The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0132192, filed on October 31, 2018 and Korean Patent Application No. 10-2019-0134501, filed on October 28, 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 excellent in colorability, weather resistance, tensile strength, flexural strength and impact strength.
[5]
background
[6]
A thermoplastic resin composition comprising a diene-based graft copolymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to a diene-based rubber polymer has excellent impact resistance, rigidity, chemical resistance and processability, and has excellent electrical, electronic, and architectural properties. It is used in various fields such as automobiles and automobiles. However, it was not suitable as an outdoor material due to its weak weather resistance.
[7]
Accordingly, a thermoplastic resin composition including an acrylic graft copolymer having excellent weather resistance and aging resistance, and graft polymerization of an aromatic vinyl monomer and a vinyl cyanide monomer to an acrylic rubber polymer, has received attention as an alternative. However, the thermoplastic resin composition including the acrylic graft copolymer has weak colorability, so it is difficult to apply to products requiring high quality.
[8]
Accordingly, research to develop a thermoplastic resin composition having excellent colorability as well as weather resistance is continuing.
[9]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[10]
An object of the present invention is to provide a thermoplastic resin composition excellent in weather resistance, colorability, tensile strength, flexural strength and impact strength.
[11]
means of solving the problem
[12]
In order to solve the above problems, the present invention provides a first graft copolymer comprising a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based 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 aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; And C 1 To C 3 Alkyl-substituted styrenic monomers, vinyl cyan-based monomers and C 1 to C 3 It includes a first styrenic copolymer which is a copolymer of a monomer mixture comprising an alkyl (meth)acrylate-based monomer, The first graft copolymer and the second graft copolymer provide a thermoplastic resin composition having different average particle diameters of cores.
[13]
Effects of the Invention
[14]
The thermoplastic resin composition according to the present invention has excellent mechanical properties such as tensile strength, flexural strength, and impact strength while remarkably improved colorability and weather resistance. Specifically, the thermoplastic resin composition according to the present invention is a copolymer of a monomer mixture comprising a C 1 to C 3 alkyl-substituted styrene-based monomer, a vinyl cyan-based monomer and a C 1 to C 3 alkyl (meth)acrylate-based monomer. By using the first styrenic copolymer, excellent colorability and weather resistance can be realized without deterioration of mechanical properties.
[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 average particle diameter of the first and second graft copolymers can be measured using a dynamic light scattering method, and in detail, measured using Nicomp 380 HPL equipment (product name, manufacturer: Nicomp) can do.
[20]
In the present specification, the average particle diameter is preferably an arithmetic average particle diameter in the particle size distribution measured by the dynamic light scattering method, that is, the average particle diameter of the scattering intensity.
[21]
[22]
In the present invention, the graft rates of the first and second graft copolymers can be calculated by the following formula.
[23]
[24]
Graft ratio (%): Weight of grafted monomer (g) / Weight of crosslinked polymer (g) × 100
[25]
[26]
Weight of grafted monomer (g): Weight of insoluble material (gel) after dissolving 1 g of graft copolymer in 30 g of acetone and centrifugation
[27]
Weight of crosslinked polymer (g): Weight of theoretically added C 4 to C 10 alkyl (meth)acrylate monomer in the graft copolymer powder
[28]
[29]
In the present invention, the weight average molecular weight of the first styrenic copolymer, the second styrenic copolymer, and the (meth)acrylic polymer is obtained by using tetrahydrofuran as an eluent, and by gel permeation chromatography on a standard PS (standard polystyrene) sample. can be measured relative to
[30]
[31]
In the present invention, the polymer should be understood as a concept including both a homopolymer formed by polymerization of one type of monomer and a copolymer formed by polymerization of two or more types of monomers.
[32]
[33]
1. Thermoplastic resin composition
[34]
The thermoplastic resin composition according to an embodiment of the present invention is 1) a first graft copolymer comprising a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit. ; 2) C 4 to C 10 A second graft copolymer comprising an alkyl (meth) acrylate-based monomer unit, an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit; and 3) a first styrenic copolymer which is a copolymer of a monomer mixture including a C 1 to C 3 alkyl-substituted styrenic monomer, a vinyl cyan-based monomer, and a C 1 to C 3 alkyl (meth)acrylate-based monomer. and the average particle diameter of the core of the first graft copolymer and the second graft copolymer is different from each other.
