The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0113966 filed on September 21, 2018 and Korean Patent Application No. 10-2019-0110895 filed on September 6, 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 more particularly, to a thermoplastic resin composition in which injection molding time is shortened without deterioration of external properties.
[5]
background
[6]
The thermoplastic resin composition containing the ABS graft copolymer has chemical resistance, rigidity, impact resistance, and processability, and has excellent surface gloss and excellent secondary processing characteristics such as plating, printing, and painting. It is widely used for a variety of purposes.
[7]
When the thermoplastic resin composition is manufactured into home appliance parts or automobile parts, an injection molding process is often used. For this reason, in order to improve productivity during injection molding, various efforts have been made to shorten the injection molding time. In detail, methods such as adjusting the design such as product thickness or optimizing the mold design have been proposed, but there are limitations, and when processing conditions such as lowering the injection temperature are adjusted, there is a problem that the appearance quality is deteriorated. Currently, the injection molding time, especially the cooling time, is further increased due to the enlargement of the parts.
[8]
Accordingly, in order to improve the productivity of injection-molded products made of the thermoplastic resin composition, it is necessary to develop a material capable of shortening the injection molding time.
[9]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[10]
SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin composition that can improve productivity by shortening injection molding time without deterioration of appearance properties, and also have excellent appearance properties.
[11]
means of solving the problem
[12]
In order to solve the above problems, the present invention provides a first copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer and a vinyl cyan-based monomer unit; and a second copolymer comprising an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit, wherein the first copolymer has a graft ratio of 32 to 50%, and the second copolymer has a weight average The molecular weight is 85,000 to 115,000 g/mol, and the thermoplastic resin composition provides a thermoplastic resin composition comprising 30 wt% or less of the first copolymer and 1.1 wt% or less of residual oligomers.
[13]
Effects of the Invention
[14]
Since the thermoplastic resin composition of the present invention has a high solidification rate, the cooling time can be shortened without deterioration of appearance characteristics during injection molding. Accordingly, the molded article made of the thermoplastic resin composition of the present invention may have improved productivity.
[15]
Modes for carrying out the invention
[16]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[17]
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.
[18]
[19]
In the present invention, the residual oligomer may be measured by gas chromatography (GC). Specifically, after dissolving 2 g of the thermoplastic resin composition in pellet form in 10 ml of chloroform, precipitating it with 30 ml of methanol, taking the supernatant and filtering (0.2 μm disc syringe filter), followed by ALS -GC / FID ( a utomatic L iquid S ampler- G as C hromatography / F lame I onization D analyzed by etector) can be measured.
[20]
[21]
According to ASTM D1238, the flow index in the present invention can be measured under conditions of 220 °C and 10 kg.
[22]
[23]
In the present invention, the graft rate of the first copolymer is obtained by dissolving 2 g of the first copolymer powder in 300 ml of acetone with stirring for 24 hours, separating by a centrifugal separator, and dropping the separated acetone solution into methanol without being grafted. A portion is obtained, which is dried at 60 to 120° C. to obtain a dry product. The weight of this dried product can be measured and can be measured based on the following formula.
[24]
[25]
Graft rate (%) = [(weight of dry matter) - (weight of conjugated diene-based polymer)] /[weight of conjugated diene-based polymer] × 100
[26]
[27]
Weight of conjugated diene-based polymer = solids weight of the conjugated diene-based polymer theoretically added to 2 g of the graft copolymer powder; Or the weight of the conjugated diene-based polymer measured by analyzing the graft copolymer by infrared spectroscopy.
[28]
[29]
In the present invention, the weight average molecular weight of the cell of the first copolymer may mean the weight average molecular weight of a copolymer including an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit grafted to a conjugated diene-based polymer.
[30]
In the present invention, the weight average molecular weight of the shell of the first copolymer is obtained by dissolving the dried product described in the graft rate measurement method in a tetrahydrofuran (THF) solution at a concentration of 1% by weight, and then filtering it through a 1 μm filter, followed by gel permeation chromatography It can be measured as a value relative to a standard PS (standard polystyrene) sample through the graph.
[31]
[32]
In the present invention, the average particle diameter of the conjugated diene-based polymer can be measured using a dynamic light scattering method, and in detail, it can be measured using a Nicomp 380 equipment (product name, manufacturer: PSS).
[33]
In the present specification, the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, that is, an average particle diameter of scattering intensity.
