Title of Invention: Thermoplastic resin composition and thermoplastic resin molded article
technical field
[One]
[Citation with related applications]
[2]
The present invention claims the benefit of priority based on Korean Patent Application No. 10-2019-0019094, filed on February 19, 2019 and Korean Patent Application No. 10-2020-0014203, filed on February 6, 2020, All content disclosed in the literature is incorporated herein by reference.
[3]
[Technical field]
[4]
The present invention relates to a thermoplastic resin composition and a thermoplastic resin molded article, and to a thermoplastic resin composition and a thermoplastic resin molded article excellent in heat resistance, impact resistance, colorability and scratch resistance.
[5]
background
[6]
A diene-based thermoplastic resin composition comprising a diene-based graft copolymer obtained by graft copolymerizing 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, It is used in various fields such as architecture, automobiles, etc. However, it was not suitable as an outdoor material due to its weak weather resistance.
[7]
Accordingly, an acrylic thermoplastic resin composition having excellent weather resistance and aging resistance, and including an acrylic graft copolymer obtained by graft copolymerization of an acrylic rubber polymer with an aromatic vinyl monomer and a vinyl cyanide monomer, has received attention as an alternative. However, since the acrylic thermoplastic resin composition has weak colorability and scratch resistance, it is difficult to apply to products requiring high quality.
[8]
Accordingly, in order to improve colorability and scratch resistance, a method of applying poly(methyl methacrylate) to the acrylic thermoplastic resin composition has been proposed, but a problem of reduced impact resistance occurred. In order to solve this problem, a method of applying a styrene/acrylonitrile/methyl methacrylate copolymer to an acrylic thermoplastic resin composition has been proposed, but a problem of lowering impact resistance and heat resistance occurred.
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[9]
It is an object of the present invention to provide a thermoplastic resin composition and a thermoplastic resin molded article excellent in weather resistance, heat resistance, impact resistance, colorability and scratch resistance.
[10]
means of solving the problem
[11]
In order to solve the above problems, the present invention is a first copolymer comprising an acrylic graft copolymer; a second copolymer including an alkyl-substituted styrene-based monomer unit, a vinyl cyanide-based monomer unit, and a (meth)acrylate-based monomer unit; and a third copolymer including an alkyl unsubstituted styrene-based monomer unit, a vinyl cyanide-based monomer unit, and a (meth)acrylate-based monomer unit.
[12]
In addition, the present invention provides a thermoplastic resin molded article made of the above-described thermoplastic resin composition, the heat deflection temperature is 90 ℃ or more, the L value is 25.5 or less, and the pencil hardness is F or more.
[13]
Effects of the Invention
[14]
The thermoplastic resin composition and the thermoplastic resin molded article according to the present invention can be remarkably improved in weather resistance, heat resistance, impact resistance, colorability and scratch resistance.
[15]
Modes for carrying out the invention
[16]
Hereinafter, the present invention will be described in more detail for better understanding of the present invention.
[17]
The terms or words used in the present specification and claims should not 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 acrylic rubber polymer can be measured using a dynamic light scattering method, and in detail, it can be measured using Nicomp 380 HPL equipment (product name, manufacturer: PSS Nicomp).
[20]
In the present specification, the average particle diameter may mean an arithmetic average particle diameter in the particle size distribution measured by the dynamic light scattering method, that is, the scattering intensity average particle diameter.
[21]
[22]
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 gel permeation chromatography using tetrahydrofuran as an eluent.
[23]
[24]
In the present invention, the alkyl-substituted styrenic monomer unit may be a unit derived from an alkyl-substituted styrenic monomer. For example, the 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, among which α-methyl styrene is preferable.
[25]
[26]
In the present invention, the alkyl unsubstituted styrenic monomer unit may be a unit derived from an alkyl unsubstituted styrenic monomer. For example, 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.
[27]
[28]
In the present invention, the vinyl cyanide-based monomer unit may be a unit derived from a vinyl cyanide-based monomer. For example, the vinyl cyanide monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and 2-chloroacrylonitrile, of which acrylonitrile is preferable. .