[35]
[36]
Since the average particle diameters of the cores of the first graft copolymer and the second graft copolymer are different from each other, the thermoplastic resin composition according to an embodiment of the present invention can implement both excellent weather resistance and mechanical properties.
[37]
[38]
In addition, the thermoplastic resin composition according to an embodiment of the present invention may further include 4) a second styrenic copolymer, which is a copolymer of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyan-based monomer.
[39]
[40]
In addition, the thermoplastic resin composition according to an embodiment of the present invention may further include 5) a (meth)acrylic polymer including a C 1 to C 3 alkyl (meth)acrylate-based monomer unit.
[41]
[42]
Hereinafter, components of the thermoplastic resin composition according to an embodiment of the present invention will be described in detail.
[43]
[44]
1) first graft copolymer
[45]
The first graft copolymer includes a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit.
[46]
[47]
The first graft copolymer may impart excellent weather resistance, tensile strength, flexural strength, and impact strength to the thermoplastic resin composition. Specifically, the C 4 to C 10 alkyl (meth)acrylate-based monomer unit may impart excellent weather resistance to the thermoplastic resin composition. In addition, the average particle diameter of the first graft copolymer may impart excellent tensile strength, flexural strength and impact strength to the thermoplastic resin composition.
[48]
[49]
The first graft copolymer may be a graft copolymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer to an acrylic rubbery polymer that is a cross-linked polymer of a C 4 to C 10 alkyl (meth)acrylate-based monomer. have.
[50]
Here, the acrylic rubber polymer may mean a core.
[51]
[52]
The first graft copolymer has an average particle diameter of the core of 350 to 600 nm, 370 to 550 nm, or 400 to 500 nm, of which 400 to 500 nm is preferable. When the above-described range is satisfied, mechanical properties such as tensile strength, flexural strength and impact strength of the thermoplastic resin composition can be further improved. In addition, the colorability of the thermoplastic resin composition can be remarkably improved.
[53]
[54]
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.
[55]
The C 4 to C 10 alkyl (meth)acrylate-based monomer unit may be included in an amount of 30 to 70 wt%, or 40 to 60 wt%, based on the total weight of the first graft copolymer, of which 40 It is preferably included in an amount of from 60% by weight to 60% by weight. If the above-described range is satisfied, the weather resistance and mechanical properties of the first graft copolymer may be further improved.
[56]
[57]
The aromatic vinyl-based 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, among which alkyl unsubstituted styrene A unit derived from styrene, which is a system monomer, is preferable.
[58]
The aromatic vinyl-based monomer unit may be included in an amount of 5 to 25 wt%, or 10 to 20 wt%, based on the total weight of the first graft copolymer, of which 10 to 20 wt% is preferably included. . When the above-described range is satisfied, the processability of the first graft copolymer may be further improved.
[59]
[60]
The vinyl cyan-based monomer unit may be a unit derived from one or more monomers selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, among which, a unit derived from acrylonitrile is preferable. .
[61]
The vinyl cyan-based monomer unit may be included in an amount of 15 to 55% by weight, or 25 to 45% by weight, based on the total weight of the first graft copolymer, and it is preferably included in an amount of 25 to 45% by weight. . If the above-described range is satisfied, the chemical resistance and rigidity of the first graft copolymer may be further improved.
[62]
[63]
The first graft copolymer may have a graft rate of 10 to 50% or 20 to 40%, of which 20 to 40% is preferable. If the above-described range is satisfied, the mechanical properties of the first graft copolymer, that is, tensile strength, flexural strength, and impact strength may be further improved.
[64]
[65]
The first graft copolymer may be included in an amount of 1 to 20% by weight or 5 to 15% by weight based on the total weight of the thermoplastic resin composition, and it is preferably included in an amount of 5 to 15% by weight. When the above-described range is satisfied, the thermoplastic resin composition may implement excellent mechanical properties.
[66]
[67]
2) the second graft copolymer
[68]
The second graft copolymer includes a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit.
[69]
[70]
The second graft copolymer may impart excellent weather resistance to the thermoplastic resin composition. Specifically, due to the C 4 to C 10 alkyl (meth)acrylate-based monomer unit and the above-described average particle diameter, excellent weather resistance can be imparted to the thermoplastic resin composition.
[71]
[72]
The second graft copolymer may be a graft copolymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer to an acrylic rubbery polymer that is a cross-linked polymer of a C 4 to C 10 alkyl (meth)acrylate-based monomer. have.
[73]
Here, the acrylic rubber polymer may mean a core.
