[21]
Here, the styrenic monomer unit may be at least one selected from the group consisting of C 1 to C 3 alkyl-substituted styrenic monomer units and unsubstituted styrenic monomer units.
[22]
[23]
In the present invention, the weight average molecular weight of the shell of the graft copolymer is determined by dissolving the graft copolymer in acetone and centrifuging, and then dissolving the portion (sol) dissolved in acetone in tetrahydrofuran, followed by gel permeation chromatography ( It can be measured as a relative value with respect to a standard PS (standard polystyrene) sample using GPC, water breeze).
[24]
[25]
In the present invention, the graft ratio of the graft copolymer can be calculated based on the following formula.
[26]
[27]
Graft rate (%): Weight of grafted monomer (g) / Weight of rubbery polymer (g) × 100
[28]
[29]
Weight of grafted monomer (g): weight of insoluble material (gel) after dissolving graft copolymer powder in acetone and centrifuging
[30]
Weight (g) of rubbery polymer: Weight of C 4 to C 10 alkyl (meth)acrylate-based monomers theoretically added during the manufacturing process of the graft copolymer powder
[31]
[32]
In the present invention, the average particle diameter of the seed, core, and graft copolymer can be measured using a dynamic light scattering method, and in detail, it can be measured using Nicomp 380 equipment (product name, manufacturer: PSS). can
[33]
In the present invention, the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, specifically, an average particle diameter of scattering intensity.
[34]
[35]
In the present invention, the weight average molecular weight can be measured as a relative value with respect to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent.
[36]
[37]
1. Thermoplastic resin composition
[38]
A thermoplastic resin composition according to an embodiment of the present invention includes: A) a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, a styrene-based monomer unit, and a vinyl cyan-based monomer unit; B-1) a first styrenic copolymer comprising a C 1 to C 3 alkyl-substituted styrenic monomer unit and a vinyl cyan-based monomer unit; and B-2) a second styrenic copolymer including an unsubstituted styrene-based monomer unit and a vinyl cyan-based monomer unit.
[39]
[40]
The thermoplastic resin composition according to an embodiment of the present invention may further include an olefin-based copolymer including C) C 1 to C 3 alkyl (meth)acrylate-based monomer units.
[41]
[42]
Hereinafter, each component of the thermoplastic resin composition of the present invention will be described in detail.
[43]
[44]
A) graft copolymer
[45]
The graft copolymer includes a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, a styrene-based monomer unit, and a vinyl cyan-based monomer unit.
[46]
[47]
The graft copolymer may impart excellent weather resistance and mechanical properties to the thermoplastic resin composition. Specifically, the C 4 to C 10 alkyl (meth)acrylate-based monomer unit can provide excellent weather resistance to the thermoplastic resin composition, and the core of the graft copolymer provides excellent mechanical properties to the thermoplastic resin composition. can
[48]
[49]
The graft copolymer may include a core made of a cross-linked polymer including at least one selected from the group consisting of C 4 to C 10 alkyl (meth)acrylate monomer units, styrenic monomer units, and vinyl cyan monomer units; And it may have a core-shell structure including a shell including a styrene-based monomer unit and a vinyl cyan-based monomer unit grafted to the core.
[50]
[51]
The C 4 to C 10 alkyl (meth) acrylate-based monomer unit is butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylic It may be a unit derived from at least one monomer selected from the group consisting of rate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate and decyl (meth) acrylate; , of which units derived from butyl acrylate are preferred.
[52]
The C 4 to C 10 alkyl (meth)acrylate-based monomer unit may be included in an amount of 40 to 60% by weight or 45 to 55% by weight, of which 45 to 55% by weight, based on the total weight of the graft copolymer. It is preferable to include When the above-described range is satisfied, mechanical properties such as impact resistance of the first graft copolymer may be further improved.
[53]
[54]
The styrenic monomer unit may be a unit derived from at least one monomer selected from the group consisting of styrene, α-methyl styrene, p-methyl styrene and 2,4-dimethyl styrene, of which styrene and α-methyl styrene It may be a unit derived from one or more monomers selected from the group consisting of.
[55]
The styrenic monomer unit may be included in an amount of 25 to 50% by weight or 30 to 45% by weight, preferably 30 to 45% by weight, based on the total weight of the graft copolymer. When the above-described range is satisfied, polymerization of the graft copolymer may be easier. In addition, compatibility between the graft copolymer and the first and second styrenic copolymers may be improved, and processability of the thermoplastic resin composition may be further improved.
[56]
[57]
The vinyl cyan-based monomer unit may be a unit derived from at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, and among these, a unit derived from acrylonitrile is preferable.
[58]
The vinyl cyan-based monomer unit may be included in an amount of 3 to 20% by weight or 6 to 17% by weight, preferably 6 to 17% by weight, based on the total weight of the graft copolymer. When the above-described range is satisfied, the chemical resistance of the graft copolymer may be further improved.
[59]
[60]
The graft copolymer is a butyl acrylate-styrene-acrylonitrile copolymer, a butyl acrylate-α-methyl styrene-acrylonitrile copolymer and a butyl acrylate-styrene-α-methyl styrene-acrylonitrile copolymer. It may be selected from the group consisting of, of which butyl acrylate-styrene-acrylonitrile copolymer is preferred.
[61]
[62]
The graft copolymer may be included in an amount of 5 to 45 parts by weight or 10 to 35 parts by weight based on 100 parts by weight of the total of the graft copolymer, the first styrenic copolymer, and the second styrenic copolymer, of which It is preferably included in an amount of 10 to 35 parts by weight. When the above-described range is satisfied, mechanical properties such as impact resistance of the thermoplastic resin composition can be remarkably improved.