[29]
[30]
In the present invention, the (meth)acrylate-based monomer unit may be at least one selected from the group consisting of units derived from acrylate-based monomers and methacrylate-based monomer units. The (meth)acrylate-based monomer may be at least one selected from the group consisting of a C 1 to C 10 alkyl acrylate monomer unit and a C 1 to C 10 alkyl methacrylate unit. For example, the (meth) acrylate-based monomer is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 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 decyl (meth) acrylate It may be at least one selected from the group consisting of. Among them, at least one selected from the group consisting of methyl methacrylate and butyl acrylate is preferable.
[31]
[32]
In the present invention, the vinyl-based monomer may mean at least one selected from the group consisting of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. Here, the aromatic vinyl-based monomer may mean at least one selected from the group consisting of an alkyl-substituted styrene-based monomer and an alkyl unsubstituted styrene-based monomer.
[33]
[34]
1. Thermoplastic resin composition
[35]
A thermoplastic resin composition according to an embodiment of the present invention includes: 1) a first copolymer including an acrylic graft copolymer; 2) a second copolymer including an alkyl-substituted styrene-based monomer unit, a vinyl cyanide-based monomer unit, and a (meth)acrylate-based monomer unit; and 3) a third copolymer including an alkyl unsubstituted styrene-based monomer unit, a vinyl cyanide-based monomer unit, and a (meth)acrylate-based monomer unit.
[36]
[37]
The thermoplastic resin composition according to an embodiment of the present invention may further include 4) a (meth)acrylate-based polymer.
[38]
[39]
In addition, the thermoplastic resin composition according to an embodiment of the present invention may further include 5) an additive including a silicone compound.
[40]
[41]
Hereinafter, components of the thermoplastic resin composition according to an embodiment of the present invention will be described in detail.
[42]
[43]
1) first copolymer
[44]
The first copolymer may impart excellent weather resistance, impact resistance, elongation, colorability, chemical resistance, processability, surface gloss properties and whitening properties to the thermoplastic resin composition.
[45]
[46]
The first copolymer may include an acrylic graft copolymer, and the acrylic graft copolymer may be obtained by graft copolymerization of a vinyl monomer to an acrylic rubber polymer, preferably an acrylic rubber polymer with an aromatic vinyl monomer and A vinyl cyan-based monomer may be graft copolymerized.
[47]
The acrylic rubber polymer may have an average particle diameter of 30 to 650 nm or 50 to 550 nm, of which 50 to 550 nm is preferable. When the above-described range is satisfied, the weather resistance, impact resistance, elongation, colorability, chemical resistance, processability, surface gloss properties and whitening properties of the thermoplastic resin composition can be further improved.
[48]
[49]
On the other hand, the first copolymer is a first acrylic graft copolymer having different average particle diameters of the acrylic rubber polymer in order to further improve weather resistance, impact resistance, elongation, colorability, chemical resistance, processability, surface gloss properties and whitening properties. and a second acrylic graft copolymer.
[50]
The first acrylic graft copolymer may be one obtained by graft copolymerization of an acrylic rubber polymer having an average particle diameter of 300 to 650 nm or 350 to 550 nm and a vinyl monomer, of which, vinyl is added to an acrylic rubber polymer having an average particle diameter of 350 to 550 nm. It is preferable to graft copolymerize the system monomers. When the above-described conditions are satisfied, the impact resistance can be further improved.
[51]
The second acrylic graft copolymer may be an acrylic rubber polymer having an average particle diameter of 30 to 250 nm or 50 to 150 nm by graft copolymerization of a vinyl monomer, of which, vinyl is added to an acrylic rubber polymer having an average particle diameter of 50 to 150 nm. It is preferable to graft copolymerize the system monomers. If the above conditions are satisfied, weather resistance, colorability, chemical resistance, appearance quality, elongation and whitening characteristics can be further improved. Specifically, the smaller the average particle diameter of the acrylic rubber polymer, the greater the specific surface area, so the weather resistance can be improved. In addition, since visible light can pass through the acrylic rubbery polymer, colorability can be improved. In addition, since it can be uniformly dispersed in a relatively high content in the thermoplastic resin composition, elongation and whitening properties can be improved.
[52]
Here, the acrylic rubbery polymer may be prepared by crosslinking a (meth)acrylate-based monomer, preferably a C 4 to C 10 alkyl (meth)acrylate-based monomer, more preferably butyl acrylate.