[74]
[75]
The second graft copolymer has an average particle diameter of 30 to 200 nm or 50 to 150 nm of the core, of which 30 to 200 nm is preferable. When the above-mentioned range is satisfied, the specific surface area of ​​the second graft copolymer is widened, and weather resistance can be remarkably improved.
[76]
[77]
The type of the C 4 to C 10 alkyl (meth)acrylate-based monomer unit is the same as described above.
[78]
The C 4 to C 10 alkyl (meth)acrylate-based monomer unit may be included in an amount of 30 to 70 wt%, or 40 to 60 wt%, based on the total weight of the second graft copolymer, of which 40 It is preferably included in an amount of from 60% by weight to 60% by weight. If the above-described range is satisfied, the weather resistance and mechanical properties of the second graft copolymer may be further improved.
[79]
[80]
The type of the aromatic vinyl-based monomer unit is the same as described above.
[81]
The aromatic vinyl-based monomer unit may be included in an amount of 5 to 25 wt%, or 10 to 20 wt%, based on the total weight of the second graft copolymer, of which 10 to 20 wt% is preferable. . When the above-described range is satisfied, the processability of the second graft copolymer may be further improved.
[82]
[83]
The type of the vinyl cyan-based monomer unit is the same as described above.
[84]
The vinyl cyan-based monomer unit may be included in an amount of 15 to 55% by weight, or 25 to 45% by weight, based on the total weight of the second graft copolymer, and preferably included in an amount of 25 to 45% by weight. . If the above-described range is satisfied, the chemical resistance and rigidity of the second graft copolymer may be further improved.
[85]
[86]
The second graft copolymer may have a graft rate of 10 to 50% or 20 to 40%, of which 20 to 40% is preferable. If the above-described range is satisfied, the mechanical properties of the first graft copolymer, that is, tensile strength, flexural strength, and impact strength may be further improved.
[87]
[88]
The second graft copolymer may be included in an amount of 20 to 45% by weight or 25 to 40% by weight based on the total weight of the thermoplastic resin composition, and it is preferably included in an amount of 25 to 40% by weight. When the above-mentioned range is satisfied, the thermoplastic resin composition may implement excellent weather resistance and colorability.
[89]
[90]
3) the first styrenic copolymer
[91]
The first styrenic copolymer is a copolymer of a monomer mixture including a C 1 to C 3 alkyl-substituted styrenic monomer, a vinyl cyan-based monomer, and a C 1 to C 3 alkyl (meth)acrylate-based monomer.
[92]
[93]
The first styrenic copolymer may impart remarkably excellent weather resistance, heat resistance, and colorability to the thermoplastic resin composition.
[94]
In detail, the C 1 to C 3 alkyl-substituted styrenic monomer added during the preparation of the first styrenic copolymer may impart remarkably excellent weather resistance and heat resistance to the thermoplastic resin composition. In addition, the C 1 to C 3 alkyl (meth)acrylate-based monomer added during the preparation of the first styrenic copolymer may impart remarkably excellent colorability to the thermoplastic resin composition.
[95]
[96]
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 preferable. do.
[97]
The C 1 to C 3 alkyl-substituted styrene-based monomer may be included in an amount of 50 to 75% by weight, 55 to 70% by weight, or 60 to 65% by weight, of which 60 to 65% by weight, based on the total weight of the monomer mixture. It is preferably included in %. When included in the above range, it is possible to impart remarkably excellent weather resistance and heat resistance to the thermoplastic resin composition.
[98]
[99]
The type of the vinyl cyanide-based monomer is the same as described above.
[100]
The vinyl cyan-based monomer may be included in an amount of 15 to 40 wt%, 20 to 35 wt%, or 25 to 30 wt%, based on the total weight of the monomer mixture, of which 25 to 30 wt% is preferable. . When included in the above range, it is possible to impart excellent chemical resistance and rigidity to the thermoplastic resin composition.
[101]
[102]
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 methacrylate is preferred.
[103]
The C 1 to C 3 alkyl (meth)acrylate-based monomer may be included in an amount of 1 to 20% by weight, 5 to 15% by weight, or 9 to 13% by weight based on the total weight of the monomer mixture, of which 9 It is preferably included in an amount of from 13% by weight to 13% by weight. When included in the above-mentioned range, it is possible to impart remarkably excellent colorability to the thermoplastic resin composition without a decrease in impact strength.