[34]
[35]
In the present invention, the weight average molecular weight of the second copolymer may be measured as a relative value with respect to a standard PS (standard polystyrene) sample through gel permeation chromatography using tetrahydrofuran (THF) as an eluent.
[36]
[37]
1. Thermoplastic resin composition
[38]
A thermoplastic resin composition according to an embodiment of the present invention includes: 1) a first copolymer including a conjugated diene-based polymer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer unit; and 2) a second copolymer including an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit, wherein 1) the first copolymer has a graft ratio of 32 to 50%, and 2) the second copolymer has a weight The average molecular weight is 85,000 to 115,000 g/mol, and the thermoplastic resin composition contains 30 wt% or less of the first copolymer and 1.1 wt% or less of the residual oligomer.
[39]
[40]
The thermoplastic resin composition preferably contains 1 wt% or less of residual oligomers. In the case of the residual oligomer, it is prepared as a by-product when preparing each of the first copolymer and the second copolymer, and is included in the first copolymer and the second copolymer. And, unlike residual monomers, only a small amount of residual oligomer volatilizes during processing of the thermoplastic resin composition. Therefore, in consideration of the content of residual oligomers in the first and second copolymers, the thermoplastic resin composition is prepared to contain residual oligomers in the above-mentioned content or less. must be manufactured When the residual oligomer is included in the above-described content, it is possible to increase the solidification rate during injection molding of the thermoplastic resin composition, thereby remarkably reducing the cooling time during injection molding. In addition, even if the cooling time is significantly reduced, appearance defects such as ejecting pin marks do not occur, so the appearance characteristics are excellent. When the above content is exceeded, the residual oligomer acts as a plasticizer in the thermoplastic resin composition to slow the solidification rate during injection of the thermoplastic resin composition, and consequently, the cooling time during injection molding is prolonged.
[41]
[42]
The thermoplastic resin composition according to an embodiment of the present invention contains the first copolymer in an amount of 30 wt% or less. When the content exceeds the above-mentioned content, the flow index of the thermoplastic resin composition is lowered, and the injection moldability is lowered.
[43]
[44]
The thermoplastic resin composition according to an embodiment of the present invention may include 10 to 30% by weight of the first copolymer and 90 to 70% by weight of the second copolymer, preferably the first copolymer 18 It is preferable to include to 28% by weight and 82 to 72% by weight of the second copolymer. When the above-described content is satisfied, the flow index of the thermoplastic resin composition may be properly maintained, and thus injection moldability may be improved. Accordingly, since the thermoplastic resin composition can be injected at an appropriate temperature, the cooling time during injection molding can be reduced. In addition, it is possible to provide a thermoplastic resin composition having excellent mechanical properties.
[45]
[46]
The thermoplastic resin composition may have a flow index of at least 30 g/10 min or 30 to 50 g/10 min under 220° C. and 10 kg conditions, of which 30 to 50 g/10 min is preferable. The flow index is a factor that is affected by the graft rate of the first copolymer and the weight average molecular weight of the second copolymer. Cooling time can be reduced.
[47]
[48]
Hereinafter, the first and second copolymers included in the thermoplastic resin composition according to an embodiment of the present invention will be described in detail.
[49]
[50]
1) first copolymer
[51]
The first copolymer includes a first copolymer including a conjugated diene-based polymer, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit.
[52]
The first copolymer may impart excellent impact resistance, chemical resistance and processability to the thermoplastic resin composition.
[53]
[54]
The first copolymer may have a graft rate of 32 to 50%, preferably 35 to 45%. When the above-mentioned range is satisfied, the flow index of the thermoplastic resin composition may be properly maintained, and thus injection moldability may be improved. Accordingly, since the thermoplastic resin composition can be injected at an appropriate temperature, the cooling time during injection molding can be reduced. When the above-mentioned range is exceeded, the flow index of the thermoplastic resin composition is lowered to lower the injection moldability, and thus the injection temperature must be increased, thereby increasing the cooling time during injection molding. If it is less than the above-mentioned range, the impact resistance of a thermoplastic resin composition will fall.
[55]
[56]
The first copolymer may have a weight average molecular weight of 55,000 to 95,000 g/mol or 60,000 to 90,000 g/mol of the shell, of which 60,000 to 90,000 g/mol is preferable. When the above-mentioned range is satisfied, the flow index of the thermoplastic resin composition may be properly maintained, and thus injection moldability may be improved. Accordingly, since the thermoplastic resin composition can be injected at an appropriate temperature, the cooling time during injection molding can be reduced. In addition, the thermoplastic resin composition can implement excellent impact resistance.