[53]
[54]
The weight ratio of the first acrylic graft copolymer and the second acrylic graft copolymer may be 5:95 to 25:75 or 10:90 to 20:80, of which 10:90 to 20:80 is preferable. . When the above-mentioned conditions are satisfied, a thermoplastic resin composition in which impact resistance, weather resistance, colorability, chemical resistance, appearance quality, elongation and whitening properties are balanced can be prepared.
[55]
[56]
The first copolymer may be prepared directly or a commercially available material may be used.
[57]
[58]
The first copolymer may be included in an amount of 20 to 50 parts by weight, 25 to 45 parts by weight, or 32 to 42 parts by weight, based on 100 parts by weight of the total of the first copolymer, the second copolymer and the third copolymer, Among them, 32 to 42 parts by weight may be included. If the above conditions are satisfied, elongation, weather resistance, chemical resistance, colorability, processability, surface gloss characteristics, and whitening characteristics of the thermoplastic resin composition can be remarkably improved.
[59]
[60]
2) second copolymer
[61]
The second copolymer may impart excellent heat resistance and weather resistance to the thermoplastic resin composition. In addition, excellent heat resistance, weather resistance, scratch resistance and coloring properties can be imparted to the thermoplastic resin composition by a synergistic action with the third copolymer, which will be described later.
[62]
[63]
The second copolymer is a non-graft copolymer and includes an alkyl-substituted styrene-based monomer unit, a vinyl cyanide-based monomer unit, and a (meth)acrylate-based monomer unit. Since the second copolymer includes an alkyl-substituted styrene-based monomer unit, excellent heat resistance, weather resistance, and scratch resistance may be imparted to the thermoplastic resin composition. In addition, since the second copolymer includes a vinyl cyanide-based monomer unit, excellent chemical resistance and rigidity may be imparted to the thermoplastic resin composition. In addition, since the second copolymer includes a (meth)acrylate-based monomer unit, excellent colorability may be imparted to the thermoplastic resin composition.
[64]
[65]
The second copolymer may be a copolymer of a monomer mixture including an alkyl-substituted styrene-based monomer, a vinyl cyanide-based monomer, and a (meth)acrylate-based monomer.
[66]
The monomer mixture may include 30 to 50% by weight or 35 to 45% by weight of the alkyl-substituted styrene-based monomer, and it is preferable to include it in 35 to 45% by weight. When the above conditions are satisfied, the heat resistance, weather resistance and scratch resistance of the thermoplastic resin composition can be further improved.
[67]
The monomer mixture may contain 20 to 40% by weight or 25 to 35% by weight of the vinyl cyanide monomer, and it is preferable to include it in an amount of 25 to 35% by weight. When the above conditions are satisfied, the chemical resistance and rigidity of the thermoplastic resin composition can be further improved.
[68]
The monomer mixture may include 20 to 40% by weight or 25 to 35% by weight of the (meth)acrylate-based monomer, and preferably includes 25 to 35% by weight of the (meth)acrylate-based monomer. When the above conditions are satisfied, the colorability can be further improved without lowering the impact resistance of the thermoplastic resin composition.
[69]
Here, the (meth)acrylate-based monomer is preferably a C 1 to C 3 alkyl (meth)acrylate-based monomer.
[70]
[71]
The second copolymer may have a weight average molecular weight of 80,000 to 110,000 g/mol, 85,000 to 105,000 g/mol, or 80,000 to 100,000 g/mol, of which 80,000 to 100,000 g/mol is preferable. When the above-described conditions are satisfied, the fluidity and mechanical properties of the thermoplastic resin composition may be properly maintained.
[72]
[73]
The second copolymer may be an α-methylstyrene/acrylonitrile/methylmethacrylate copolymer.
[74]
[75]
The second copolymer may be prepared by using a commercially available material or by suspension or bulk polymerization of the monomer mixture, and is preferably prepared by bulk polymerization to prepare a high-purity copolymer.
[76]
[77]
The second copolymer may be included in an amount of 20 to 45 parts by weight, 25 to 40 parts by weight, or 32 to 38 parts by weight, based on 100 parts by weight of the total of the first copolymer, the second copolymer and the third copolymer, Among them, it is preferably included in an amount of 30 to 40 parts by weight. When the above-described conditions are satisfied, the heat resistance, scratch resistance and colorability of the thermoplastic resin composition may be further improved. In addition, it is possible to achieve a balance between heat resistance, scratch resistance and colorability of the thermoplastic resin composition.
