[One][Citation with related applications]
[2]The present invention claims the benefit of priority based on Korean Patent Application No. 10-2019-0134003 filed on October 25, 2019, and includes all contents disclosed in the literature of the Korean patent application 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 capable of providing a resin having excellent fluidity and providing an injection-molded article having excellent brightness, appearance quality and chemical resistance.
background
[5]
Recently, by adding a metallic pigment to a diene-based graft copolymer, research on a metallic resin capable of giving a color similar to that of a metal has been gradually expanded.
[6]
However, when a metallic pigment is added to the diene-based graft copolymer, there is a problem in that the fluidity of the resin is significantly reduced. In addition, there is a problem in that the difference in flow rate between the metallic pigment and the polymer fluid is large, so that there is a problem in that the appearance quality is deteriorated in the section where the thickness of the molded article manufactured using the metallic resin changes or the end of the molded article.
[7]
On the other hand, existing studies to solve the above problems are not to improve the physical properties of the resin itself, but to improve the characteristics of the molded product itself by controlling the conditions when molding the resin to manufacture the molded product. there is.
[8]
Accordingly, there is a need for a thermoplastic resin composition capable of providing a molded article having excellent physical properties such as appearance quality and chemical resistance without reducing the fluidity of the resin even when a metallic pigment is added to the diene-based graft copolymer.
[9]
[10]
[Prior art literature]
[11]
[Patent Literature]
[12]
(Patent Document 1) CN109836683A
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[13]
It is an object of the present invention to provide a thermoplastic resin composition capable of providing a resin having excellent fluidity and providing an injection-molded article having excellent brightness, appearance quality and chemical resistance.
[14]
However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.
means of solving the problem
[15]
In order to solve the above problems, one embodiment of the present invention is a base resin comprising a diene-based rubber graft copolymer and vinyl cyanide-aromatic vinyl-based copolymer; an olefin-based copolymer including a crystalline unit; and a metallic pigment; provides a thermoplastic resin composition comprising.
Effects of the Invention
[16]
The thermoplastic resin composition according to an exemplary embodiment of the present invention may provide a resin having excellent fluidity, and may provide an injection-molded article having excellent brightness, appearance quality, and chemical resistance.
Modes for carrying out the invention
[17]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[18]
[19]
The terms or words used in this specification should not be construed as being limited to their ordinary or dictionary meanings, and on the principle that the inventor can appropriately define the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[20]
[21]
In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.
[22]
[23]
An exemplary embodiment of the present invention is a base resin comprising a diene-based rubber graft copolymer and a vinyl cyanide-aromatic vinyl-based copolymer; an olefin-based copolymer including a crystalline unit; and a metallic pigment; provides a thermoplastic resin composition comprising.
[24]
According to an exemplary embodiment of the present invention, the base resin may further include an acrylic rubber graft copolymer.
[25]
[26]
Hereinafter, the components of the thermoplastic resin composition according to an embodiment of the present invention will be described in detail.
[27]
[28]
1. Base resin
[29]
1) diene-based rubber graft copolymer
[30]
The diene-based rubber graft copolymer may impart excellent heat resistance, impact resistance, and processability to the thermoplastic resin composition.
[31]
[32]
The diene-based rubber graft copolymer may be a diene-based rubber polymer by graft copolymerization of a vinyl-based monomer, preferably, a diene-based rubber polymer by graft copolymerizing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. there is.
[33]
[34]
The diene-based rubber polymer may be a polymer of a diene-based monomer, and the diene-based monomer may be at least one selected from 1,3-butadiene, isoprene, chloroprene and piperylene, specifically, the diene-based monomer is 1, 3-butadiene.
[35]
The aromatic vinyl-based monomer may be at least one selected from styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, and specifically, the aromatic vinyl-based monomer may be styrene.
[36]
The vinyl cyan-based monomer may be at least one selected from acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, and specifically, the vinyl cyan-based monomer may be acrylonitrile .
[37]
[38]
According to an exemplary embodiment of the present invention, the diene-based rubber graft copolymer may have a rubber particle size of 0.05 μm or more and 0.5 μm or less. When the rubber particle size of the diene-based rubber graft copolymer is within the above range, heat resistance, impact resistance, and processability of the thermoplastic resin composition may be further improved.
