The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0132191 filed on October 31, 2018, and includes all contents disclosed in the literature of the Korean patent application as 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 chemical resistance and appearance characteristics.
[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 a substrate, a problem of melting due to poor chemical resistance occurs.
[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]
SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin composition with improved chemical resistance, heat resistance and appearance characteristics while excellent in basic physical properties such as processability, hardness, colorability, and impact resistance.
[12]
means of solving the problem
[13]
In order to solve the above problems, the present invention provides a C 4 to C 10 alkyl (meth) acrylate-based monomer unit, a C 1 to C 3 alkyl-substituted styrene-based monomer unit, and a vinyl cyan-based monomer unit comprising a 1 graft copolymer; A second graft copolymer comprising a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, an alkyl unsubstituted 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; a second styrenic copolymer including an alkyl unsubstituted styrene-based monomer unit and a vinyl cyan-based monomer unit; and C 1 to C 3 It provides a thermoplastic resin composition comprising an olefin-based copolymer including an alkyl (meth)acrylate-based monomer unit.
[14]
Effects of the Invention
[15]
The thermoplastic resin composition of the present invention is excellent in basic physical properties such as processability, hardness, colorability, and impact resistance, and can significantly improve chemical resistance, heat resistance and appearance characteristics.
[16]
Best mode 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 aromatic vinyl-based monomer unit and the vinyl cyan-based monomer unit grafted to the core.
[21]
Here, the aromatic vinyl- based monomer unit may be at least one selected from the group consisting of a C 1 to C 3 alkyl-substituted styrenic monomer unit and an alkyl unsubstituted styrene-based monomer unit.
[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 (%): Grafted monomer weight (g) / rubber weight (g) × 100
[28]
[29]
Weight of grafted monomer (g): weight of insoluble material (gel) after dissolving graft copolymer powder in acetone and centrifuging
[30]
Rubber weight (g): The weight of C 4 to C 10 alkyl (meth)acrylate-based monomer 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]
The thermoplastic resin composition according to an embodiment of the present invention provides A-1) C 4 to C 10 alkyl (meth)acrylate-based monomer units, C 1 to C 3 alkyl-substituted styrenic monomer units, and A first graft copolymer comprising a vinyl cyan-based monomer unit; A-2) a second graft copolymer comprising a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, an alkyl unsubstituted 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; B-2) a second styrenic copolymer comprising an alkyl unsubstituted styrene-based monomer unit and a vinyl cyan-based monomer unit; And C) C 1 to C 3 It includes an olefin-based copolymer comprising an alkyl (meth) acrylate-based monomer unit.
[39]
[40]
Hereinafter, each component of the thermoplastic resin composition of the present invention will be described in detail.
[41]
[42]
A-1) first graft copolymer
[43]
The first graft copolymer includes a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, a C 1 to C 3 alkyl-substituted styrenic monomer unit, and a vinyl cyan-based monomer unit.
[44]
[45]
Since the first graft copolymer includes a C 1 to C 3 alkyl-substituted styrenic monomer unit, remarkably excellent heat resistance and appearance characteristics may be imparted to the thermoplastic resin composition. In addition, compatibility with the first styrenic copolymer, which will be described later, is remarkably improved, and may be uniformly dispersed in the thermoplastic resin composition.
[46]
In addition, the first graft copolymer may impart excellent impact resistance to the thermoplastic resin composition.
[47]
[48]
The first graft copolymer may include a core made of a cross-linked polymer including a C 4 to C 10 alkyl (meth)acrylate-based monomer unit; and a shell including an alkyl-substituted styrene-based monomer unit and a vinyl cyan-based monomer unit grafted to the core-shell structure.
[49]
[50]
The C 4 to C 10 alkyl (meth)acrylate-based monomer unit may be a unit derived from a C 4 to C 10 alkyl (meth)acrylate-based monomer.
[51]
The C 4 to C 10 alkyl (meth) acrylate-based monomer is butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate and may be at least one selected from the group consisting of decyl (meth) acrylate, of which butyl acrylate desirable.
[52]
[53]
The C 4 to C 10 alkyl (meth)acrylate-based monomer unit may be included in an amount of 40 to 60 wt% or 45 to 55 wt%, of which 45 to 55 wt%, based on the total weight of the first graft copolymer. It is preferably included in weight %. When the above-described range is satisfied, the impact resistance of the first graft copolymer may be further improved.