[78]
[79]
3) third copolymer
[80]
The third copolymer may impart excellent colorability and processability to the thermoplastic resin composition. In addition, excellent scratch resistance can be imparted to the thermoplastic resin composition by a synergistic action with the above-described second copolymer.
[81]
[82]
The third copolymer is a non-graft copolymer and includes an alkyl unsubstituted styrene-based monomer unit, a vinyl cyanide-based monomer unit, and a (meth)acrylate-based monomer unit. Since the third copolymer includes an alkyl unsubstituted styrene-based monomer unit, excellent colorability and processability may be imparted to the thermoplastic resin composition. In addition, since the third copolymer includes a vinyl cyanide-based monomer, excellent chemical resistance and rigidity may be imparted to the thermoplastic resin composition. In addition, excellent scratch resistance can be imparted to the thermoplastic resin composition by a synergistic action with the above-described second copolymer.
[83]
[84]
The third copolymer may include an alkyl unsubstituted styrene-based monomer unit in an amount of 10 to 35% by weight or 15 to 30% by weight, of which 15 to 30% by weight is preferable. When the above-described conditions are satisfied, better processability may be imparted to the thermoplastic resin composition.
[85]
The third copolymer may include 3 to 15% by weight, or 5 to 10% by weight of a vinyl cyanide-based monomer unit, and it is preferable to include it in an amount of 5 to 10% by weight. When the above-described conditions are satisfied, it is possible to impart superior chemical resistance and rigidity to the thermoplastic resin composition.
[86]
The third copolymer may include (meth) acrylate-based monomer units in an amount of 60 to 80% by weight or 65 to 75% by weight, of which 65 to 75% by weight is preferable. If the above conditions are satisfied, the colorability can be further improved without lowering the impact resistance of the thermoplastic resin composition.
[87]
Here, the (meth)acrylate-based monomer unit is preferably a unit derived from a C 1 to C 3 alkyl (meth)acrylate-based monomer.
[88]
[89]
The third copolymer may be a methyl methacrylate/styrene/acrylonitrile copolymer.
[90]
[91]
The third copolymer may be prepared directly or a commercially available material may be used.
[92]
[93]
The third copolymer may be 10 to 40 parts by weight, 15 to 35 parts by weight, or 20 to 30 parts by weight, based on 100 parts by weight of the sum of the first copolymer, the second copolymer, and the third copolymer, 20 to 30 parts by weight is preferred. When the above-mentioned range is satisfied, the impact resistance and processability of the thermoplastic resin composition can be further improved,
[94]
[95]
4) ( meth ) acrylate-based polymer
[96]
The (meth)acrylate-based polymer may impart excellent processability, colorability, scratch resistance and weather resistance to the thermoplastic resin composition.
[97]
[98]
The (meth) acrylate-based polymer is a non-graft copolymer, and may include a (meth) acrylate-based monomer unit, and preferably includes a C 1 to C 3 alkyl (meth) acrylate-based monomer unit. .
[99]
[100]
The (meth)acrylate-based polymer may have a weight average molecular weight of 15,000 to 150,000 g/mol, 20,000 to 120,000 g/mol, or 24,000 to 98,000 g/mol, of which 24,000 to 98,000 g/mol is preferable. If the above conditions are satisfied, the colorability and processability of the thermoplastic resin composition may be further improved. In addition, as the weight average molecular weight of the (meth)acrylate-based polymer decreases, the processability of the thermoplastic resin composition may be further improved.
[101]
[102]
The (meth)acrylate-based polymer may be poly(methylmethacrylate).
[103]
[104]
The (meth)acrylate-based polymer may be prepared directly or a commercially available material may be used.
[105]
[106]
The (meth)acrylate-based polymer is 1 to 20 parts by weight, 3 to 17 parts by weight based on 100 parts by weight of the first copolymer, the second copolymer, the third copolymer, and the (meth)acrylate-based polymer. Alternatively, it may be included in an amount of 5 to 15 parts by weight, of which it is preferably included in an amount of 5 to 15 parts by weight. If the above conditions are satisfied, the colorability, scratch resistance and processability of the thermoplastic resin composition may be further improved.
[107]
[108]
5) Additives
[109]
The additive may include a silicone compound.