[57]
[58]
The conjugated diene-based polymer may impart excellent impact resistance and surface gloss properties to the first copolymer.
[59]
The conjugated diene-based polymer may include a conjugated diene-based polymer modified by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer to the conjugated diene-based polymer.
[60]
The conjugated diene-based polymer may be prepared by polymerization, preferably, emulsion polymerization, of a conjugated diene-based polymer, and the conjugated diene-based monomer is 1 selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene. It may be more than one species, of which 1,3-butadiene is preferable.
[61]
[62]
The conjugated diene-based polymer may have an average particle diameter of 0.05 to 0.5 μm or 0.1 to 0.4 μm, of which 0.1 to 0.4 μm is preferable. When the above-described conditions are satisfied, the impact resistance and surface gloss properties of the first copolymer may be further improved.
[63]
The conjugated diene-based polymer may be included in an amount of 50 to 70% by weight or 55 to 65% by weight, based on the total weight of the first copolymer, and it is preferably included in an amount of 55 to 65% by weight. When the above-described conditions are satisfied, the rigidity, mechanical properties, processability, and surface gloss properties of the first copolymer may be further improved.
[64]
[65]
The aromatic vinyl-based monomer unit may impart excellent processability, rigidity, and mechanical properties to the first copolymer.
[66]
The aromatic vinyl-based monomer unit may be a unit derived from at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, and among these, a unit derived from styrene is preferable. .
[67]
The aromatic vinyl-based monomer may be included in an amount of 20 to 40% by weight or 25 to 35% by weight, preferably 25 to 35% by weight, based on the total weight of the first copolymer. When the above-described range is satisfied, the processability, rigidity, and mechanical properties of the first copolymer may be further improved.
[68]
[69]
The vinyl cyan-based monomer unit may impart excellent chemical resistance to the first copolymer.
[70]
The vinyl cyan-based monomer unit may be a unit derived from at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, of which acrylonitrile units are preferred.
[71]
The vinyl cyan-based monomer unit may be included in an amount of 1 to 20% by weight or 5 to 15% by weight, preferably 5 to 15% by weight, based on the total weight of the first copolymer. When the above-described range is satisfied, the chemical resistance of the first copolymer may be further improved.
[72]
[73]
The first copolymer may contain residual oligomer in an amount of 1.5 wt% or less or 1.3 wt% or less, of which 1.3 wt% or less is preferably included. When the above-described range is satisfied, the thermoplastic resin composition may contain as little as possible residual oligomers, specifically, 1.1 wt% or less of residual oligomers.
[74]
[75]
The first copolymer may be prepared by emulsification or bulk polymerization of a conjugated diene-based polymer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer, and of which the first copolymer is emulsion-polymerized to realize excellent impact resistance and surface gloss properties. It is preferable to manufacture by
[76]
[77]
2) second copolymer
[78]
The second copolymer includes an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit.
[79]
The second copolymer may impart excellent chemical resistance, impact resistance and processability to the thermoplastic resin composition.
[80]
[81]
The second copolymer has a weight average molecular weight of 85,000 g/mol to 115,000 g/mol, preferably 90,000 g/mol to 115,000 g/mol, and more preferably 90,000 g/mol to 110,000 g/mol. can be When the above-described content is satisfied, the flow index of the thermoplastic resin composition may be properly maintained, and thus injection moldability may be improved. Accordingly, since the thermoplastic resin composition can be injected at an appropriate temperature, the cooling time during injection molding can be reduced. In addition, excellent impact resistance can be imparted to the thermoplastic resin composition. If it is less than the above range, the flow index of the thermoplastic resin composition is lowered to lower the injection moldability, and thus the injection temperature must be increased, thereby increasing the cooling time during injection molding. When it exceeds the above-mentioned range, the impact resistance of a thermoplastic resin composition will fall.
[82]
[83]
The second copolymer may include an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit in a weight ratio of 65:35 to 80:20 or 70:30 to 80:20, of which 70:30 to 80:20 It is preferable to include it in a weight ratio of When the above-described range is satisfied, it is possible to impart superior chemical resistance, impact resistance and processability to the thermoplastic resin composition.
[84]
[85]
The second copolymer may contain residual oligomers in an amount of 1.6 wt% or less or 1.5 wt% or less, and preferably 1.5 wt% or less of these. When the above-described range is satisfied, the thermoplastic resin composition may contain as little as possible residual oligomers, specifically, 1.1 wt% or less of residual oligomers.