[54]
[55]
The C 1 to C 3 alkyl-substituted styrenic monomer unit may be a unit derived from a C 1 to C 3 alkyl-substituted styrenic monomer.
[56]
The C 1 to C 3 alkyl-substituted styrene-based monomer may be at least one selected from the group consisting of α-methyl styrene, p-methyl styrene, and 2,4-dimethyl styrene, of which α-methyl styrene is desirable.
[57]
The C 1 to C 3 alkyl-substituted styrenic monomer unit may be included in an amount of 25 to 45% by weight or 30 to 40% by weight, of which 30 to 40% by weight, based on the total weight of the first graft copolymer. It is preferable to include When the above-described range is satisfied, heat resistance, appearance characteristics, and impact resistance of the thermoplastic resin composition may be further improved.
[58]
[59]
The vinyl cyan-based monomer unit may be a unit derived from a vinyl cyan-based monomer.
[60]
The vinyl cyan-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, among which acrylonitrile is preferable.
[61]
The vinyl cyan-based monomer unit may be included in an amount of 5 to 25% by weight or 10 to 20% by weight, preferably 10 to 20% by weight, based on the total weight of the first graft copolymer. When the above-described range is satisfied, the chemical resistance of the first graft copolymer may be further improved.
[62]
[63]
The first graft copolymer may further include an alkyl unsubstituted styrenic monomer unit to facilitate polymerization. The alkyl unsubstituted styrenic monomer unit may be a unit derived from an alkyl unsubstituted styrenic monomer. The alkyl unsubstituted styrene-based monomer may be at least one selected from the group consisting of styrene, p-bromo styrene, o-bromo styrene, and p-chloro styrene, among which styrene is preferable.
[64]
The alkyl unsubstituted styrenic monomer unit may be included in an amount of 0.1 to 15 wt% or 1 to 10 wt%, based on the total weight of the first graft copolymer, of which 1 to 10 wt% desirable. When the above-described range is satisfied, polymerization of the first graft copolymer may be more easily performed.
[65]
[66]
In the first graft copolymer, the average particle diameter of the core may be different from that of the second graft copolymer, and specifically, the first graft copolymer has a larger average particle diameter than the second graft copolymer. can
[67]
Since the thermoplastic resin composition includes two or more types of graft copolymers having different average particle diameters of cores, impact resistance, weather resistance, colorability, surface gloss properties, and appearance properties can all be improved.
[68]
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 ranges are satisfied, the impact resistance and surface gloss properties of the thermoplastic resin composition may be further improved. If it is less than the above range, the impact resistance of the thermoplastic resin composition may be reduced, and if it exceeds the above range, the surface gloss properties may be reduced.
[69]
[70]
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, the impact resistance and dispersibility of the thermoplastic resin composition may be further improved.
[71]
[72]
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, the impact resistance of the thermoplastic resin composition may be further improved.
[73]
[74]
The first graft copolymer may be selected from the group consisting of a butyl acrylate-α-methyl styrene-acrylonitrile copolymer and a butyl acrylate-styrene-α-methyl styrene-acrylonitrile copolymer, of which A butyl acrylate-styrene-α-methyl styrene-acrylonitrile copolymer is preferred.
[75]
[76]
The first graft copolymer is 5 to 30 parts by weight 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. , may be included in 10 to 25 parts by weight or 10 to 15 parts by weight, of which it is preferably included in 10 to 15 parts by weight. When the above-mentioned range is satisfied, the impact resistance of the thermoplastic resin composition can be remarkably improved. When included in less than the above range, the impact resistance and appearance properties of the thermoplastic resin composition are significantly reduced, when included in excess of the above range, the appearance properties may be significantly reduced.
[77]
[78]
On the other hand, the first graft copolymer is 1) C 4 to C 10 alkyl (meth) acrylate-based monomer, C 1 to C 3 alkyl-substituted styrenic monomer, alkyl unsubstituted styrenic monomer, and vinyl cyanide. preparing a core by polymerizing at least one selected from the group consisting of monomers; 2) In the presence of the core, C 1 to C 3 It may be prepared by a manufacturing method comprising the step of polymerizing an alkyl-substituted styrene-based monomer, and a vinyl cyanide-based monomer to prepare a shell.