[63]
[64]
On the other hand, the graft copolymer 1) preparing a core by polymerizing at least one selected from the group consisting of a C 4 to C 10 alkyl (meth)acrylate-based monomer, a styrene-based monomer, and a vinyl cyan-based monomer. ; 2) It may be prepared by a manufacturing method comprising the step of preparing a shell by polymerizing a styrene-based monomer and a vinyl cyan-based monomer in the presence of the core.
[65]
[66]
The manufacturing of the core may include: preparing a seed by polymerizing at least one selected from the group consisting of a C 4 to C 10 alkyl (meth)acrylate-based monomer, a styrene-based monomer, and a vinyl cyanide-based monomer; And in the presence of the seed, by polymerizing a C 4 to C 10 alkyl (meth)acrylate-based monomer may include preparing a core.
[67]
[68]
The C 4 to C 10 alkyl (meth)acrylate-based monomer, the styrene-based monomer, and the vinyl cyan-based monomer are the same as described above.
[69]
[70]
The polymerization may be emulsion polymerization, and may be carried out at 50 to 85 °C or 60 to 80 °C, of ​​which it is preferably carried out at 60 to 80 °C. When the above-mentioned range is satisfied, emulsion polymerization can be stably performed.
[71]
[72]
The step of preparing the seed and the core may be performed in the presence of at least one selected from the group consisting of an emulsifier, an initiator, a crosslinking agent, a grafting agent, an electrolyte, and water.
[73]
The emulsifier may be at least one selected from the group consisting of a metal salt derivative of a C 12 to C 18 alkylsulfosuccinic acid and a metal salt derivative of a C 12 to C 20 alkyl sulfate ester.
[74]
The metal salt derivative of the C 12 to C 18 alkylsulfosuccinic acid is sodium dicyclohexylsulfosuccinate, sodium dihexylsulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, potassium di-2-ethylhexylsulfosuccinate and di-2 It may be at least one selected from the group consisting of -ethylhexyl sulfosuccinate lithium.
[75]
The metal salt derivative of the C 12 to C 20 alkyl sulfate ester is selected from the group consisting of sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate and potassium octadecyl sulfate. There may be more than one type.
[76]
[77]
The initiator may be an inorganic peroxide or an organic peroxide. The inorganic peroxide is a water-soluble initiator, and may be at least one kind from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate. The organic peroxide is a fat-soluble initiator, and may be at least one selected from the group consisting of cumene hydroperoxide and benzoyl peroxide.
[78]
[79]
The crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol It may be at least one selected from the group consisting of dimethacrylate, trimethylolpropane trimethacrylate, and trimethylolmethane triacrylate.
[80]
[81]
The grafting agent may be at least one selected from the group consisting of allyl methacrylate, triallyl isocyanurate, triallylamine and diallylamine.
[82]
[83]
The electrolyte is KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 4 , Na 2 S 2 O 7 , K 4 P 2 O 7 , K 3 PO 4 , Na 3 PO 4 or Na 2 HPO 4 , may be at least one selected from the group consisting of KOH and NaOH, of which KOH is preferred.
[84]
[85]
The water serves as a medium during emulsion polymerization, and may be ion-exchanged water.
[86]
[87]
On the other hand, in the step of producing the shell, the styrene-based monomer and the vinyl cyanide-based monomer can be polymerized while continuously input at a constant rate, and when added in the above-described manner, it is possible to easily suppress runaway due to heat removal and excessive overheating during polymerization. can
[88]
[89]
The polymerization may be emulsion polymerization, and may be carried out at 50 to 85 °C or 60 to 80 °C, of ​​which it is preferably carried out at 60 to 80 °C. When the above-mentioned range is satisfied, emulsion polymerization can be stably performed.
[90]
[91]
The step of preparing the shell may be performed in the presence of at least one selected from the group consisting of an emulsifier, an initiator, and water.
[92]
The emulsifier, the initiator, and the water are preferably polymerized while continuously added together with the styrenic monomer and the vinyl cyanide monomer. When the above-mentioned conditions are satisfied, the pH is kept constant, so that graft polymerization is easy, the stability of the graft copolymer particles is excellent, and the inside of the particles can be uniformly prepared.
[93]
[94]
The emulsifier may be a metal carboxylate derivative, and the metal carboxylate derivative may be at least one selected from the group consisting of a C 12 to C 20 fatty acid metal salt and a rosin acid metal salt.
[95]
The C 12 to C 20 fatty acid metal salt may be at least one selected from the group consisting of sodium fatty acid, sodium laurate, sodium oleate and potassium oleate.
[96]
The metal rosin acid salt may be at least one selected from the group consisting of sodium rosin acid salt and potassium rosin acid salt.
[97]
[98]
The type of the initiator is as described above, and among these, an organic peroxide is preferable, and t-butylperoxy ethylhexyl carbonate is more preferable.
[99]
[100]
On the other hand, the graft copolymer prepared by the above-described manufacturing method may be in the form of latex.
[101]
[102]
The latex-type graft copolymer may be prepared in powder form by performing agglomeration, aging, washing, dehydration and drying.
[103]
[104]
On the other hand, the graft copolymer is two types of graft copolymers having different average particle diameters of cores, that is, the first graft copolymer, in order to improve the impact resistance, weather resistance, colorability, surface gloss characteristics and appearance characteristics of the thermoplastic resin composition. a copolymer and a second graft copolymer.
[105]
[106]
The first graft copolymer may have an average particle diameter of the core of 300 to 500 nm or 350 to 450 nm, of which 350 to 450 nm is preferable. When the above-described range is satisfied, mechanical properties such as impact resistance of the thermoplastic resin composition may be improved.