[110]
[111]
The silicone compound may impart excellent scratch resistance and abrasion resistance to the thermoplastic resin composition. In addition, it is possible to improve the releasability that allows the injection-molded article made of the thermoplastic resin composition to be well separated from the mold. In addition, it can act as a good lubricant in the thermoplastic resin composition to improve injection moldability. In addition, when the thermoplastic resin composition is melted, the flow index is excellent and processability can be improved. In addition, it is possible to reduce the surface friction force of the molded article made of the thermoplastic resin composition, and improve the surface gloss properties. In addition, since compatibility with the first copolymer, the second copolymer, the third copolymer, and the (meth)acrylate-based polymer, which are components of the thermoplastic resin composition, is excellent, it may be uniformly mixed in the thermoplastic resin composition.
[112]
[113]
The silicone compound is a slip agent, and may be polyester modified siloxane.
[114]
[115]
The silicone compound may be prepared directly or a commercially available material may be used, and among commercially available materials, TEGOMER H-SI 6440P or TEGOMER H-SI 6441P of EVONIC NUTRITION & CARE GMBH may be used.
[116]
[117]
The additive is a sum of 100 parts by weight of the first copolymer, the second copolymer, and the third copolymer or 100 parts by weight of the sum of the first copolymer, the second copolymer, the third copolymer and the (meth)acrylate-based polymer With respect to, it may be included in 0.1 to 3 parts by weight or 0.5 to 2 parts by weight, of which it is preferably included in 0.5 to 2 parts by weight. When the above conditions are satisfied, the thermoplastic resin composition has excellent compatibility with components, and the scratch resistance, abrasion resistance, moldability and surface gloss of the thermoplastic resin composition can be improved, and the surface friction force of the thermoplastic resin composition is reduced. can do it
[118]
[119]
2. Thermoplastic resin molded products
[120]
Another embodiment of the present invention, a thermoplastic resin molded article, is made of the thermoplastic resin composition according to an embodiment of the present invention, has a heat deflection temperature of 90 ℃ or more, an L value of 25.5 or less, and a pencil hardness of F or more. The thermoplastic resin molded article has a heat deformation temperature of 90 to 105 ° C, an L value of 24 to 25.5, and a pencil hardness of F or more, a heat deformation temperature of 91 to 105 ° C., and an L value of 24 to 25.2, It is more preferable that pencil hardness is H or more. Since the thermoplastic resin molded article satisfies the above-described conditions, excellent heat resistance, color characteristics, and scratch resistance can be realized.
[121]
[122]
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.
[123]
[124]
Preparation Example 1
[125]
95 parts by weight of a monomer mixture containing 40% by weight of α-methyl styrene, 30% by weight of acrylonitrile and 30% 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 is transferred to a devolatilization tank, and unreacted monomers and reaction solvents are recovered and removed under a temperature of 235° C. and a pressure of 20.6 torr to obtain a pellet-type copolymer of α-methyl styrene/acrylonitrile/methylmethacrylate copolymer. (weight average molecular weight: 95,000 g/mol) was prepared.
[126]
[127]
Examples and Comparative Examples
[128]
[129]
The specifications of the components used in the following Examples and Comparative Examples are as follows.
[130]
[131]
(A) acrylic graft copolymer
[132]
(A-1) First acrylic 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.
[133]
(A-2) Second acrylic graft copolymer: SA100 (a graft copolymer obtained by graft polymerization of styrene and acrylonitrile to a butyl acrylate rubber polymer having an average particle diameter of 100 nm) was used.
[134]
[135]
(B) Alkyl-substituted styrenic copolymer
[136]
(B-1): The copolymer prepared in Preparation Example 1 was used.
[137]
(B-2): 200UH (α-methylstyrene/acrylonitrile copolymer) manufactured by LG Chem was used.
[138]
[139]
(C) Alkyl unsubstituted styrene-based copolymer: XT510 (styrene/acrylonitrile/methyl methacrylate copolymer) manufactured by LG Chem was used.
[140]
[141]
(D) (meth)acrylate-based polymer
[142]
(D-1): LG MMA's IH830 (poly(methyl methacrylate), weight average molecular weight: 98,000 g/mol) was used.
[143]
(D-2): BA611 (poly(methyl methacrylate), weight average molecular weight: 45,000 g/mol) manufactured by LG MMA was used.