[79]
[80]
The step of preparing the core is a C 4 to C 10 alkyl (meth)acrylate-based monomer, a C 1 to C 3 alkyl-substituted styrenic monomer, an alkyl unsubstituted styrenic monomer, and a group consisting of a vinyl cyanide monomer. preparing a seed by polymerizing one or more selected from; 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.
[81]
[82]
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.
[83]
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.
[84]
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.
[85]
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.
[86]
[87]
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 selected 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.
[88]
[89]
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.
[90]
[91]
The grafting agent may be at least one selected from the group consisting of allyl methacrylate, triallyl isocyanurate, triallylamine and diallylamine.
[92]
[93]
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.
[94]
[95]
The water serves as a medium during emulsion polymerization, and may be ion-exchanged water.
[96]
[97]
On the other hand, in the step of preparing the shell, the C 1 to C 3 alkyl-substituted styrenic monomer and the vinyl cyan-based monomer may be polymerized while continuously input at a constant rate, and when added in the above-described method, heat removal and excess during polymerization Runaway due to overheating can be easily suppressed.
[98]
[99]
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.
[100]
[101]
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.
[102]
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.
[103]
[104]
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.
[105]
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.
[106]
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.
[107]
[108]
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.
[109]
[110]
On the other hand, the graft copolymer prepared by the above-described manufacturing method may be in the form of latex.
[111]
[112]
The latex-type graft copolymer may be prepared in powder form by performing agglomeration, aging, washing, dehydration and drying.
[113]
[114]
A-2) Second graft copolymer
[115]
The second graft copolymer includes a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, an alkyl unsubstituted styrene-based monomer unit, and a vinyl cyan-based monomer unit.
[116]
[117]
The second graft copolymer may impart excellent weather resistance, colorability, impact resistance, chemical resistance and surface gloss properties to the thermoplastic resin composition.
[118]
In addition, since the second graft copolymer includes an alkyl unsubstituted styrenic monomer unit, compatibility with a second styrenic copolymer, which will be described later, is remarkably improved and can be uniformly dispersed in the thermoplastic resin composition. .
[119]
[120]
The second graft copolymer includes at least one selected from the group consisting of C 4 to C 10 alkyl (meth)acrylate monomer units, alkyl unsubstituted styrene monomer units, and vinyl cyan monomer units. a core made of a crosslinked polymer; And it may have a core-shell structure including a shell including an alkyl unsubstituted styrene-based monomer unit and a vinyl cyan-based monomer unit grafted to the core.
[121]
[122]
The C 4 to C 10 alkyl (meth)acrylate-based monomer unit may be included in an amount of 40 to 60 wt% or 45 to 55 wt%, of which 45 to 55 wt%, based on the total weight of the second graft copolymer. It is preferably included in weight %. If the above-described range is satisfied, the weather resistance and impact resistance of the second graft copolymer may be further improved.
[123]
[124]
The alkyl unsubstituted styrenic monomer unit may be included in an amount of 25 to 45% by weight or 30 to 40% by weight based on the total weight of the second graft copolymer, and preferably included in an amount of 30 to 40% by weight. do. When the above-described range is satisfied, the processability and impact resistance of the second graft copolymer may be further improved.
[125]
[126]
The vinyl cyan-based monomer unit may be included in an amount of 5 to 25% by weight or 10 to 20% by weight based on the total weight of the second graft copolymer, and it is preferably included in an amount of 10 to 20% by weight. When the above-described range is satisfied, the chemical resistance of the second graft copolymer may be further improved.
[127]
[128]
The C 4 to C 10 alkyl unsubstituted styrene-based monomer unit, the alkyl unsubstituted styrene-based monomer unit, and the vinyl cyan-based monomer unit have been described above.
[129]
[130]
The second graft copolymer may have an average particle diameter of 50 to 150 nm or 75 to 125 nm of the core, preferably 75 to 125 nm. When the above-mentioned range is satisfied, the specific surface area of ​​the core in the thermoplastic resin composition is increased, so that the weather resistance is remarkably improved, and since visible light can penetrate without being scattered from the core, the colorability can be remarkably improved. In addition, chemical resistance, appearance properties, and surface gloss properties of the thermoplastic resin composition may be further improved. If it is less than the above range, the weather resistance, chemical resistance, appearance characteristics and surface gloss properties of the thermoplastic resin composition may be significantly reduced, and if it exceeds the above range, the weather resistance and colorability may be significantly reduced.