[107]
[108]
The first graft copolymer may have a graft rate of 20 to 100%, 40 to 80%, or 45 to 60%, of which 40 to 60% is preferable. When the above-described range is satisfied, compatibility with the first and second styrenic copolymers is improved, so that the graft copolymer may be uniformly dispersed in the thermoplastic resin composition. In addition, the mechanical properties of the thermoplastic resin composition can be remarkably improved.
[109]
[110]
The first graft copolymer may have a weight average molecular weight of the shell of 100,000 to 300,000 g/mol or 150,000 to 250,000 g/mol, of which 150,000 to 250,000 g/mol is preferable. When the above-described range is satisfied, compatibility with the first and second styrenic copolymers is improved, so that the graft copolymer may be uniformly dispersed in the thermoplastic resin composition. In addition, the mechanical properties of the thermoplastic resin composition can be remarkably improved.
[111]
[112]
The first graft copolymer is 5 to 30 parts by weight based on 100 parts by weight of the sum of the first graft copolymer, the second graft copolymer, the first styrenic copolymer, and the second styrenic copolymer It may be included in an amount of 10 to 25 parts by weight, of which it is preferably included in an amount of 10 to 25 parts by weight. When the above-described range is satisfied, mechanical properties such as impact resistance of the thermoplastic resin composition can be remarkably improved.
[113]
[114]
On the other hand, the second graft copolymer may have an average particle diameter of 50 to 150 nm or 75 to 125 nm of the core, more preferably 75 to 125 nm. When the above-mentioned range is satisfied, the specific surface area of ​​the core increases, so that the weather resistance of the thermoplastic resin composition can be remarkably improved. In addition, since visible light can pass through without being scattered from the core, colorability can also be improved. Also, surface gloss properties and appearance properties can be improved.
[115]
[116]
The second graft copolymer may have a graft rate of 20 to 80% or 25 to 60%, of which 25 to 60% is preferable. When the above-described range is satisfied, compatibility with the first and second styrenic copolymers is improved, so that the graft copolymer may be uniformly dispersed in the thermoplastic resin composition. In addition, the colorability and surface glossiness of the thermoplastic resin composition may be remarkably improved.
[117]
[118]
The second graft copolymer may have a weight average molecular weight of 50,000 to 200,000 g/mol or 70,000 to 170,000 g/mol of the shell, of which 70,000 to 170,000 g/mol is preferable. When the above-described range is satisfied, compatibility with the first and second styrenic copolymers may be further improved, and mechanical properties of the thermoplastic resin composition may be further improved.
[119]
[120]
The second graft copolymer is 0.1 to 15 parts by weight or 1 based on 100 parts by weight of the sum of the first graft copolymer, the second graft copolymer, the first styrenic copolymer, and the second styrenic copolymer. It may be included in an amount of from 1 to 10 parts by weight, of which it is preferably included in an amount of 1 to 10 parts by weight. When the above-mentioned range is satisfied, the weather resistance, colorability, and surface gloss properties of the thermoplastic resin composition can be remarkably improved.
[121]
[122]
The graft copolymer may include the first graft copolymer and the second graft copolymer in a weight ratio of 50:50 to 99:1 or 60:40 to 95:5, of which 60:40 It is preferable to include it in a weight ratio of 95:5. When the above-mentioned range is satisfied, the thermoplastic resin composition may implement excellent mechanical properties, weather resistance, colorability, and surface gloss properties.
[123]
[124]
B-1) first styrenic copolymer
[125]
The first styrenic copolymer is a matrix copolymer and includes a C 1 to C 3 alkyl styrenic monomer unit and a vinyl cyanide monomer unit.
[126]
[127]
The first styrenic copolymer may impart excellent heat resistance and appearance characteristics to the thermoplastic resin composition. Specifically, due to excellent heat resistance, it is possible to improve the dimensional stability of the molded article made of the thermoplastic resin composition, it is possible to minimize the press marks.
[128]
[129]
The C 1 to C 3 alkyl styrene-based monomer unit may be a unit derived from at least one selected from the group consisting of α-methyl styrene, p-methyl styrene, and 2,4-dimethyl styrene, of which α- Units derived from methyl styrene are preferred.
[130]
[131]
The type of the vinyl cyan-based monomer unit is the same as described above.
[132]
[133]
The first styrenic copolymer may be a copolymer of a monomer mixture including a C 1 to C 3 alkyl styrenic monomer and a vinyl cyanide monomer.
[134]
The monomer mixture may include the C 1 to C 3 alkyl styrene-based monomer and the vinyl cyan-based monomer in a weight ratio of 60:40 to 90:10 or 65:35 to 85:15, of which 65:35 to It is preferable to include it in a weight ratio of 85:15. If the above-described range is satisfied, heat resistance may be further improved.
[135]
[136]
The first styrenic copolymer may further include an unsubstituted styrenic monomer unit to facilitate polymerization. That is, the first styrenic copolymer may be a copolymer of a monomer mixture including a C 1 to C 3 alkyl styrene-based monomer, a vinyl cyan-based monomer, and an unsubstituted styrene-based monomer. The unsubstituted styrene-based monomer unit may be a unit derived from styrene.
[137]
[138]
In this case, the monomer mixture may include 55 to 75% by weight of the C 1 to C 3 alkyl styrenic monomer, 20 to 40% by weight of the vinyl cyanide monomer, and 0.1 to 15% by weight of the unsubstituted styrenic monomer. have. Preferably, the monomer mixture contains 60 to 70% by weight of the C 1 to C 3 alkyl styrenic monomer, 25 to 35% by weight of the vinyl cyanide monomer, and the unsubstituted styrene based on the total weight of the monomer mixture. It may be included in an amount of 1 to 10% by weight of the system monomer. When the above-described range is satisfied, polymerization of the first styrenic copolymer may proceed more easily.