[86]
[87]
The second copolymer may be prepared by suspension or bulk polymerization of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer, and among them, it is preferable to prepare a high-purity copolymer by bulk polymerization.
[88]
The second copolymer is specifically prepared by (1) adding an aromatic vinyl-based monomer and a vinyl cyan-based monomer and performing bulk polymerization to prepare a polymerization product; and (2) devolatilizing the polymerization product.
[89]
The bulk polymerization may be carried out at 130 to 150 °C, and when the above-described temperature is satisfied, the formation of oligomers, which are reaction byproducts, may be suppressed as much as possible.
[90]
In addition, it is preferable to use an initiator having a one-hour half-life temperature of 105 to 145° C. so that the bulk polymerization can be easily performed at the above-mentioned temperature.
[91]
The initiator may be an organic peroxide, dicumyl peroxide, 2,2-bis(4,4-di-t-butylperoxy cyclohexane) propane, 1,1-bis(t-butylperoxy) cyclohexane , 1,1-bis(t-hexylperoxy) may be at least one selected from the group consisting of cyclohexane, preferably dicumyl peroxide.
[92]
In step (1), a reaction solvent and a molecular weight modifier may be further added to the reactor.
[93]
The reaction solvent may be at least one selected from the group consisting of ethylbenzene, toluene, xylene, methyl ethyl ketone and methyl isobutyl ketone, of which toluene is preferable.
[94]
The molecular weight modifier is a group consisting of n-dodecyl mertaptan, n-amyl mercaptan, t-butyl mercaptan, t-dodecyl mertaptan, n-hexyl mertaptan, n-octyl mertaptan and n-nonyl mercaptan. It may be at least one selected from, among which t-dodecyl mercaptan is preferable.
[95]
[96]
In step (2), the polymerization product is first devolatilized at 150 to 160° C. and 400 torr or less, and the first devolatilized polymerization product is secondarily devolatilized at 230 to 250° C., 20 torr or less pressure condition. It may be a step of devolatilization. When the polymerization product is devolatilized under the above-described conditions, the reaction solvent and residual oligomer contained in the polymerization product can be removed as much as possible.
[97]
[98]
Since the second copolymer is prepared by the above-described manufacturing method, the content of residual oligomer may be significantly less than that of the conventional copolymer.
[99]
[100]
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.
[101]
[102]
Examples and Comparative Examples
[103]
The graft copolymer and the matrix copolymer were uniformly mixed in the amounts shown in Tables 1 and 2 below to prepare a thermoplastic resin composition.
[104]
[105]
Experimental Example 1
[106]
The thermoplastic resin compositions of Examples and Comparative Examples were put into a twin-screw extruder having a barrel temperature of 230° C., and pellets were prepared. And, the physical properties of the thermoplastic resin composition in the form of pellets were measured in the following manner, and the results are shown in Tables 1 and 2.
[107]
[108]
① Residual oligomer (wt%): After dissolving 2 g of the thermoplastic resin composition in pellet form in 10 ml of chloroform, precipitating it with 30 ml of methanol, and filtering the supernatant (0.2 μm disc syringe filter) after, ALS-GC / FID ( a utomatic L iquid S ampler- G as C hromatography / F lame I onization D was measured by analysis to etector).
[109]
[110]
② Flow index (g/10 min): According to ASTM D1238, it was measured at 220 °C and 10 kg.
[111]
[112]
Experimental Example 2
[113]
A specimen was prepared by injecting the thermoplastic resin composition in the form of pellets prepared in Experimental Example 1, and the physical properties of the specimen were measured in the following manner, and the results are shown in Tables 1 and 2.
[114]
[115]
③ Required cooling time (seconds): Using a custom-made mold, injection was performed at an injection machine temperature of 220 ° C and a mold temperature of 60 ° C. Time was measured.
[116]
[117]
④ Heat deflection temperature (HDT, ℃): According to ASTM D648, it was measured under the condition of 18.6 kg.