[131]
[132]
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-mentioned range is satisfied, the second graft copolymer having excellent colorability, dispersibility and surface gloss properties can be prepared.
[133]
[134]
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. If the above-mentioned range is satisfied, the second graft copolymer having excellent dispersibility and mechanical properties can be prepared.
[135]
[136]
The second graft copolymer may be a butyl acrylate-styrene-acrylonitrile copolymer.
[137]
[138]
The second graft copolymer is 0.1 to 15 parts by weight 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. , may be included in 1 to 10 parts by weight or 5 to 8 parts by weight, of which 5 to 8 parts by weight is preferably included. When the above-described range is satisfied, the weather resistance, chemical resistance, colorability, appearance characteristics, and surface gloss characteristics of the thermoplastic resin composition can be remarkably improved. If it is less than the above range, the appearance characteristics, weather resistance and colorability of the thermoplastic resin composition may be reduced, and if it exceeds the above range, the impact resistance of the thermoplastic resin composition may be reduced.
[139]
[140]
On the other hand, the second graft copolymer 1) polymerization of at least one selected from the group consisting of C 4 to C 10 alkyl (meth)acrylate-based monomers, alkyl unsubstituted styrenic monomers and vinyl cyan-based monomers. to prepare a core; 2) may be prepared by a manufacturing method comprising the step of preparing a shell by polymerizing an alkyl unsubstituted styrene-based monomer and a vinyl cyan-based monomer in the presence of the core.
[141]
[142]
The step of preparing the core is to prepare a seed by polymerizing at least one selected from the group consisting of C 4 to C 10 alkyl (meth)acrylate-based monomers, alkyl unsubstituted styrene-based monomers and vinyl cyan-based monomers. step; 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.
[143]
[144]
In addition, the manufacturing method of the second graft copolymer is the same as described in the manufacturing method of the first graft copolymer.
[145]
[146]
Meanwhile, in the present invention, the combined content of the first graft copolymer and the second graft copolymer is the first graft copolymer, the second graft copolymer, the first styrenic copolymer, and the second Based on 100 parts by weight of the total of the styrenic copolymer, 10 to 35 parts by weight, preferably 15 to 30 parts by weight. When the above-mentioned range is satisfied, the thermoplastic resin composition may implement excellent impact resistance, appearance characteristics, and hardness. When included in less than the above range, the impact resistance of the thermoplastic resin composition is remarkably reduced, and when included in excess of the above range, the flow index is lowered, and the appearance characteristics can be significantly reduced.
[147]
[148]
In addition, in the present invention, the weight ratio of the first graft copolymer and the second graft copolymer is 1.5:1 to 10:1, preferably 1.5:1 to 5:1, more preferably 1.5:1 to 3:1. When the above-described range is satisfied, the impact resistance and appearance characteristics of the thermoplastic resin composition may be further improved. If it is less than the above-mentioned range, the impact resistance of the thermoplastic resin composition may be reduced, and if it exceeds the above-mentioned range, the appearance characteristics of the thermoplastic resin composition may be reduced.
[149]
[150]
B-1) first styrenic copolymer
[151]
The first styrenic copolymer is a matrix copolymer and includes a C 1 to C 3 alkyl-substituted styrenic monomer unit and a vinyl cyan-based monomer unit.
[152]
[153]
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.
[154]
In addition, since the first styrenic copolymer includes a C 1 to C 3 alkyl-substituted styrenic monomer unit, compatibility with the first graft copolymer may be excellent.
[155]
[156]
The C 1 to C 3 alkyl-substituted styrene-based monomer unit and the vinyl cyan-based monomer unit are the same as described above.
[157]
[158]
The first styrenic copolymer may be a copolymer of a monomer mixture including a C 1 to C 3 alkyl-substituted styrenic monomer and a vinyl cyanide monomer.
[159]
The monomer mixture may include a C 1 to C 3 alkyl-substituted styrene-based monomer and a vinyl cyan-based monomer in a weight ratio of 60:40 to 90:10 or 65:35 to 85:15, of which 65:35 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.
[160]
[161]
The first styrenic copolymer may further include an alkyl unsubstituted styrenic monomer unit to facilitate polymerization.