[139]
[140]
The first styrenic copolymer may have a weight average molecular weight of 50,000 to 150,000 g/mol or 70,000 to 130,000 g/mol, of which 70,000 to 130,000 g/mol is preferable. When the above-described range is satisfied, excellent chemical resistance and mechanical properties may be realized.
[141]
[142]
The first styrenic copolymer may be selected from the group consisting of α-methyl styrene-acrylonitrile copolymer and α-methyl styrene-styrene-acrylonitrile copolymer, of which α-methyl styrene-acrylonitrile copolymer Copolymers are preferred.
[143]
[144]
The first styrenic copolymer may be included in an amount of 2 to 25 parts by weight or 7 to 20 parts by weight based on 100 parts by weight of the total of the graft copolymer, the first styrenic copolymer, and the second styrenic copolymer, Among them, it is preferably included in an amount of 7 to 20 parts by weight. When the above-described range is satisfied, the heat resistance and processability of the thermoplastic resin composition may be further improved, and the appearance characteristics of the thermoplastic resin molded article may be further improved.
[145]
Even when the graft copolymer includes both the first graft copolymer and the second graft copolymer, the first styrenic copolymer may be included in the thermoplastic resin composition in the above-described content.
[146]
[147]
The first styrenic copolymer may be a copolymer prepared by suspension or bulk polymerization of a monomer mixture including a C 1 to C 3 alkyl styrenic monomer and a vinyl cyanide monomer, and a high-purity polymer may be prepared among them. It is preferable that it is a copolymer prepared by bulk polymerization.
[148]
[149]
B-2) second styrenic copolymer
[150]
The second styrenic copolymer is a matrix copolymer and includes an unsubstituted styrenic monomer unit and a vinyl cyanide monomer unit.
[151]
[152]
The second styrenic copolymer may impart excellent processability, chemical resistance, and mechanical properties to the thermoplastic resin composition.
[153]
[154]
The types of the unsubstituted styrene-based monomer and the vinyl cyan-based monomer are the same as described above.
[155]
[156]
The second styrenic copolymer may be a copolymer of a monomer mixture including an unsubstituted styrenic monomer and a vinyl cyanide monomer.
[157]
The monomer mixture may include the unsubstituted styrenic monomer and the vinyl cyanide monomer in a weight ratio of 60:40 to 90:10 or 65:35 to 85:15, of which the weight ratio is 65:35 to 85:15. It is preferable to include When the above-described range is satisfied, processability and chemical resistance may be further improved.
[158]
[159]
The second styrenic copolymer may have a weight average molecular weight of 100,000 to 250,000 g/mol or 130,000 to 220,000 g/mol, of which 130,000 to 220,000 g/mol is preferable. When the above-described range is satisfied, excellent chemical resistance and mechanical properties may be realized.
[160]
[161]
The second styrene copolymer is preferably a styrene-acrylonitrile copolymer.
[162]
[163]
The second styrenic copolymer may be included in an amount of 50 to 80 parts by weight or 55 to 75 parts by weight based on 100 parts by weight of the total of the graft copolymer, the first styrenic copolymer, and the second styrenic copolymer, Among them, it is preferably included in an amount of 55 to 75 parts by weight. When the above-described range is satisfied, the processability, chemical resistance and mechanical properties of the thermoplastic resin composition may be further improved.
[164]
Even when the graft copolymer includes both the first graft copolymer and the second graft copolymer, the second styrenic copolymer may be included in the thermoplastic resin composition in the above-described content.
[165]
[166]
Meanwhile, the first styrenic copolymer and the second styrenic copolymer may be included in the thermoplastic resin composition in a weight ratio of 5:95 to 32:68, 9:91 to 25:75, or 10:90 to 20:80. and it is preferably included in the thermoplastic resin composition in a weight ratio of 10:90 to 20:80. When the above-described range is satisfied, the deterioration of basic physical properties such as hardness, mechanical properties, and heat resistance may be minimized, and external properties and chemical resistance may be further improved.
[167]
[168]
The second styrenic copolymer may be a copolymer prepared by suspension or bulk polymerization of a monomer mixture containing an unsubstituted styrene-based monomer and a vinyl cyanide monomer, and among them, a high-purity copolymer can be prepared by bulk polymerization. It is preferable that it is a manufactured copolymer.
[169]
[170]
C) Olefin-based copolymer
[171]
The olefin-based copolymer may include, as an additive, a C 1 to C 3 alkyl (meth)acrylate-based monomer unit.
[172]
[173]
The olefin-based copolymer may impart excellent chemical resistance to the thermoplastic resin composition.
[174]
[175]
The olefin- based copolymer may be a copolymer of a monomer mixture including a C 2 to C 4 olefin-based monomer and a C 1 to C 3 alkyl (meth)acrylate-based monomer. The C 2 to C 4 olefinic monomer may be at least one selected from the group consisting of ethylene, propylene, and butene, among which ethylene is preferable. The C 1 to C 3 alkyl (meth) acrylate-based monomer may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate and propyl (meth) acrylate, of which Methyl acrylate is preferred.
[176]
[177]
The olipene-based copolymer is a C 2 to C 4 olefin-based monomer unit and a C 1 to C 3 alkyl (meth)acrylate-based monomer unit in a weight ratio of 85:15 to 65:35 or 80:20 to 70:30. It may be included, and it is preferable to include it in a weight ratio of 80:20 to 70:30. When the above-described range is satisfied, the chemical resistance of the olefin-based copolymer may be further improved. Specifically, when the content of the alkyl (meth)acrylate-based monomer unit is too small, compatibility with the graft copolymer, the first styrenic copolymer, and the second styrenic copolymer decreases, and the thermoplastic resin Since it cannot be uniformly dispersed in the composition, the effect of improving chemical resistance may be insignificant. When the content of the alkyl (meth) acrylate-based monomer unit is too large, compatibility with the graft copolymer, the first styrenic copolymer, and the second styrenic copolymer is improved, but the content of the olefin-based monomer unit is reduced Therefore, the effect of improving chemical resistance may be insufficient.