[118]
[Table 1]
division Example
One 2 3 4 5 6 7
Graft copolymer (parts by weight) 1-1 10 18 24 28 - 24 24
1-2 - - - - 24 - -
Matrix copolymer (parts by weight) 2-1 90 82 76 72 76 60 40
2-2 - - - - - 16 36
Residual oligomer (wt%) 0.4 0.4 0.5 0.5 0.5 0.7 0.9
Flow index (g/10 min) 50 45 38 34 37 40 42
Required cooling time (sec) 20 20 21 22 20 23 25
HDT(℃) 95 94 94 93 94 91 90
1-1 : ABS graft copolymer (brand name: DP270M, manufacturer: LG Chem, average particle diameter of core: 0.3 μm, graft rate: 37%, weight average molecular weight of shell: 80,000 g/mol, residual oligomer: 1.0 wt%) 1-2 : ABS graft copolymer (trade name: DP280, manufacturer: LG Chem, average particle diameter of core: 0.3 μm, graft rate: 45%, weight average molecular weight of shell: 70,000 g/mol, residual oligomer: 1.2 wt%) 2-1 : SAN copolymer (brand name: 95RF, manufacturer: LG Chem, acrylonitrile unit content: 31 wt%, weight average molecular weight: 90,000 g/mol, residual oligomer: 0.3 wt%) 2-2 : SAN copolymer (Product name: 81HF, Manufacturer: LG Chem, acrylonitrile unit content: 24 wt%, weight average molecular weight: 110,000 g/mol, residual oligomer: 1.5 wt%)
[119]
[Table 2]
division comparative example
One 2 3 4 5 6 7 8 9
Graft copolymer (parts by weight) 1-1 24 35 24 - - - 24 24 24
1-3 - - - 24 - - - - -
1-4 - - - - 24 - - - -
1-5 - - - - - 24 - - -
Matrix copolymer (parts by weight) 2-1 - 65 - 76 76 - - - -
2-2 76 - - - - 76 - - -
2-3 - - 76 - - - - - -
2-4 - - - - - - 76 - -
2-5 - - - - - - - 76 -
2-6 - - - - - - - - 76
Residual oligomer (wt%) 1.4 0.5 0.5 0.5 0.5 0.5 2.3 2.7 2.5
Flow index (g/10 min) 40 24 24 29 26 28 38 9 44
Required cooling time (sec) 39 38 35 31 33 37 40 42 40
HDT(℃) 88 89 93 90 90 89 87 88 88
1-1 : ABS graft copolymer (brand name: DP270M, manufacturer: LG Chem, average particle diameter of core: 0.3 μm, graft rate: 37%, weight average molecular weight of shell: 80,000 g/mol, residual oligomer: 1.0 wt%) 1-3 : ABS graft copolymer (Manufacturer: LG Chem, average particle diameter of core: 0.3 μm, graft rate: 77%, weight average molecular weight of shell: 40,000 g/mol, residual oligomer: 1.1 wt%) 1-4 : ABS graft copolymer (Manufacturer: LG Chem, average particle diameter of core: 0.3 μm, graft rate: 55%, weight average molecular weight of shell: 110,000 g/mol, residual oligomer: 1.3 wt%) 1-5 : ABS graft air Coalescing (Manufacturer: LG Chem, average particle diameter of core: 0.3 μm, graft rate: 27%, weight average molecular weight of shell: 100,000 g/mol, residual oligomer: 1.1 wt%) 2-1 : SAN copolymer (brand name: 95RF, Manufacturer: LG Chemical, acrylonitrile unit content: 31 wt%, weight average molecular weight: 90,000 g/mol, residual oligomer: 0.3 wt%) 2-2 : SAN copolymer (brand name: 81HF, manufacturer: LG Chem, Acrylic) Content of ronitrile unit: 24 wt%, weight average molecular weight: 110,000 g/mol, residual oligomer: 1.5 wt%) 2-3 : SAN copolymer (brand name: 92RF, manufacturer: LG Chem, acrylonitrile unit content: 27 wt%, weight average molecular weight: 120,000 g/mol, residual oligomer: 0.4 wt%) 2-4 : SAN copolymer (brand name) : 82TR, Manufacturer: LG Chemical, Acrylonitrile unit content: 18 wt%, Weight average molecular weight: 130,000 g/mol, Residual oligomer: 2.7 wt%) 2-5 : SAN copolymer (Product name: 97HC, Manufacturer: LG Chemical, content of acrylonitrile unit: 31 wt%, weight average molecular weight: 170,000 g/mol, residual oligomer: 3.2 wt%) 2-6 : SAN copolymer (manufacturer: LG Chemical, content of acrylonitrile unit: 32 wt%, weight average molecular weight: 80,000 g/mol, residual oligomer: 3.0 wt%)
[120]
Referring to Tables 1 and 2, in Examples 1 to 7 including the first copolymer and the second copolymer, the content of residual oligomer and the flow index maintain an appropriate level, so it can be confirmed that the required cooling time is short. there was. And, when the residual oligomer and the flow index of the thermoplastic resin composition are at an appropriate level, if the type of the first copolymer is the same, the lower the content of the first copolymer, the shorter the required cooling time and the higher the heat deflection temperature, It could be predicted that the injection moldability and heat resistance would be excellent.