[162]
That is, the first styrenic copolymer may be a copolymer of a monomer mixture including a C 1 to C 3 alkyl-substituted styrene-based monomer, a vinyl cyanide-based monomer, and an alkyl unsubstituted styrene-based monomer. The type of the alkyl unsubstituted styrene-based monomer unit is the same as described above.
[163]
[164]
In this case, the monomer mixture comprises 55 to 75 wt% of the C 1 to C 3 alkyl-substituted styrenic monomer, 20 to 40 wt% of the vinyl cyanide-based monomer, and 0.1 to 15 wt% of the alkyl unsubstituted styrenic monomer and preferably 60 to 70 wt% of the C 1 to C 3 alkyl-substituted styrenic monomer, 25 to 35 wt% of the vinyl cyanide-based monomer, and 1 to 10 wt% of the alkyl unsubstituted styrenic monomer may include When the above-described range is satisfied, polymerization of the first styrenic copolymer may proceed more easily.
[165]
[166]
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. If it is less than the above-mentioned range, the mechanical properties of the thermoplastic resin composition may be deteriorated. If the above-mentioned range is exceeded, workability may be deteriorated.
[167]
[168]
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.
[169]
[170]
The first styrenic copolymer is used in an amount of 2 to 25 parts by weight 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. , 7 to 20 parts by weight, 14 to 20 parts by weight or 14 to 16 parts by weight may be included, of which 14 to 16 parts by weight is preferably included. When the above-described range is satisfied, heat resistance, processability, and appearance characteristics of the thermoplastic resin composition may be further improved. Specifically, when it is included in less than the above-mentioned range, the heat resistance of the thermoplastic resin composition may be lowered and the appearance characteristics may be lowered. If it exceeds the above range, processability and chemical resistance may be reduced.
[171]
[172]
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-substituted styrenic monomer and a vinyl cyanide monomer, of which a high-purity polymer is prepared It is preferable that it is a copolymer prepared by bulk polymerization that can be performed.
[173]
[174]
B-2) Second Styrenic Copolymer
[175]
The second styrenic copolymer is a matrix copolymer and includes an alkyl unsubstituted styrenic monomer unit and a vinyl cyanide monomer unit.
[176]
[177]
The second styrenic copolymer may impart excellent processability, chemical resistance, and mechanical properties to the thermoplastic resin composition. Since the second styrenic copolymer includes an alkyl unsubstituted styrenic monomer unit, compatibility with the second graft copolymer is improved, and the second graft copolymer is uniformly dispersed in the thermoplastic resin composition. can make it
[178]
[179]
The types of the alkyl unsubstituted styrene-based monomer unit and the vinyl cyan-based monomer unit are the same as described above.
[180]
[181]
The second styrenic copolymer may be a copolymer of a monomer mixture including an alkyl unsubstituted styrenic monomer and a vinyl cyanide monomer.
[182]
The monomer mixture may include an alkyl unsubstituted styrenic monomer and a 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.
[183]
[184]
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. If it is less than the above range, the mechanical properties of the thermoplastic resin composition may be reduced, and if it exceeds the above range, the processability of the thermoplastic resin composition may be reduced.
[185]
[186]
The second styrene copolymer is preferably a styrene-acrylonitrile copolymer.
[187]
[188]
The second styrenic copolymer is 50 to 80 parts by weight 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; It may be included in 55 to 75 parts by weight or 62 to 66 parts by weight, of which 62 to 66 parts by weight is preferably included. When the above-described range is satisfied, the processability, chemical resistance and mechanical properties of the thermoplastic resin composition may be further improved. When included in less than the above range, the chemical resistance and processability of the thermoplastic resin composition is lowered, when included in excess of the above range, the mechanical properties of the thermoplastic resin composition may be reduced.
[189]
[190]
The second styrenic copolymer may be a copolymer prepared by suspension or bulk polymerization of an alkyl unsubstituted styrene-based monomer and a vinyl cyanide monomer, and among them, a copolymer prepared by bulk polymerization capable of producing a high-purity copolymer it is preferable
[191]
[192]
Meanwhile, in the present invention, the combined content of the first styrenic copolymer and the second styrenic copolymer is the first graft copolymer, the second graft copolymer, the first styrenic copolymer and the second Based on 100 parts by weight of the total of the styrenic copolymer, 65 to 90 parts by weight, preferably 70 to 85 parts by weight. When included below the above range, the processability of the thermoplastic resin composition may be reduced, and if it exceeds the above range, the impact resistance of the thermoplastic resin composition may be reduced.