[178]
[179]
The olefin-based copolymer may have a weight average molecular weight of 50,000 to 200,000 g/mol, 70,000 to 150,000 g/mol, or 90,000 to 120,000 g/mol, of which 90,000 to 120,000 g/mol is preferable. When the above-described range is satisfied, it is possible to provide a thermoplastic resin composition having excellent compatibility with the graft copolymer, the first styrenic copolymer, and the second styrenic copolymer, and excellent mechanical properties. Specifically, when it is less than the above range, the mechanical properties are lowered, and when it exceeds the above range, the compatibility with the graft copolymer, the first styrenic copolymer and the second styrenic copolymer decreases, Since it cannot be uniformly dispersed in the thermoplastic resin composition, the effect of improving chemical resistance may be reduced.
[180]
[181]
The olefin-based copolymer is preferably an ethylene-methyl acrylate copolymer.
[182]
[183]
The olefin-based copolymer may be included in an amount of 0.01 to 2 parts by weight or 0.5 to 1 parts by weight, based on 100 parts by weight of the total of the graft copolymer, the first styrenic copolymer, and the second styrenic copolymer, of which It is preferably included in an amount of 0.5 to 1 part by weight. When the above-described range is satisfied, the chemical resistance may be further improved without affecting the hardness, mechanical properties, and heat resistance of the thermoplastic resin composition.
[184]
Even when the graft copolymer includes both the first graft copolymer and the second graft copolymer, the olefin-based copolymer may be included in the thermoplastic resin composition in the above-described content.
[185]
[186]
The olefin-based copolymer may be used by using a commercially available material or by directly preparing it.
[187]
When the olefin-based copolymer is directly prepared, it may be prepared by at least one polymerization method selected from the group consisting of solution polymerization, slurry polymerization, gas phase polymerization, and high pressure polymerization.
[188]
[189]
On the other hand, the thermoplastic resin composition according to an embodiment of the present invention is an anti-drip agent, a flame retardant, an antibacterial agent, an antistatic agent, a stabilizer, a release agent, a heat stabilizer, an ultraviolet stabilizer, an inorganic additive, a lubricant, an antioxidant, a light stabilizer, a pigment, a dye and an inorganic It may further include one or more additives selected from the group consisting of fillers.
[190]
The thermoplastic resin composition according to an embodiment of the present invention preferably includes at least one selected from the group consisting of lubricants, antioxidants and UV stabilizers.
[191]
[192]
The molded article made of the thermoplastic resin composition according to an embodiment of the present invention may be a sheet, preferably a decorative sheet for furniture.
[193]
[194]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.
[195]
[196]
Preparation Example 1
[197]

[198]
In a nitrogen-substituted reactor, 3 parts by weight of styrene, 3 parts by weight of acrylonitrile, 0.1 parts by weight of sodium dodecyl sulfate as an emulsifier, 0.03 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, 0.02 parts by weight of allyl methacrylate as a grafting agent, 0.025 parts by weight of KOH and 53.32 parts by weight of distilled water were collectively added as an electrolyte, and the temperature was raised to 70° C., and then 0.03 parts by weight of potassium persulfate as an initiator was collectively added to initiate polymerization. After polymerization for 2 hours, the polymerization was terminated to obtain seeds (average particle diameter: 200 nm).
[199]
The average particle diameter of the seed was measured by a dynamic light scattering method using Nicomp 380 equipment (product name, manufacturer: PSS).
[200]
[201]

[202]
In the reactor in which the seed was obtained, 50 parts by weight of butyl acrylate, 0.6 parts by weight of sodium dodecyl sulfate as an emulsifier, 0.1 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, 0.04 parts by weight of allyl methacrylate as a grafting agent, 30 parts by weight of distilled water A mixture of 0.05 parts by weight of potassium persulfate as a part and an initiator was polymerized while continuously added at a constant rate for 4 hours at 70° C., and further polymerized for 1 hour after the addition was completed, followed by completion of the core (average particle diameter: 400 nm) was obtained.
[203]
The average particle diameter of the core was measured by a dynamic light scattering method using Nicomp 380 equipment (product name, manufacturer: PSS).
[204]
[205]

[206]
35 parts by weight of styrene, 9 parts by weight of acrylonitrile, and 39 parts by weight of distilled water were added to the reactor in which the core was obtained, 1.9 parts by weight of potassium rosinate as an emulsifier, and 0.19 parts by weight of t-butylperoxyethylhexyl carbonate as an initiator The first mixture containing the first mixture and the second mixture containing 0.16 parts by weight of sodium pyrophosphate as an activator, 0.24 parts by weight of dextrose, and 0.004 parts by weight of ferrous sulfate were continuously introduced at 75° C. for 3 hours at a constant rate and polymerized. . After the continuous input was completed, the reaction was further carried out at 75 ° C. for 1 hour, and the polymerization reaction was terminated by cooling to 60 ° C. to prepare a graft copolymer latex (average particle diameter: 500 nm) including a shell.
[207]
The average particle diameter of the graft copolymer latex was measured by dynamic light scattering using Nicomp 380 equipment (product name, manufacturer: PSS).
[208]
[209]

[210]
0.8 parts by weight of an aqueous calcium chloride solution (concentration: 23% by weight) was added to the graft copolymer latex and agglomerated under atmospheric pressure for 7 minutes at 70° C., then aged at 93° C. for 7 minutes, dehydrated and washed with hot air at 90° C. After drying for 30 minutes, a graft copolymer powder was prepared.