[104]
[105]
The first styrenic copolymer may have a weight average molecular weight of 80,000 to 105,000 g/mol, 85,000 to 100,000 g/mol, or 90,000 to 95,000 g/mol, of which 90,000 to 95,000 g/mol is preferable. When the above-described range is satisfied, the processability of the thermoplastic resin composition may be further improved.
[106]
[107]
The first styrenic copolymer may be included in an amount of 40 to 70 wt% or 45 to 65 wt%, based on the total weight of the thermoplastic resin composition, and preferably included in an amount of 45 to 60 wt%. When the above-mentioned range is satisfied, the thermoplastic resin composition may implement excellent weather resistance and colorability.
[108]
[109]
4) the second styrenic copolymer
[110]
The second styrenic copolymer may be a copolymer of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyan-based monomer.
[111]
[112]
The second styrenic copolymer may impart excellent processability, chemical resistance, rigidity and heat resistance to the thermoplastic resin composition.
[113]
[114]
The monomer mixture may include the aromatic vinyl-based monomer and the vinyl cyan-based monomer in a weight ratio of 55:45 to 80:20 or 60:40 to 75:25, of which 60:40 to 75:25 by weight It is preferable to include When the above-described range is satisfied, the second styrenic copolymer may balance workability, chemical resistance, rigidity, and heat resistance.
[115]
[116]
The type of the aromatic vinyl-based monomer is the same as described above, and among them, at least one selected from the group consisting of styrene and α-methyl styrene is preferable.
[117]
The type of the vinyl cyanide monomer is the same as described above, and among them, acrylonitrile is preferable.
[118]
[119]
The second styrenic copolymer may be at least one selected from the group consisting of a styrene-acrylonitrile copolymer and an α-methyl styrene-acrylonitrile copolymer, and in order to further improve the processability of the thermoplastic resin composition, styrene -Acrylonitrile copolymer is preferred.
[120]
[121]
The second styrenic copolymer 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 thermoplastic resin composition. When the above-mentioned range is satisfied, the processability of the thermoplastic resin composition can be further improved.
[122]
[123]
5) ( meth )acrylic polymer
[124]
The (meth)acrylic polymer may include a C 1 to C 3 alkyl (meth)acrylate-based monomer unit.
[125]
[126]
The (meth)acrylic polymer may impart excellent weather resistance and colorability to the thermoplastic resin composition.
[127]
[128]
The type of the C 1 to C 3 alkyl (meth)acrylate-based monomer is the same as described above.
[129]
[130]
The (meth)acrylic polymer may have a weight average molecular weight of 80,000 to 100,000 g/mol or 85,000 to 95,000 g/mol, of which 85,000 to 95,000 g/mol is preferable. If the above conditions are satisfied, the colorability of the thermoplastic resin composition may be further improved.
[131]
[132]
On the other hand, the (meth)acrylic polymer further comprises one or more selected from the group consisting of an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit in addition to a C 1 to C 3 alkyl (meth)acrylate-based monomer unit ( It may be a meth)acrylic copolymer.
[133]
In this case, the (meth)acrylic copolymer is a copolymer of a C 1 to C 3 alkyl (meth)acrylate-based monomer and at least one monomer mixture selected from the group consisting of an aromatic vinyl-based monomer and a vinyl cyan-based monomer. can
[134]
The monomer mixture is 30 to 55 parts by weight of at least one selected from the group consisting of an aromatic vinyl monomer and a vinyl cyanide monomer, based on 100 parts by weight of the C 1 to C 3 alkyl (meth)acrylate monomer, or It may be included in 35 to 50 parts by weight, of which 35 to 55 parts by weight is preferably included. When the above-described range is satisfied, compatibility with the first and second styrenic copolymers may be further improved.
[135]
[136]
The (meth)acrylic polymer may be included in an amount of 1 to 10% by weight or 2 to 7% by weight based on the total weight of the thermoplastic resin composition, and is preferably included in an amount of 2 to 7% by weight. When the above-described range is satisfied, the weather resistance and colorability of the thermoplastic resin composition may be further improved.
[137]
[138]
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.
[139]
[140]
Preparation Example 1
[141]
95 parts by weight of a monomer mixture containing 60% by weight of α-methyl styrene, 30% by weight of acrylonitrile and 10% by weight of methyl methacrylate, 5 parts by weight of toluene as a reaction solvent and 1,1-bis(t-butyl as an initiator) A polymerization solution was prepared by adding 0.075 parts by weight of peroxy)cyclohexane and 0.195 parts by weight of polyether poly-t-butylperoxy carbonate. The polymerization reaction was carried out by continuously introducing the polymerization solution into a reactor under a temperature condition of 110 °C. The prepared polymerization product was transferred to a devolatilization tank, and unreacted monomers and reaction solvent were recovered and removed under a temperature of 235° C. and a pressure of 20.6 torr to prepare a heat-resistant styrene-based resin in the form of pellets.