[39]
According to an exemplary embodiment of the present invention, the diene-based rubber graft copolymer may be included in an amount of 10 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the base resin. Specifically, the content of the diene-based rubber graft copolymer is 10 parts by weight or more and 30 parts by weight or less, 10 parts by weight or more and 20 parts by weight or less, 10 parts by weight or more and 15 parts by weight or less, or 15 parts by weight based on 100 parts by weight of the base resin. It may be more than 20 parts by weight or less. When the content of the diene-based rubber graft copolymer is within the above range, heat resistance, impact resistance, and processability of the thermoplastic resin composition may be further improved.
[40]
[41]
2) Vinyl cyanide-aromatic vinyl-based copolymer
[42]
The vinyl cyanide-aromatic vinyl copolymer can impart excellent transparency, glossiness, impact resistance, chemical resistance, and heat resistance to the thermoplastic resin composition.
[43]
[44]
The vinyl cyanide-aromatic vinyl-based copolymer may be a copolymer of an aromatic vinyl-based compound and a vinyl cyan-based compound, and preferably may be a copolymer of an aromatic vinyl-based monomer and a vinyl cyan-based monomer. The aromatic vinyl-based monomer and the vinyl cyan-based monomer may be the same monomers as described in 1.1).
[45]
[46]
According to an exemplary embodiment of the present invention, the vinyl cyanide-aromatic vinyl-based copolymer may be included in an amount of 60 parts by weight or more and 80 parts by weight or less based on 100 parts by weight of the base resin. Specifically, the content of the vinyl cyanide-aromatic vinyl-based copolymer is 70 parts by weight or more and 80 parts by weight or less, 75 parts by weight or more and 80 parts by weight or less, 77 parts by weight or more and 80 parts by weight or less, 75 parts by weight based on 100 parts by weight of the base resin. It may be more than 77 parts by weight or not more than 70 parts by weight and not more than 77 parts by weight. When the content of the vinyl cyanide-aromatic vinyl copolymer is within the above range, transparency, glossiness, impact resistance, chemical resistance, and heat resistance of the thermoplastic resin composition may be further improved.
[47]
[48]
3) Acrylic rubber graft copolymer
[49]
The acrylic rubber graft copolymer may impart excellent weather resistance, impact resistance, elongation, colorability, chemical resistance, processability, surface gloss properties and whitening properties to the thermoplastic resin composition.
[50]
[51]
The acrylic rubber graft copolymer may be obtained by graft copolymerizing an acrylic rubber polymer with a vinyl monomer, and preferably may be obtained by graft copolymerizing an acrylic rubber polymer with an aromatic vinyl monomer and a vinyl cyanide monomer. The acrylic rubber polymer may be prepared by crosslinking a (meth)acrylate-based monomer, preferably a C4 to C10 alkyl (meth)acrylate-based monomer, more preferably butylacrylate. The aromatic vinyl-based monomer and the vinyl cyan-based monomer may be the same monomers as described in 1.1).
[52]
[53]
According to an exemplary embodiment of the present invention, the acrylic rubber graft copolymer may have a rubber particle size of 0.05 μm or more and 0.6 μm or less. When the rubber particle size of the acrylic rubber graft copolymer is within the above range, 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.
[54]
According to an exemplary embodiment of the present invention, the acrylic rubber graft copolymer may be included in an amount of 5 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the base resin. The content of the acrylic rubber graft copolymer is specifically 5 parts by weight or more and 15 parts by weight or less, 5 parts by weight or more and 10 parts by weight or less, 5 parts by weight or more and 8 parts by weight or less, or 8 parts by weight based on 100 parts by weight of the base resin. It may be more than 10 parts by weight or less. When the content of the acrylic rubber graft copolymer is within the above range, the elongation, weather resistance, chemical resistance, colorability, processability, surface gloss properties, and whitening properties of the thermoplastic resin composition can be remarkably improved.
[55]
[56]
2. Olefin-based copolymer comprising crystalline units
[57]
The olefin-based copolymer including the crystalline unit has excellent fluidity, thereby improving processability and chemical resistance of the thermoplastic resin composition. Specifically, the olefin-based copolymer including the crystalline unit may enable the thermoplastic resin composition to implement a resin having excellent fluidity, and to implement a molded article having excellent brightness, appearance quality, and chemical resistance.