[144]
(D-3): LG MMA's BN600 (poly(methyl methacrylate), weight average molecular weight: 24,000 g/mol) was used.
[145]
[146]
(E) Silicone compound: EVONIK's TEGOMER 6441P was used.
[147]
[148]
A thermoplastic resin composition was prepared by mixing and stirring the above-mentioned components according to the contents shown in [Table 1] to [Table 3].
[149]
[150]
Experimental Example 1
[151]
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 shown in [Table 1] to [Table 3] ] was described.
[152]
[153]
(1) Flow index (g/10 min): According to ASTM D1238, using GOTTFERT's MI-4, the weight was measured for 10 minutes under conditions of a temperature of 220 °C and a load of 10 kg.
[154]
(2) Heat deflection temperature (°C): The heat deflection temperature was measured with Auto HDT Tester 6A-2 (trade name, manufacturer: TOYOSEIKI) in accordance with ASTM D648.
[155]
[156]
Experimental Example 2
[157]
A specimen was prepared by injecting the pellets prepared in Experimental Example 1, evaluated by the method described below, and the results are described in [Table 1] to [Table 3] below.
[158]
[159]
(1) Izod impact strength (kg·cm/cm, Notched, 1/4 In): It was measured at 23° C. using IMPACT Tester manufactured by TOYOSEIKI in accordance with ASTM D256.
[160]
(2) Colorability: The L value was measured in SCI mode using Color-Eye 7000A from GRETAGMACBETH.
[161]
(3) Pencil hardness: After fixing a pencil at a load of 0.5 kg and an angle of 45 °, the surface of the specimen was scraped by pencil hardness to determine whether or not to be scratched with the naked eye to measure scratch resistance.
[162]
[Table 1]
division Comparative Example 1 Example 1 Comparative Example 2 Example 2 Example 3
(A) acrylic graft copolymer (parts by weight) (A-1) 5 5 5 5 5
(A-2) 30 30 30 30 30
(B) Alkyl-substituted styrenic copolymer (parts by weight) (B-1) - 35 - 35 40
(B-2) 35 - 35 - -
(C) alkyl unsubstituted styrenic copolymer (parts by weight) 30 30 30 30 25
(D) (meth)acrylate-based polymer (parts by weight) (D-1) - - - - -
(D-2) - - - - -
(D-3) - - - - -
(E) silicone compound (parts by weight) - - One One One
flow index 8 8 8 8 8
heat deflection temperature 91 90 90 90 93
Izod impact strength 9 9 9 9 9
colorability 25.9 25.4 25.9 25.4 25.5
pencil hardness HB F F H H
(A) Acrylic graft copolymer (A-1) First acrylic graft copolymer: SA927 of LG Chem (a butyl acrylate rubber polymer having an average particle diameter of 450 nm, graft polymerization of styrene and acrylonitrile) (A-2) Second acrylic graft copolymer: SA100 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 100 nm) (B) Alkyl -substituted styrene-based copolymer (B-1): the copolymer prepared in Preparation Example 1 (α-methylstyrene/acrylonitrile/methylmethacrylate copolymer) (B-2): LG Chem 200UH (α-methylstyrene/acrylonitrile copolymer) (C) alkyl unsubstituted styrenic copolymer : LG Chem’s XT510 (styrene/acrylonitrile/methylmethacrylate copolymer) (D) ( meth ) Acrylate-based polymer (D-1): IH830 (poly(methyl methacrylate), weight average molecular weight: 98,000 g/mol) from LG MMA (D-2): BA611 (poly(methyl methacrylic) from LG MMA) rate), weight average molecular weight: 45,000 g/mol) (D-3): BN600 of LG MMA (poly(methyl methacrylate), weight average molecular weight: 24,000 g/mol) (E) Silicone compound : EVONIK's TEGOMER 6441P
[163]
[Table 2]
division Comparative Example 3 Example 4 Example 5 Example 6
(A) acrylic graft copolymer (parts by weight) (A-1) 5 5 5 5
(A-2) 30 30 30 30
(B) Alkyl-substituted styrenic copolymer (parts by weight) (B-1) - 35 35 35
(B-2) 35 - - -
(C) alkyl unsubstituted styrenic copolymer (parts by weight) 20 20 20 20
(D) (meth)acrylate-based polymer (parts by weight) (D-1) 10 10 - -
(D-2) - - 10 -
(D-3) - - - 10