[211]
[212]
Preparation 2
[213]

[214]
In a nitrogen-substituted reactor, 6 parts by weight of butyl acrylate, 0.5 parts by weight of sodium dodecyl sulfate as an emulsifier, 0.03 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, 0.02 parts by weight of allyl methacrylate as a grafting agent, 0.025 parts by weight of KOH as an electrolyte After adding 53.32 parts by weight and 53.32 parts by weight of distilled water, the temperature was raised to 70° C., and then 0.03 parts by weight of potassium persulfate as an initiator to initiate polymerization. After polymerization for 2 hours, the polymerization was terminated to obtain seeds (average particle diameter: 54 nm).
[215]
The average particle diameter of the seed was measured by a dynamic light scattering method using Nicomp 380 equipment (product name, manufacturer: PSS).
[216]
[217]

[218]
In the reactor in which the seed was obtained, 43 parts by weight of butyl acrylate, 0.5 parts by weight of sodium dodecyl sulfate as an emulsifier, 0.1 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, 0.1 parts by weight of allyl methacrylate as a grafting agent, 30 parts by weight of distilled water A mixture of 0.05 parts by weight of potassium persulfate as a part and an initiator was polymerized while continuously added at a constant rate for 2.5 hours at 70° C., and further polymerized for 1 hour after the addition was completed. was obtained.
[219]
The average particle diameter of the core was measured by a dynamic light scattering method using Nicomp 380 equipment (product name, manufacturer: PSS).
[220]
[221]

[222]
36 parts by weight of styrene, 15 parts by weight of acrylonitrile, and 39 parts by weight of distilled water were added to the reactor in which the core was obtained, 1.5 parts by weight of potassium rosin acid salt as an emulsifier, 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight control agent, and initiation A first mixture containing 0.04 parts by weight of zero t-butylperoxy ethylhexyl carbonate, and a second mixture containing 0.1 parts by weight of sodium pyrophosphate as an activator, 0.12 parts by weight of textrose, and 0.002 parts by weight of ferrous sulfate were prepared at 75 ° C. Polymerization was carried out while continuously inputting at a constant rate for 2.5 hours. After the continuous input was completed, the reaction was further carried out at 75° C. for 1 hour, and the polymerization reaction was terminated by cooling to 60° C. to prepare a graft copolymer latex (average particle diameter: 130 nm) including a shell.
[223]
The average particle diameter of the graft copolymer latex was measured by dynamic light scattering using Nicomp 380 equipment (product name, manufacturer: PSS).
[224]
[225]

[226]
A graft copolymer powder was prepared in the same manner as in Preparation Example 1.
[227]
[228]
Preparation 3
[229]
A 125 ml high-pressure reactor was evacuated, filled with nitrogen, and then 30 ml of toluene was added. Thereafter, the reactor was placed in an appropriate thermostat, 31 mmol of aluminum (III) chloride was added, and then 31 mmol of methyl acrylate (about 2.67 g) was added, and the reaction temperature was stabilized for 30 minutes. Thereafter, 0.0031 mmol of Azobisisobutyronitrile (AIBN) was dissolved in 5 ml of chlorobenzene and injected into the reactor. Then, ethylene was charged to the reactor at 35 bar, and the reaction temperature was raised to 70 °C to carry out polymerization for 20 hours. After the polymerization reaction was completed, the reaction temperature was lowered to room temperature, and then ethanol as a non-solvent was added to precipitate the prepared copolymer as a solid. Remove the supernatant by sinking the solid phase, wash the solid phase again by adding ethanol, remove the supernatant by sinking, add water to solidify the particles in the remaining solid phase and stir, then filter it Only the copolymer was recovered. The copolymer thus obtained was dried in a vacuum oven at 60° C. for one day.
[230]
Meanwhile, the obtained copolymer had a weight average molecular weight of 104,000 g/mol, and contained 76 wt% of ethylene units and 24 wt% of methyl acrylate units.
[231]
The weight average molecular weight of the obtained copolymer was measured as a relative value with respect to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent.
[232]
[233]
Examples and Comparative Examples
[234]
[235]
The specifications of the components used in the following Examples and Comparative Examples are as follows.
[236]
[237]
(A-1) First graft copolymer: The graft copolymer powder prepared in Preparation Example 1 was used.
[238]
[239]
(A-2) Second graft copolymer: The graft copolymer powder prepared in Preparation Example 2 was used.
[240]
[241]
(B-1) First styrenic copolymer: 98UHM of LG Chem (a copolymer of α-methyl styrene and acrylonitrile, weight average molecular weight: 100,000 g/mol) was used.
[242]
The weight average molecular weight was measured as a relative value with respect to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent.
[243]
[244]
(B-2) Second styrenic copolymer: 97HC of LG Chem (copolymer of styrene and acrylonitrile, weight average molecular weight: 170,000 g/mol) was used.
[245]
The weight average molecular weight was measured as a relative value with respect to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent.
[246]
[247]
(C) Olefin-based copolymer: The copolymer prepared in Preparation Example 3 was used.
[248]
[249]
A thermoplastic resin composition was prepared by mixing and stirring the above-mentioned components according to the contents shown in [Table 1] to [Table 3].
[250]
[251]
Experimental Example 1
[252]
The thermoplastic resin compositions of Examples and Comparative Examples were put into a twin-screw extrusion kneader set at 230° C., and pellets were prepared. The pellets were evaluated for physical properties by the method described below and described in [Table 1] to [Table 3].
[253]
[254]
① Melt Flow Index (g/10 min): Based on ASTM D1238, it was measured at 220 °C.