[193]
[194]
C) Olefin-based copolymer
[195]
The olefin-based copolymer includes, as an additive, a C 1 to C 3 alkyl (meth)acrylate-based monomer unit.
[196]
[197]
Excellent chemical resistance may be imparted to the olefin-based copolymer thermoplastic resin composition.
[198]
[199]
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.
[200]
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.
[201]
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.
[202]
[203]
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, the first graft copolymer, the second graft copolymer, the first styrenic copolymer and the second styrenic copolymer and compatibility is lowered, so that it cannot be uniformly dispersed in the thermoplastic resin composition, the effect of improving chemical resistance may be reduced. When the content of the alkyl (meth)acrylate-based monomer unit is too large, compatibility with the first graft copolymer, the second graft copolymer, the first styrenic copolymer and the second styrenic copolymer is improved. , the content of the olefin-based monomer unit may decrease, thereby reducing the effect of improving chemical resistance.
[204]
[205]
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-mentioned range is satisfied, a thermoplastic resin composition having excellent compatibility with the first graft copolymer, the second graft copolymer, the first styrenic copolymer and the second styrenic copolymer and excellent mechanical properties is provided. can do. Specifically, when it is less than the above range, the mechanical properties are reduced, and when it exceeds the above range, the first graft copolymer, the second graft copolymer, the first styrenic copolymer and the second styrenic copolymer The compatibility with the compound may be lowered, and thus may not be uniformly dispersed in the thermoplastic resin composition, thereby reducing the effect of improving chemical resistance.
[206]
[207]
The olefin-based copolymer is preferably an ethylene-methyl acrylate copolymer.
[208]
[209]
The olefin-based copolymer may be used in an amount of 0.01 to 2 parts by weight or 0.5 to 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. It may be included in the thermoplastic resin composition in an amount of 1 part by weight, of which 0.5 to 1 part by weight is preferably included. 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. When included in less than the above-mentioned range, the chemical resistance of the thermoplastic resin composition may be reduced, and when included in excess of the above-mentioned range, the impact resistance of the thermoplastic resin composition may be reduced.
[210]
[211]
The olefin-based polymer may be used by using a commercially available material or by directly preparing it.
[212]
When the olefin-based polymer 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.
[213]
[214]
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.
[215]
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.
[216]
[217]
2. Thermoplastic resin molded products
[218]
A thermoplastic resin molded article according to another embodiment of the present invention is manufactured from the thermoplastic resin composition according to an embodiment of the present invention, the heat deformation temperature is 87 ° C. or more, the impact strength may be 6.5 kg · cm / cm or more, and heat It is preferable that the deformation temperature is 89°C or more and the impact strength is 6.7 kg·cm/cm or more.
[219]
When the above conditions are satisfied, a thermoplastic resin molded article having excellent appearance characteristics, heat resistance and impact resistance can be manufactured.
[220]
[221]
The thermoplastic resin molded article according to an embodiment of the present invention may be a sheet, preferably a decorative sheet for furniture.
[222]
[223]
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.
[224]
[225]
Preparation Example 1
[226]

[227]
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).
[228]
The average particle diameter of the seed was measured by a dynamic light scattering method using Nicomp 380 equipment (product name, manufacturer: PSS).
[229]
[230]

[231]
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.
[232]
The average particle diameter of the core was measured by a dynamic light scattering method using Nicomp 380 equipment (product name, manufacturer: PSS).
[233]
[234]

[235]
35 parts by weight of α-methyl 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 rosin acid salt as an emulsifier, and t-butylperoxy ethylhexyl carbonate as an initiator The first mixture containing 0.19 parts by weight and the second mixture containing 0.16 parts by weight of sodium pyrophosphate as an activator, 0.24 parts by weight of textrose, and 0.004 parts by weight of ferrous sulfate were continuously added at a constant rate at 75° C. for 3 hours, respectively. while polymerization. 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.
[236]
The average particle diameter of the graft copolymer latex was measured by dynamic light scattering using Nicomp 380 equipment (product name, manufacturer: PSS).