[142]
[143]
Examples and Comparative Examples
[144]
[145]
The specifications of the components used in the following Examples and Comparative Examples are as follows.
[146]
[147]
(A-1) First graft copolymer: SA927 of LG Chem (a graft copolymer obtained by graft polymerization of styrene and acrylonitrile to a butyl acrylate rubber polymer having an average particle diameter of 450 nm) was used.
[148]
[149]
(A-2) Second graft copolymer: SA100 (a graft copolymer obtained by graft polymerization of styrene and acrylonitrile to a butyl acrylate rubbery polymer having an average particle diameter of 100 nm) was used.
[150]
[151]
(B) First styrenic copolymer: The copolymer prepared in Preparation Example 1 was used.
[152]
[153]
(C) a second styrenic copolymer:
[154]
(C-1) Heat-resistant SAN copolymer: 200UH (a copolymer of α-methyl styrene and acrylonitrile) manufactured by LG Chem was used.
[155]
(C-2) SAN copolymer: LG Chem's 95RF (copolymer of styrene and acrylonitrile) was used.
[156]
[157]
(D) (meth)acrylic polymer:
[158]
(D-1) Poly(methyl methacrylate): IH830 manufactured by LG PMMA was used.
[159]
(D-2) (meth)acrylic copolymer: XT510 (copolymer of methyl methacrylate, styrene, and acrylonitrile) manufactured by LG Chem was used.
[160]
[161]
A thermoplastic resin composition was prepared by mixing and stirring the above-mentioned components according to the contents shown in [Table 1] below.
[162]
[163]
Experimental Example 1
[164]
The thermoplastic resin compositions of Examples and Comparative Examples were put into an extrusion kneader (cylinder temperature: 240 ° C.) and extruded to prepare pellets, and the physical properties were evaluated by the method described below, and the results are described in [Table 1].
[165]
[166]
(1) Flow index (g/10min, 220°C, 10 kg): Measured according to ISO 1133.
[167]
[168]
Experimental Example 2
[169]
A specimen was prepared by injecting the pellets prepared in Experimental Example 1, and evaluated by the method described below, and the results are described in [Table 1] below.
[170]
[171]
(2) Softening temperature (Vicat Softening Temperature, ℃): It was measured according to ISO 306.
[172]
(3) Tensile strength (MPa): It was measured according to ISO 527.
[173]
(4) Flexural strength (MPa): Measured according to ISO 178.
[174]
(5) Charpy impact strength (KJ/m2, Notched): Measured according to ISO 179.
[175]
(6) Colorability: The L value was measured in SCI mode using Color-Eye 7000A manufactured by GRETAGMACBETH.
[176]
(7) Weather resistance: A Ci4000 Weather-O meter (brand name, manufacturer: Atlas) was used and tested under the PV3929 condition among VW weather resistance standards. The weather resistance was visually compared and evaluated for the degree of discoloration of the specimen before and after the test based on the gray scale.