[255]
[256]
Experimental Example 2
[257]
A specimen was prepared by injecting the pellets prepared in Experimental Example 1, and the physical properties of the specimen were evaluated by the method described below, and the results are described in [Table 1] to [Table 3].
[258]
[259]
② Hardness: Measured according to ASTM 785.
[260]
③ Izod impact strength (kg·cm/cm): Measured according to ASTM 256.
[261]
④ Heat deflection temperature (℃): It was measured according to ASTM D648.
[262]
[263]
Experimental Example 3
[264]
A 0.3 mm film was prepared with a film extruder using the pellets prepared in Experimental Example 1, and the film was evaluated for physical properties by the method described below, and the results are described in [Table 1] to [Table 3]. .
[265]
[266]
⑤ Film appearance: The film press marks and projections were visually evaluated.
[267]
×: film deformation, ○: good, ◎: very good
[268]
⑥ Chemical resistance: In a beaker containing methyl ethyl ketone, the film was immersed for 2 minutes. The chemical resistance was evaluated according to the time at which the film started to melt.
[269]
×: 20 seconds or less, ○: more than 40, less than 100 seconds, ◎: 100 seconds or more
[270]
[Table 1]
division Example
One 2 3 4
(A-1) First graft copolymer (parts by weight) 14 14 14 14
(A-2) Second graft copolymer (parts by weight) 7 7 7 7
(B-1) first styrenic copolymer (parts by weight) 15 15 15 15
(B-2) second styrenic copolymer (parts by weight) 64 64 64 64
(C) Olefin-based copolymer (parts by weight) - 0.5 0.7 One
Weight ratio of the first and second styrenic copolymers about 19:81 about 19:81 about 19:81 about 19:81
flow index 12 12.9 13.1 13.3
Hardness 114 112.1 111.5 110.9
impact strength 7.5 7 6.8 6.5
heat deflection temperature 90 89.8 89.5 89
film appearance ◎ ◎ ○ ○
chemical resistance ○ ◎ ◎ ◎
(A-1) First graft copolymer: ASA graft copolymer of Preparation Example 1 (average particle diameter of core: 400 nm) (A-2) Second graft copolymer: ASA graft copolymer of Preparation Example 2 Copolymer (average particle diameter of core: 101 nm) (B-1) First styrenic copolymer: 98UHM of LG Chem (copolymer of α-methyl styrene and acrylonitrile, weight average molecular weight: 100,000 g/mol) ( B-2) Second styrenic copolymer: 97HC of LG Chem (copolymer of styrene and acrylonitrile, weight average molecular weight: 170,000 g/mol) (C) Olefin-based copolymer: copolymer of Preparation Example 3 ( 24 wt% of methyl acrylate units, 76 wt% of ethylene units, weight average molecular weight: 104,000 g/mol
[271]
[Table 2]
division comparative example Example
One 2 5 6 7
(A-1) First graft copolymer (parts by weight) 3 14 14 14 14
(A-2) Second graft copolymer (parts by weight) 35 7 7 7 7
(B-1) first styrenic copolymer (parts by weight) - - One 7 8
(B-2) second styrenic copolymer (parts by weight) 62 79 78 72 71
(C) Olefin-based copolymer (parts by weight) 0.5 0.5 0.5 0.5 0.5
Weight ratio of the first and second styrenic copolymers - - about 1:99 about 9:91 about 10:90
flow index 7 12.4 12.4 12.3 12.3
Hardness 103 112.3 112.3 112.1 112.1
impact strength 5.9 6.9 6.9 7 7
heat deflection temperature 84 84.7 84.9 86.9 87.4
film appearance × × ○ ○ ◎
chemical resistance ○ ◎ ◎ ◎ ◎
(A-1) First graft copolymer: ASA graft copolymer of Preparation Example 1 (average particle diameter of core: 400 nm) (A-2) Second graft copolymer: ASA graft copolymer of Preparation Example 2 Copolymer (average particle diameter of core: 101 nm) (B-1) First styrenic copolymer: 98UHM of LG Chem (copolymer of α-methyl styrene and acrylonitrile, weight average molecular weight: 100,000 g/mol) ( B-2) Second styrenic copolymer: 97HC of LG Chem (copolymer of styrene and acrylonitrile, weight average molecular weight: 170,000 g/mol) (C) Olefin-based copolymer: copolymer of Preparation Example 3 ( 24 wt% of methyl acrylate units, 76 wt% of ethylene units, weight average molecular weight: 104,000 g/mol
[272]
[Table 3]
division Example comparative example
8 9 10 3
(A-1) First graft copolymer (parts by weight) 14 14 14 14
(A-2) Second graft copolymer (parts by weight) 7 7 7 7
(B-1) first styrenic copolymer (parts by weight) 25 27 30 79
(B-2) second styrenic copolymer (parts by weight) 54 52 49 -
(C) Olefin-based copolymer (parts by weight) 0.5 0.5 0.5 0.5
Weight ratio of the first and second styrenic copolymers about 32:68 about 34:66 about 38:62 -
flow index 12.3 12.3 12.1 12
Hardness 111.9 111.7 111.6 111.4
impact strength 7.2 7.2 7.3 7.6
heat deflection temperature 91.3 91.5 91.8 97
film appearance ◎ ○ ○ ○
chemical resistance ○ ○ ○ ×
(A-1) First graft copolymer: ASA graft copolymer of Preparation Example 1 (average particle diameter of core: 400 nm) (A-2) Second graft copolymer: ASA graft copolymer of Preparation Example 2 Copolymer (average particle diameter of core: 101 nm) (B-1) First styrenic copolymer: 98UHM of LG Chem (copolymer of α-methyl styrene and acrylonitrile, weight average molecular weight: 100,000 g/mol) ( B-2) Second styrenic copolymer: 97HC of LG Chem (copolymer of styrene and acrylonitrile, weight average molecular weight: 170,000 g/mol) (C) Olefin-based copolymer: copolymer of Preparation Example 3 ( 24 wt% of methyl acrylate units, 76 wt% of ethylene units, weight average molecular weight: 104,000 g/mol
[273]
Referring to Tables 1 to 3, Example 1 including the first graft copolymer, the second graft copolymer, the first styrenic copolymer and the second styrenic copolymer has hardness, impact strength, and thermal deformation. It was confirmed that the temperature, film appearance, and chemical resistance were all excellent. And, it was confirmed that Examples 2 to 4, which further included an olefin-based copolymer compared to Example 1, had improved chemical resistance compared to Example 1. And, comparing Examples 2 to 4, it was confirmed that, in Example 2 containing a small amount of the olefin-based copolymer, the decrease in hardness, impact strength and thermal deformation temperature was minimized, and chemical resistance was improved.