[237]
[238]

[239]
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.
[240]
[241]
Preparation 2
[242]

[243]
6 parts by weight of butyl acrylate in a nitrogen-substituted reactor, 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).
[244]
The average particle diameter of the seed was measured by a dynamic light scattering method using Nicomp 380 equipment (product name, manufacturer: PSS).
[245]
[246]

[247]
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.
[248]
The average particle diameter of the core was measured by a dynamic light scattering method using Nicomp 380 equipment (product name, manufacturer: PSS).
[249]
[250]

[251]
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 regulator, 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.
[252]
The average particle diameter of the graft copolymer latex was measured by dynamic light scattering using Nicomp 380 equipment (product name, manufacturer: PSS).
[253]
[254]

[255]
A graft copolymer powder was prepared in the same manner as in Preparation Example 1.
[256]
[257]
Preparation 3
[258]
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 (about 2.67 g) of methyl acrylate 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.
[259]
On the other hand, the weight average molecular weight of the obtained copolymer was 104,000 g/mol, and 24 wt% of methyl acrylate units and 76 wt% of ethylene units were included.
[260]
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.
[261]
[262]
Examples and Comparative Examples
[263]
[264]
The specifications of the components used in the following Examples and Comparative Examples are as follows.
[265]
[266]
(A-1) First graft copolymer: The graft copolymer powder prepared in Preparation Example 1 was used.
[267]
[268]
(A-2) Second graft copolymer: The graft copolymer powder prepared in Preparation Example 2 was used.
[269]
[270]
(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.
[271]
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.
[272]
[273]
(B-2) Second styrenic copolymer: 97HC of LG Chem (copolymer of styrene and acrylonitrile, weight average molecular weight: 170,000 g/mol) was used.
[274]
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.
[275]
[276]
(C) Olefin-based copolymer: The copolymer prepared in Preparation Example 3 was used.
[277]
[278]
A thermoplastic resin composition was prepared by mixing and stirring the above-mentioned components according to the contents shown in [Table 1] below.
[279]
[280]
Experimental Example 1
[281]
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 are described in [Table 1] below.
[282]
[283]
① Flow index (g/10 min): Measured at 220 ℃ according to ASTM D1238.
[284]
[285]
Experimental Example 2
[286]
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 shown in Table 1 below.
[287]
[288]
② Hardness: Measured by ASTM 785 method.
[289]
③ Izod impact strength (kg·cm/cm): Measured according to ASTM 256.
[290]
④ Heat deflection temperature (℃): It was measured according to ASTM D648.
[291]
[292]
Experimental Example 3
[293]
A film of 0.3 mm was prepared from the pellets prepared in Experimental Example 1 with a film extruder, and the film was evaluated for physical properties by the method described below, and the results are described in [Table 1] below.
[294]
[295]
⑤ Film appearance: The film press marks and projections were visually evaluated.
[296]
×: film deformation, ○: good, ◎: very good
[297]
[298]
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.
[299]
×: 20 seconds or less, ○: more than 40 seconds, less than 100 seconds, ◎: 100 seconds or more
[300]
[301]
[Table 1]
division Example comparative example
One 2 3 4 5 One 2 3 4 5
(A-1) First graft copolymer (parts by weight) 14 19 15 14 17 3 14 14 - 22
(A-2) Second graft copolymer (parts by weight) 7 2 6 7 4 35 7 7 23 -
(B-1) first styrenic copolymer 15 12 12 15 12 - 79 15 15 15
(B-2) second styrenic copolymer 64 67 67 64 67 62 - 64 62 63
(C) olefinic copolymer 0.5 0.5 0.5 0.7 0.5 0.5 0.5 - 0.5 0.5
flow index 10.1 12.4 13 10.3 12.7 7.7 9.9 9 15.8 8.7
Hardness 112.6 112 112.3 112 112.1 104 111.9 114 113 112
impact strength 7.1 7.1 6.7 6.6 6.9 6 7.9 7.7 4.4 7
heat deflection temperature 91.3 89.3 89.4 90 89.3 85 98.5 91.5 90.5 90
Film Appearance Characteristics ◎ ○ ○ ◎ ○ × ◎ ◎ × ×
chemical resistance ◎ ◎ ◎ ◎ ◎ ○ × × ◎ ×
[302]
[303]
Referring to Table 1, it was confirmed that Examples 1 to 5 were excellent in flow index, hardness, impact strength, film appearance characteristics and chemical resistance, and also had a high thermal deformation temperature.