(E) silicone compound (parts by weight) One One One One
flow index 8 8 12 14
heat deflection temperature 91 91 91 90
Izod impact strength 9 9 9 9
colorability 25.7 25.2 25.2 25.2
pencil hardness F H H H
(A) Acrylic graft copolymer (A-1) First acrylic graft copolymer: SA927 of LG Chem (a butyl acrylate rubber polymer having an average particle diameter of 450 nm, graft polymerization of styrene and acrylonitrile) (A-2) Second acrylic graft copolymer: SA100 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 100 nm) (B) Alkyl -substituted styrene-based copolymer (B-1): the copolymer prepared in Preparation Example 1 (α-methylstyrene/acrylonitrile/methylmethacrylate copolymer) (B-2): LG Chem 200UH (α-methylstyrene/acrylonitrile copolymer) (C) alkyl unsubstituted styrenic copolymer : XT510 (styrene/acrylonitrile/methyl methacrylate copolymer) from LG Chem (D) ( meth ) Acrylate-based polymer (D-1): IH830 (poly(methyl methacrylate), weight average molecular weight: 98,000 g/mol) from LG MMA (D-2): BA611 (poly(methyl methacrylic) from LG MMA) rate), weight average molecular weight: 45,000 g/mol) (D-3): BN600 of LG MMA (poly(methyl methacrylate), weight average molecular weight: 24,000 g/mol) (E) Silicone compound : EVONIK's TEGOMER 6441P
[164]
[Table 3]
division comparative example
4 5 6
(A) acrylic graft copolymer (parts by weight) (A-1) 5 5 5
(A-2) 30 30 30
(B) Alkyl-substituted styrenic copolymer (parts by weight) (B-1) - - 65
(B-2) - - -
(C) alkyl unsubstituted styrenic copolymer (parts by weight) 65 - -
(D) (meth)acrylate-based polymer (parts by weight) (D-1) - 65 -
(D-2) - - -
(D-3) - - -
(E) silicone compound (parts by weight) One One One
flow index 8 4 7
heat deflection temperature 83 87 96
Izod impact strength 7 6 9
colorability 25.1 24.8 25.7
pencil hardness F H F
(A) Acrylic graft copolymer (A-1) First acrylic graft copolymer: SA927 of LG Chem (a butyl acrylate rubber polymer having an average particle diameter of 450 nm, graft polymerization of styrene and acrylonitrile) (A-2) Second acrylic graft copolymer: SA100 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 100 nm) (B) Alkyl -substituted styrene-based copolymer (B-1): the copolymer prepared in Preparation Example 1 (α-methylstyrene/acrylonitrile/methylmethacrylate copolymer) (B-2): LG Chem 200UH (α-methylstyrene/acrylonitrile copolymer) (C) alkyl unsubstituted styrenic copolymer : XT510 (styrene/acrylonitrile/methyl methacrylate copolymer) from LG Chem (D) ( meth ) Acrylate-based polymer (D-1): IH830 (poly(methyl methacrylate), weight average molecular weight: 98,000 g/mol) from LG MMA (D-2): BA611 (poly(methyl methacrylic) from LG MMA) rate), weight average molecular weight: 45,000 g/mol) (D-3): BN600 of LG MMA (poly(methyl methacrylate), weight average molecular weight: 24,000 g/mol) (E) Silicone compound : EVONIK's TEGOMER 6441P
[165]
Referring to Table 1, the thermoplastic resin composition of Example 1 including α-methylstyrene/acrylonitrile/methylmethacrylate copolymer, Comparative Example 1 including styrene/acrylonitrile/methacrylate copolymer The colorability and scratch resistance were excellent compared to the thermoplastic resin composition of In addition, the thermoplastic resin composition of Example 2 including the α-methylstyrene/acrylonitrile/methylmethacrylate copolymer and the silicone compound was compared with the styrene/acrylonitrile/methacrylate copolymer and the silicone compound. Compared to the thermoplastic resin composition of Example 2, the colorability and scratch resistance were excellent.
[166]
When Example 1 and Example 2 were compared, the thermoplastic resin composition of Example 2 further including a silicone compound had superior scratch resistance compared to the thermoplastic resin composition of Example 1.