[58]
In addition, the olefin-based copolymer including the crystalline unit may be included in the thermoplastic resin composition together with the metallic pigment, thereby improving the appearance characteristics of the resin and molded article prepared from the composition. Specifically, the olefin-based copolymer including a crystalline unit has excellent compatibility with a polymer carrier that may be included in a metallic pigment to be described later, so that it is possible to maximize the orientation and dispersion of the metallic pigment in the thermoplastic resin. The appearance quality of the molded article manufactured from the thermoplastic resin composition may be excellent.
[59]
[60]
According to an exemplary embodiment of the present invention, the crystalline unit may be at least one selected from an ethylene unit and a propylene unit, and preferably an ethylene unit.
[61]
[62]
According to an exemplary embodiment of the present invention, the olefin-based copolymer may include one or more functional groups selected from an acetate group and an acrylate group, and may preferably include an acetate group. In this case, the olefin-based copolymer including the crystalline unit may have excellent compatibility with the base resin, and accordingly, the thermoplastic resin composition may realize a resin having excellent fluidity.
[63]
[64]
The olefinic copolymer including a crystalline unit may be at least one selected from ethyl-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer, preferably ethyl-vinyl acetate copolymer. may be synthetic. In this case, the fluidity of the resin prepared from the thermoplastic resin composition, the brightness of the molded article prepared from the composition from the thermoplastic resin composition, appearance quality, and chemical resistance can be improved.
[65]
[66]
According to an exemplary embodiment of the present invention, the olefin-based copolymer may be included in an amount of 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the base resin. Specifically, the content of the olefin-based copolymer may be 1 part by weight or more and 5 parts by weight or less, or 5 parts by weight or more and 10 parts by weight or less, based on 100 parts by weight of the base resin. When the content of the olefin-based copolymer is within the above range, the compatibility between the base resin and the olefin-based copolymer is excellent, so that the appearance quality and chemical resistance of a molded article prepared from the thermoplastic resin composition can be improved.
[67]
[68]
3. Metallic Pigments
[69]
The metallic pigment may enable the thermoplastic resin composition to realize a molded article having excellent brightness, appearance quality, and chemical resistance.
[70]
[71]
According to an exemplary embodiment of the present invention, the metallic pigment may include metal flakes and a polymer carrier. When the metallic pigment includes the polymer carrier, the polymer carrier has excellent compatibility with the olefin-based copolymer including the crystalline unit, thereby maximizing the orientation and dispersion of the metallic pigment.
[72]
The metal flakes may be at least one selected from aluminum flakes, zinc flakes, copper flakes, nickel flakes, and stainless steel flakes. The metal flakes may preferably be aluminum flakes, and in this case, the brightness and appearance quality of a molded article prepared from the composition from the thermoplastic resin composition may be improved.
[73]
According to an exemplary embodiment of the present invention, the polymer carrier may be at least one selected from a polyethylene carrier, a polymethyl methacrylate carrier, and a styrene-acrylonitrile copolymer carrier. The polymer carrier may preferably be a polyethylene carrier, and most preferably a polyethylene wax carrier. In this case, it is possible to improve the brightness, appearance quality, and chemical resistance of a molded article prepared from the composition from the thermoplastic resin composition.
[74]
[75]
According to an exemplary embodiment of the present invention, the metallic pigment may be included in an amount of 0.05 parts by weight or more to 12 parts by weight or less based on 100 parts by weight of the base resin. Specifically, the content of the metallic pigment is 0.1 parts by weight or more to 10 parts by weight or less, 1 part by weight or more to 10 parts by weight or less, 1 part by weight or more to 5 parts by weight or more, or 5 parts by weight or more based on 100 parts by weight of the base resin. to 10 parts by weight or less. When the content of the metallic pigment is within the above range, the fluidity of the resin prepared from the thermoplastic resin composition may be improved, and the appearance quality of the molded article prepared from the composition from the thermoplastic resin composition may be improved. For example, it is possible to prevent flow marks or weld lines from occurring in the molded product, and it is possible to implement the same exterior color as a desired metal.
[76]
[77]
Hereinafter, examples will be given to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present invention to those of ordinary skill in the art.
[78]
[79]
Examples and Comparative Examples
[80]
The specifications of the components used in the following Examples and Comparative Examples are as follows.
[81]
[82]
(A) diene-based rubber graft copolymer: An acrylonitrile-butadiene-styrene graft copolymer (DP270E, LG Chem) having a rubber particle size of 0.05 μm or more and 0.5 μm or less was used.