[304]
On the other hand, Comparative Example 1, which does not include the first styrenic copolymer, significantly lowered the flow index, heat deflection temperature, and impact strength compared to Examples, and it was confirmed that the film appearance characteristics were not excellent.
[305]
Comparative Example 2 not including the second styrenic copolymer and Comparative Example 3 not including the third copolymer were confirmed to have significantly reduced flow index and chemical resistance.
[306]
Comparative Example 4, which did not include the first graft copolymer, had a remarkably lowered impact strength, and it was confirmed that the film appearance properties were also not excellent.
[307]
It was confirmed that Comparative Example 5, which does not include the second graft copolymer, was not excellent in chemical resistance and film appearance characteristics.
[308]
From these results, it could be predicted that a thermoplastic resin molded article having excellent processability, hardness, impact resistance, heat resistance, chemical resistance, and appearance characteristics could be manufactured only when all components of the present invention were included.
[309]
Claims
[Claim 1]
A first graft copolymer comprising a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, a C 1 to C 3 alkyl-substituted styrenic monomer unit, and a vinyl cyan-based monomer unit; A second graft copolymer comprising a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, an alkyl unsubstituted 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; a second styrenic copolymer including an alkyl unsubstituted styrene-based monomer unit and a vinyl cyan-based monomer unit; And C 1 To C 3 A thermoplastic resin composition comprising an olefin-based copolymer comprising an alkyl (meth) acrylate-based monomer unit.
[Claim 2]
The thermoplastic resin composition of claim 1, wherein the first graft copolymer further comprises an alkyl unsubstituted styrenic monomer unit.
[Claim 3]
The thermoplastic resin composition of claim 1, wherein the first graft copolymer and the second graft copolymer have different average particle diameters of cores.
[Claim 4]
The thermoplastic resin composition of claim 1, wherein the first graft copolymer has an average particle diameter of 300 to 500 nm of the core.
[Claim 5]
The thermoplastic resin composition of claim 1, wherein the second graft copolymer has an average particle diameter of 50 to 150 nm of the core.
[Claim 6]
The method according to claim 1, wherein the olefin-based copolymer comprises a C 2 to C 4 olefin-based monomer units and C 1 to C 3 alkyl (meth) acrylate-based monomer units in a weight ratio of 85:15 to 65:35 The thermoplastic resin composition.
[Claim 7]
The thermoplastic resin composition of claim 1, wherein the olefin-based copolymer has a weight average molecular weight of 50,000 to 200,000 g/mol.
[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 first graft copolymer, the second graft copolymer, the first styrenic copolymer, and the second styrenic copolymer, the olefinic copolymer The thermoplastic resin composition comprising 0.01 to 2 parts by weight of the coal.
[Claim 9]
The method according to claim 1, 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 olefinic copolymer A thermoplastic resin composition comprising 0.5 to 1 part by weight of the coal.
[Claim 10]
The method according to claim 1, The first graft copolymer and the second graft copolymer, based on 100 parts by weight of the total of the first styrenic copolymer and the second styrenic copolymer, the first graft copolymer and the second graft copolymer. 2 The thermoplastic resin composition in which the combined content of the graft copolymer is 10 to 35 parts by weight.
[Claim 11]
The thermoplastic resin composition of claim 10, wherein the weight ratio of the first graft copolymer to the second graft copolymer is 1.5:1 to 10:1.
[Claim 12]
The method according to claim 1, With respect to 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 styrenic copolymer and the second styrenic copolymer 2 The thermoplastic resin composition in which the total content of the styrenic copolymer is 65 to 90 parts by weight.
[Claim 13]
The method according to claim 12, wherein the content of the first styrenic copolymer 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. 14 to 20 parts by weight of the thermoplastic resin composition.
[Claim 14]
The method according to claim 1, 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 15]
The method according to claim 1, 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 10 to 15 parts by weight of the copolymer; 5 to 8 parts by weight of the second graft copolymer; 14 to 16 parts by weight of the first styrenic copolymer; 62 to 66 parts by weight of the second styrenic copolymer; and 0.3 to 0.6 parts by weight of the olefin-based copolymer.