[121]
And, it was predicted that the lower the residual oligomer of the thermoplastic resin composition, the shorter the required cooling time, the higher the heat deformation temperature, and the better the injection moldability and heat resistance.
[122]
On the other hand, even if the thermoplastic resin composition of Comparative Example 1 included both the first and second copolymers, the content of the residual oligomer was high, and thus it could be predicted that the required cooling time was long and the injection moldability was significantly reduced.
[123]
Since the thermoplastic resin composition of Comparative Example 2 contains an excessive amount of the first copolymer, the flow index was significantly lowered even if the content of residual oligomer was at an appropriate level. .
[124]
Since the thermoplastic resin composition of Comparative Example 3 does not include the second copolymer and contains only the first and third copolymers, the flow index is significantly lowered even if the content of residual oligomer is at an appropriate level, so the required cooling time is prolonged and injection molding It could be predicted that the sex would decrease significantly.
[125]
Since the thermoplastic resin compositions of Comparative Examples 4 and 5 did not include the first copolymer, the flow index was significantly lowered even if the content of the residual oligomer was at an appropriate level, so it was predicted that the required cooling time was prolonged and the injection moldability decreased. .
[126]
Since the thermoplastic resin composition of Comparative Example 6 includes a graft copolymer having a graft rate of 24%, even if the content of residual oligomer in the thermoplastic resin composition is at an appropriate level, the flow index is 30 g/min, so the required cooling time is long and injection molding A decline in sex could be predicted.
[127]
Since the thermoplastic resin composition of Comparative Example 7 does not include the second copolymer and includes the sixth copolymer having a high weight average molecular weight and a high content of acrylonitrile units, the content of residual oligomers is increased, which requires cooling It was predictable that the injection moldability deteriorated as the time increased.
[128]
Since the thermoplastic resin composition of Comparative Example 8 did not include the second copolymer but included the seventh copolymer having a high weight average molecular weight, it was confirmed that the content of residual oligomers was increased. As a result, it could be predicted that the required cooling time was prolonged and the injection moldability deteriorated.
[129]
Since the thermoplastic resin composition of Comparative Example 9 did not include the second copolymer and included the eighth copolymer having a low weight average molecular weight and a high residual oligomer content, it was confirmed that the residual oligomer content was increased. As a result, it could be predicted that the required cooling time was prolonged and the injection moldability deteriorated.
[130]
Claims
[Claim 1]
a first copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; and a second copolymer comprising an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit, wherein the first copolymer has a graft ratio of 32 to 50%, and the second copolymer has a weight average The molecular weight is 85,000 to 115,000 g/mol, and the thermoplastic resin composition comprises 30 wt% or less of the first copolymer and 1.1 wt% or less of the residual oligomer.
[Claim 2]
The thermoplastic resin composition of claim 1, wherein the second copolymer is 90,000 g/mol to 115,000 g/mol.
[Claim 3]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition contains 1 wt% or less of residual oligomers.
[Claim 4]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a flow index of 30 g/10 min or more under 220 °C and 10 kg conditions.
[Claim 5]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a flow index of 30 to 50 g/10 min under conditions of 220 °C and 10 kg.
[Claim 6]
The thermoplastic resin composition of claim 1, wherein the first copolymer has a graft ratio of 35 to 45%.
[Claim 7]
The thermoplastic resin composition of claim 1, wherein the first copolymer has a shell weight average molecular weight of 55,000 to 95,000 g/mol.
[Claim 8]
The thermoplastic resin composition of claim 1, wherein the conjugated diene-based polymer has an average particle diameter of 0.05 to 0.5 μm.
[Claim 9]
The thermoplastic resin composition of claim 1, wherein the first copolymer contains 1.5 wt% or less of residual oligomer.
[Claim 10]
The thermoplastic resin composition of claim 1, wherein the second copolymer contains 1.6 wt% or less of residual oligomer.
[Claim 11]
The method according to claim 1, wherein the thermoplastic resin composition is 10 to 30% by weight of the first copolymer; and 70 to 90% by weight of the second copolymer.