[177]
◎: No change in the color of the specimen after the weather resistance test
[178]
○: After the weather resistance test, the color of the specimen is slightly changed
[179]
△: The color of the specimen changes significantly after the weather resistance test
[180]
[181]
[Table 1]
division Example comparative example
One 2 3 4 One 2 3 4 5
(A-1) first graft copolymer (% by weight) 10 10 10 10 10 10 10 10 10
(A-2) Second graft copolymer (% by weight) 30 30 30 30 30 30 30 30 30
(B) first styrenic copolymer (% by weight) 60 55 45 45 - - - - -
(C) the second styrenic copolymer (% by weight) (C-1) - - - - 60 55 45 45 -
(C-2) - - 10 10 - - 10 10 -
(D) (meth)acrylic polymer (% by weight) (D-1) - 5 5 - - 5 5 - -
(D-2) - - - 5 - - - 5 60
flow index 5 5 7 7 5 5 7 7 9
softening temperature 104 105 102 101 105 104 103 103 88
tensile strength 50 50 48 48 49 49 48 49 46
flexural strength 74 74 74 74 74 73 73 74 69
Charpy impact strength 11 11 10 10 11 11 10 10 9
colorability 26.7 26.6 26.5 26.5 27.0 26.9 26.8 26.8 25.3
weather resistance ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ △
(A-1) First graft copolymer: SA927 of LG Chem (a graft copolymer obtained by graft polymerization of styrene and acrylonitrile to a butyl acrylate rubber polymer having an average particle diameter of 450 nm) (A-2) Second graft copolymer: SA100 of LG Chem (a graft copolymer obtained by graft polymerization of butyl acrylate rubber polymer having an average particle diameter of 100 nm with styrene and acrylonitrile) (B) First styrenic copolymer: Copolymer (C-1), which is a copolymer of a monomer mixture containing 60% by weight of α-methyl styrene, 30% by weight of acrylonitrile, and 10% by weight of methyl methacrylate,Heat - resistant SAN copolymer: 200UH (α- Copolymer of methyl styrene and acrylonitrile) (C-2) SAN copolymer: 95RF of LG Chem (copolymer of styrene and acrylonitrile) (C-3) MSAN copolymer: styrene 60 wt%, acrylonitrile Copolymer (D-1) poly(methyl methacrylate ), which is a copolymer of a monomer mixture containing 30% by weight of nitrile and 10% by weightof methyl methacrylate: IH830 (D-2) (meth)acrylic copolymer fromLG PMMACopolymer: LG Chem's XT510 (copolymer of methyl methacrylate, styrene and acrylonitrile)
[182]
Referring to Table 1, it was confirmed that Examples 1 to 4 were excellent in basic physical properties and excellent in colorability and weather resistance. Example 1 and Comparative Example 1, Example 1 and Comparative Example 5, Example 2 and Comparative Example When Example 2, Example 3 and Comparative Example 3, Example 4, and Comparative Example 4 were compared, respectively, the L value differed by 0.3 or more, so it was confirmed that the colorability was particularly significantly improved.
[183]
In addition, when Example 3 and Comparative Example 3, Example 4, and Comparative Example 4 were compared respectively, it was confirmed that not only the colorability but also the weather resistance improvement effect was large.
[184]
Claims
[Claim 1]
A first graft copolymer comprising a C 4 to C 10 alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based 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 aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; And C 1 To C 3 Alkyl-substituted styrenic monomers, vinyl cyan-based monomers and C 1 to C 3 It includes a first styrenic copolymer which is a copolymer of a monomer mixture comprising an alkyl (meth)acrylate-based monomer, The first graft copolymer and the second graft copolymer have different average particle diameters of cores in a thermoplastic resin composition.
[Claim 2]
The method according to claim 1, The monomer mixture, the C 1 to C 3 Alkyl-substituted styrene-based monomer 50 to 75% by weight; 15 to 40% by weight of the vinyl cyanide monomer; and 1 to 20 wt% of the C 1 to C 3 alkyl (meth)acrylate-based monomer.
[Claim 3]
The thermoplastic resin composition of claim 1, wherein the first graft copolymer has an average particle diameter of 350 to 600 nm of the core.
[Claim 4]
The thermoplastic resin composition of claim 1, wherein the second graft copolymer has an average particle diameter of 30 to 200 nm of the core.
[Claim 5]
The thermoplastic resin composition of claim 1, wherein the first graft copolymer and the second graft copolymer are each an acrylonitrile-styrene-alkyl acrylate copolymer.
[Claim 6]
The method according to claim 1, wherein the thermoplastic resin composition is 1 to 20% by weight of the first graft copolymer; 20 to 45 wt% of the second graft copolymer; and 40 to 70% by weight of the first styrenic copolymer.
[Claim 7]
The thermoplastic resin of claim 1, wherein the thermoplastic resin composition further comprises a second styrenic copolymer, and the second styrenic copolymer is a copolymer of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyan-based monomer. composition.
[Claim 8]
The thermoplastic resin composition of claim 7, wherein the thermoplastic resin composition comprises 1 to 20% by weight of the second styrenic copolymer.
[Claim 9]
The method according to any one of claims 1 to 8, wherein the thermoplastic resin composition further comprises a (meth) acrylic polymer, the (meth) acrylic polymer is C 1 to C 3 Alkyl (meth) acrylate-based monomer units A thermoplastic resin composition comprising.
[Claim 10]
The thermoplastic resin composition of claim 9, wherein the thermoplastic resin composition comprises 1 to 10% by weight of the (meth)acrylic polymer.