[274]
Comparing Comparative Examples 2, 2, 5 to 10, and Comparative Example 3 in which the weight ratio of the first styrenic copolymer and the second styrenic copolymer was varied, the content of the first styrenic copolymer It was confirmed that the heat deflection temperature was improved as this increased, and the hardness increased as the content of the second styrenic copolymer increased. In addition, in Examples 2, 7 and 8, wherein the weight ratio of the first styrenic copolymer and the second styrenic copolymer is about 10:90 to about 32:68, the decrease in hardness and impact strength is minimized, It was confirmed that the film appearance and chemical resistance were improved. Comparative Examples 1 and 2, which do not contain the first styrenic copolymer, have significantly reduced impact strength and film appearance, and Comparative Example 3 that does not include the second styrenic copolymer has significantly reduced chemical resistance. could confirm that
[275]
Claims
[Claim 1]
a C 4 to C 10 alkyl (meth) acrylate-based monomer unit, a styrene-based monomer unit, and a vinyl cyan-based monomer unit; C 1 To C 3 A first styrenic copolymer including an alkyl-substituted styrenic monomer unit and a vinyl cyan-based monomer unit; and a second styrenic copolymer including an unsubstituted styrene-based monomer unit and a vinyl cyan-based monomer unit.
[Claim 2]
The thermoplastic resin composition of claim 1, wherein the graft copolymer includes two types of graft copolymers having different average particle diameters of cores.
[Claim 3]
The thermoplasticity according to claim 2, wherein the graft copolymer comprises a first graft copolymer having an average core diameter of 300 to 500 nm and a second graft copolymer having an average core particle diameter of 50 to 150 nm. resin composition.
[Claim 4]
The method according to claim 1, wherein the graft copolymer is butyl acrylate-styrene-acrylonitrile copolymer, butyl acrylate-α-methyl styrene-acrylonitrile copolymer and butyl acrylate-styrene-α-methyl styrene-acrylic At least one thermoplastic resin composition selected from the group consisting of ronitrile copolymers.
[Claim 5]
The thermoplastic resin composition of claim 1, wherein the first styrenic copolymer is selected from the group consisting of α-methyl styrene-acrylonitrile copolymer and α-methyl styrene-styrene-acrylonitrile copolymer.
[Claim 6]
The thermoplastic resin composition of claim 1, wherein the second styrene copolymer is a styrene-acrylonitrile copolymer.
[Claim 7]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition comprises the first styrenic copolymer and the second styrenic copolymer in a weight ratio of 5:95 to 32:68.
[Claim 8]
The method according to claim 1, wherein the thermoplastic resin composition is based on 100 parts by weight of the total of the graft copolymer, the first styrenic copolymer, and the second styrenic copolymer, 5 to 45 parts by weight of the graft copolymer; 2 to 25 parts by weight of the first styrenic copolymer; and 50 to 80 parts by weight of the second styrenic copolymer.
[Claim 9]
The method according to claim 3, wherein the thermoplastic resin composition is based on 100 parts by weight of the total of the first graft copolymer, the second graft copolymer, the first styrenic copolymer, and the second styrenic copolymer, the first graft 5 to 30 parts by weight of the copolymer; 0.1 to 15 parts by weight of the second graft copolymer; 2 to 25 parts by weight of the first styrenic copolymer; and 50 to 80 parts by weight of the second styrenic copolymer.
[Claim 10]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition further comprises an olefin-based copolymer including a C 1 to C 3 alkyl (meth)acrylate-based monomer unit.
[Claim 11]
The method according to claim 10, wherein the olefin-based copolymer comprises a C 2 to C 4 olefin-based monomer unit and a C 1 to C 3 alkyl (meth)acrylate-based monomer unit in a weight ratio of 85:15 to 65:35. The thermoplastic resin composition.
[Claim 12]
The method according to claim 10, wherein the olefin-based copolymer comprises a C 2 to C 4 olefin-based monomer unit and a C 1 to C 3 alkyl (meth)acrylate-based monomer unit in a weight ratio of 80:20 to 70:30 The thermoplastic resin composition.
[Claim 13]
The thermoplastic resin composition of claim 10, wherein the olefin-based copolymer has a weight average molecular weight of 50,000 to 200,000 g/mol.
[Claim 14]
The thermoplastic resin composition of claim 10, wherein the olefin-based copolymer is an ethylene-methyl acrylate copolymer.
[Claim 15]
The method according to claim 10, wherein the thermoplastic resin composition comprises 0.01 to 2 parts by weight of the olefinic copolymer based on 100 parts by weight of the total of the graft copolymer, the first styrenic copolymer, and the second styrenic copolymer. The thermoplastic resin composition.