[83]
[84]
(B) Vinyl cyanide-aromatic vinyl-based copolymer: A styrene-acrylonitrile copolymer having an acrylonitrile content of 24 wt% (80HF, LG Chem) was used.
[85]
[86]
(C) Acrylic rubber graft copolymer: An acrylonitrile-styrene-acrylate graft copolymer (SA927, LG Chem) having a rubber particle size of 0.05 μm or more and 0.6 μm or less was used.
[87]
[88]
(D) Olefin-based copolymer including crystalline units: An ethyl-vinyl acetate copolymer (EEA-28025, LG Chem) was used.
[89]
[90]
(E) metallic pigments:
[91]
(E-1) A metallic pigment (220-20-E, Silverline) containing a polyethylene wax carrier was used.
[92]
(E-2) A metallic pigment (838-20-P, Silverline) containing a polymethyl methacrylate carrier was used.
[93]
[94]
A thermoplastic resin composition was prepared by mixing the above-described components in the amounts shown in Tables 1 to 3 below.
[95]
[96]
Experimental Example 1
[97]
After putting the thermoplastic resin compositions of Examples and Comparative Examples into an extruder (cylinder temperature: 230 ° C.), melt and mix and extrude to prepare pellets, and evaluate the physical properties by the method described below, and the results are shown in Tables 1 to 3 described in.
[98]
[99]
1) Melt Index (MI) measurement
[100]
According to ASTM D1238, using GOTTFERT's MI-4, the weight of the resin melted for 10 minutes under conditions of a temperature of 220 °C and a load of 10 kg was measured.
[101]
[102]
Experimental Example 2
[103]
The pellets prepared in Experimental Example 1 were injection molded to prepare a specimen, and the physical properties were evaluated by the method described below, and the results are shown in Tables 1 to 3 below.
[104]
[105]
1) Color L value measurement
[106]
The Color L value of the specimen was measured using a color meter (Ci7860, x-rite).
[107]
[108]
2) Appearance quality evaluation
[109]
During injection molding, flow marks may occur because injection is performed using a mold having two gates. The appearance of the specimen was visually observed to evaluate the appearance quality according to the following evaluation criteria.
[110]
○: No or almost no flow mark
[111]
△: state in which the flow mark traces are faintly visible
[112]
X: A condition in which the flow mark is clearly visible and dark
[113]
[114]
3) Chemical resistance evaluation
[115]
In accordance with ASTM D1693, after fixing the specimen to a strain jig of 1.5% at room temperature, an isopropyl alcohol solution (concentration: 70%) is applied on the specimen, and the change of the specimen is visually observed after 10 minutes according to the following evaluation criteria Chemical resistance was evaluated.
[116]
○: No change in the specimen
[117]
X: Cracks are observed or the specimen is completely broken
[118]
[119]
[Table 1]
division Example
One 2 3 4 5 6 7
(A) diene-based rubber graft copolymer (parts by weight) 15 15 15 15 15 15 15
(B) Vinyl cyanide-aromatic vinyl-based copolymer (parts by weight) 77 77 77 77 77 77 77
(C) acrylic rubber graft copolymer (parts by weight) 8 8 8 8 8 8 8
(D) Olefin-based copolymer including crystalline units (parts by weight) One One One 10 10 10 One
(E) metallic pigment (parts by weight) (E-1) One 10 - One 10 - 12
(E-2) - - 10 - - 10 -
Melt index (g/10 min) 40 40 40 49 49 49 41
Color L 70 73 79 74 81 78 74
appearance quality ○ ○ △ ○ ○ △ △
chemical resistance ○ ○ ○ ○ ○ ○ ○
[120]
[121]
[Table 2]
division Example
8 9 10 11 12 13 14 15
(A) diene-based rubber graft copolymer (parts by weight) 15 15 15 15 15 15 15 15
(B) Vinyl cyanide-aromatic vinyl-based copolymer (parts by weight) 77 77 77 77 77 77 77 77
(C) acrylic rubber graft copolymer (parts by weight) 8 8 8 8 8 8 8 8
(D) Olefin-based copolymer including crystalline units (parts by weight) One One One One 10 10 10 10
(E) metallic pigment (parts by weight) (E-1) 0.05 5 - - 0.05 5 - -
(E-2) - - 0.05 5 - - 0.05 5
Melt index (g/10 min) 40 40 40 40 49 49 49 49
Color L 69 72 69 73 73 76 73 77
appearance quality ○ ○ ○ ○ ○ ○ ○ ○
chemical resistance ○ ○ ○ ○ ○ ○ ○ ○
[122]
[123]
[Table 3]
division comparative example
One 2 3 4
(A) diene-based rubber graft copolymer (parts by weight) 15 15 15 15
(B) Vinyl cyanide-aromatic vinyl-based copolymer (parts by weight) 77 77 77 77
(C) acrylic rubber graft copolymer (parts by weight) 8 8 8 8
(D) Olefin-based copolymer including crystalline units (parts by weight) - - - -