[167]
When Example 2 and Example 3 were compared, the thermoplastic resin composition of Example 3 containing an excess of α-methylstyrene/acrylonitrile/methyl methacrylate copolymer had heat resistance compared to the thermoplastic resin composition of Example 2 is excellent, but the colorability is slightly lowered.
[168]
Referring to Table 2, the thermoplastic resin compositions of Examples 4 to 6 including α-methylstyrene/acrylonitrile/methylmethacrylate copolymer, even if they further include poly(methyl methacrylate), are styrene/acrylic The colorability and scratch resistance were excellent compared to the thermoplastic resin composition of Comparative Example 3 including the ronitrile/methacrylate copolymer.
[169]
and. When comparing Examples 2 and 4 to 6, poly(methyl methacrylate) does not significantly affect the physical properties of the thermoplastic resin composition, but when poly(methyl methacrylate) having a low weight average molecular weight is used, the flow The higher the index, the better the processability.
[170]
Referring to Table 3, in the thermoplastic resin composition of Comparative Example 4, which did not include the α-methylstyrene/acrylonitrile/methylmethacrylate copolymer, the heat deflection temperature and impact strength were significantly reduced. In addition, the thermoplastic resin composition of Comparative Example 5, which did not include the α-methylstyrene/acrylonitrile/methylmethacrylate copolymer and the styrene/acrylonitrile copolymer, significantly lowered the flow index, heat deflection temperature, and impact strength. became In addition, the colorability of the thermoplastic resin composition of Comparative Example 6 containing no styrene/acrylonitrile copolymer was remarkably deteriorated.
Claims
[Claim 1]
A first copolymer comprising an acrylic graft copolymer; a second copolymer including an alkyl-substituted styrene-based monomer unit, a vinyl cyanide-based monomer unit, and a (meth)acrylate-based monomer unit; and a third copolymer including an alkyl unsubstituted styrene-based monomer unit, a vinyl cyanide-based monomer unit, and a (meth)acrylate-based monomer unit.
[Claim 2]
The method according to claim 1, wherein the first copolymer is a first acrylic graft copolymer obtained by graft copolymerization of a vinyl monomer to an acrylic rubber polymer having an average particle diameter of 300 to 650 nm; and a second acrylic graft copolymer obtained by graft copolymerizing a vinyl monomer to an acrylic rubber polymer having an average particle diameter of 30 to 250 nm.
[Claim 3]
The thermoplastic resin composition of claim 2, wherein the first copolymer comprises the first acrylic graft copolymer and the second acrylic graft copolymer in a weight ratio of 5:95 to 25:75.
[Claim 4]
The method according to claim 1, wherein the second copolymer is a monomer mixture comprising 30 to 50% by weight of an alkyl-substituted styrenic monomer, 20 to 40% by weight of a vinyl cyanide monomer, and 20 to 40% by weight of a (meth)acrylate-based monomer. A thermoplastic resin composition that is a copolymer.
[Claim 5]
The method according to claim 1, wherein the thermoplastic resin composition is based on 100 parts by weight of the total of the first copolymer, the second copolymer, and the third copolymer, 20 to 50 parts by weight of the first copolymer; 20 to 45 parts by weight of the second copolymer; and 10 to 40 parts by weight of the third copolymer.
[Claim 6]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition further comprises a (meth)acrylate-based polymer.
[Claim 7]
The thermoplastic resin composition of claim 6, wherein the (meth)acrylate-based polymer is poly(methyl methacrylate).
[Claim 8]
The method according to claim 6, wherein the thermoplastic resin composition is based on 100 parts by weight of the total of the first copolymer, the second copolymer, the third copolymer, and the (meth) acrylate-based polymer, the (meth) acrylate-based polymer 1 to 20 parts by weight of the thermoplastic resin composition.
[Claim 9]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition further comprises an additive including a silicone compound.
[Claim 10]
The thermoplastic resin composition of claim 9, wherein the thermoplastic resin composition comprises 0.1 to 0.3 parts by weight of the additive based on 100 parts by weight of the total of the first copolymer, the second copolymer, and the third copolymer.
[Claim 11]
A thermoplastic resin molded article made of the thermoplastic resin composition according to claim 1, having a heat deflection temperature of 90 °C or higher, an L value of 25.5 or less, and a pencil hardness of F or higher.