(E) metallic pigment (parts by weight) (E-1) 10 12 - -
(E-2) - - 10 12
Melt index (g/10 min) 39 39 39 39
Color L 71 72 78 79
appearance quality X X X X
chemical resistance X X X X
[124]
[125]
Referring to Tables 1 to 3, from the melt index and the Clolor L value, the thermoplastic resin compositions of Examples 1 to 15 contained the olefinic copolymer including crystalline units and the metallic pigment at the same time, and the thermoplastic resin compositions of Comparative Examples 1 to 4 were included. It could be confirmed that a resin having an equivalent or superior level of fluidity compared to the resin composition could be provided, and it could be confirmed that an injection-molded article having an equivalent or superior level of brightness could be provided. Specifically, it was confirmed that Example 2 had better fluidity and brightness compared to Comparative Example 1, Example 3 compared to Comparative Example 3, and Example 7 compared to Comparative Example 2.
[126]
In addition, the thermoplastic resin compositions of Examples 1 to 15 provide injection-molded articles having superior appearance quality and chemical resistance compared to the thermoplastic resin compositions of Comparative Examples 1 to 4 that do not include the olefin-based copolymer including the crystalline unit. I could confirm that I could.
[127]
In addition, from Examples 1 to 15, it was confirmed that when the metallic pigment was included in an appropriate range, the Color L value and the appearance quality could be improved at the same time.
[128]
Therefore, it can be seen that the thermoplastic resin composition according to an exemplary embodiment of the present invention can provide a resin having excellent fluidity, and can provide a molded article having excellent brightness, appearance quality and chemical resistance.

WE CLAIMS

a base resin comprising a diene-based rubber graft copolymer and a vinyl cyanide-aromatic vinyl-based copolymer; an olefin-based copolymer including a crystalline unit; And a metallic pigment; Thermoplastic resin composition comprising a.
[Claim 2]
The thermoplastic resin composition of claim 1, wherein the base resin further comprises an acrylic rubber graft copolymer.
[Claim 3]
The thermoplastic resin composition of claim 1, wherein the diene-based rubber graft copolymer has a rubber particle size of 0.05 μm or more and 0.5 μm or less.
[Claim 4]
The thermoplastic resin composition of claim 1, wherein the diene-based rubber graft copolymer is included in an amount of 10 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the base resin.
[Claim 5]
The thermoplastic resin composition of claim 1, wherein the vinyl cyanide-aromatic vinyl-based copolymer is included in an amount of 60 parts by weight or more and 80 parts by weight or less based on 100 parts by weight of the base resin.
[Claim 6]
The thermoplastic resin composition of claim 2, wherein the acrylic rubber graft copolymer has a rubber particle size of 0.05 μm or more and 0.6 μm or less.
[Claim 7]
The thermoplastic resin composition of claim 2, wherein the acrylic rubber graft copolymer is included in an amount of 5 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the base resin.
[Claim 8]
The thermoplastic resin composition of claim 1, wherein the crystalline unit is at least one selected from an ethylene unit and a propylene unit.
[Claim 9]
The thermoplastic resin composition of claim 1, wherein the olefin-based copolymer includes at least one functional group selected from an acetate group and an acrylate group.
[Claim 10]
The thermoplastic resin composition of claim 1, wherein the olefin-based copolymer is included in an amount of 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the base resin.
[Claim 11]
The thermoplastic resin composition of claim 1, wherein the metallic pigment comprises metal flakes and a polymer carrier.
[Claim 12]
The thermoplastic resin composition of claim 11, wherein the polymer carrier is at least one selected from a polyethylene carrier, a polymethyl methacrylate carrier, and a styrene-acrylonitrile copolymer carrier.
[Claim 13]
The thermoplastic resin composition of claim 1, wherein the metallic pigment is included in an amount of 0.1 parts by weight or more to 12 parts by weight or less based on 100 parts by weight of the base resin.