Title of Invention: Thermoplastic resin composition, manufacturing method thereof, and molded article manufactured therefrom
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0118528 dated September 15, 2020 and Korean Patent Application No. 10-2021-0093004, which was re-applied on July 15, 2021 based thereon, and the corresponding Korean patent application All content disclosed in the literature is incorporated as a part of this specification.
[3]
The present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article manufactured therefrom, and more particularly, it has excellent impact resistance, heat resistance and fluidity, and, in particular, has high multi-axial impact strength and its standard Thermoplastic resin composition that satisfies injection molding exterior quality and vehicle reliability evaluation by suppressing the occurrence of goniochromism while allowing for injection molding of large-sized products with low deviation and realization of deep black color, and manufacturing thereof It relates to a method and a molded article made therefrom.
background
[4]
In order to use an automobile exterior material without painting, physical properties that can satisfy automobile reliability evaluation as well as excellent quality of the appearance of injection are required. In particular, in order to be applied to a radiator grill, resin flowability and high level of heat resistance and impact strength are required to enable molding of large-sized injection products, and surface impact strength characteristics related to major reliability evaluation are required. To this end, it is necessary to mix an MMA-based resin for realizing a deep black color and a heat-resistant resin for realizing heat resistance, but the compatibility of the two resins is not good, so it is difficult to achieve the desired level of quality of the exterior appearance and uniform physical properties. When two resins with poor compatibility are mixed, a goniochromism phenomenon occurs and the deviation of physical properties increases. In particular, there is a problem in that the standard deviation value of surface impact strength, which is a major reliability evaluation item for automobiles, increases.
[5]
Accordingly, there is a demand for the development of a thermoplastic resin composition capable of achieving high black color and molding large-size injection products while having heat resistance and impact resistance, and improving the appearance quality of injection.
[6]
[7]
[Prior art literature]
[8]
[Patent Literature]
[9]
Korean Registered Patent No. 10-0417066
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[10]
In order to solve the problems of the prior art as described above, the present invention has excellent impact resistance, heat resistance and fluidity, and in particular, has a high average surface impact strength and a low standard deviation thereof, so that large products can be injection molded and a deep black color can be realized. An object of the present invention is to provide a thermoplastic resin composition that satisfies the injection appearance quality and vehicle reliability evaluation by suppressing the occurrence of goniochromism, a manufacturing method thereof, and a molded article manufactured therefrom.
[11]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[12]
In order to achieve the above object, the present invention provides A-1) 3 to 22 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 200 to 400 nm, an aromatic vinyl compound and a vinyl cyan compound; A-2) 17 to 40 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 199 nm, an aromatic vinyl compound, and a vinyl cyan compound; B) 30 to 57% by weight of a copolymer comprising a (meth)acrylic acid alkyl ester compound, an α-methyl styrene compound, and a vinyl cyan compound; and C) 6 to 30 wt% of polymethacrylate resin (except α-methyl styrene); and, according to ISO 6603-2, the maximum load energy is 10 with a specimen thickness of 2.0 mm under a speed of 4.4 m/s. It provides a thermoplastic resin composition, characterized in that the average surface impact strength measured twice is 22 J or more and the standard deviation is 6.5 or less.
[13]
[14]
In addition, the present invention is A-1) 3 to 22 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 200 to 400 nm, an aromatic vinyl compound, and a vinyl cyan compound; A-2) 17 to 40 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 199 nm, an aromatic vinyl compound, and a vinyl cyan compound; B) 30 to 57% by weight of a copolymer comprising a (meth)acrylic acid alkyl ester compound, an α-methyl styrene compound, and a vinyl cyan compound; and C) 6 to 30 wt% of polymethacrylate resin (except α-methyl styrene); and, according to ISO 6603-2, the maximum load energy is 10 with a specimen thickness of 2.0 mm under a speed of 4.4 m/s. The average surface impact strength measured twice is 22 J or more and the standard deviation is 6.5 or less, and the B) copolymer is 30 to 55% by weight of a (meth)acrylic acid alkyl ester compound, 25 to 50% by weight of an α-methylstyrene compound, and It is possible to provide a thermoplastic resin composition comprising 10 to 30% by weight of the vinyl cyanide compound.
[15]
[16]
In addition, the present invention is A-1) 3 to 22 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 200 to 400 nm, an aromatic vinyl compound, and a vinyl cyan compound; A-2) 17 to 40 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 199 nm, an aromatic vinyl compound, and a vinyl cyan compound; B) 30 to 57% by weight of a copolymer comprising a (meth)acrylic acid alkyl ester compound, an α-methyl styrene compound, and a vinyl cyan compound; and C) 6 to 30 wt% of polymethacrylate resin (except α-methyl styrene); and, according to ISO 6603-2, the maximum load energy is 10 with a specimen thickness of 2.0 mm under a speed of 4.4 m/s. The average surface impact strength measured twice is 22 J or more and the standard deviation is 6.5 or less, and the above C) polymethacrylate resin (except α-methyl styrene) contains 55 wt% or more of a methacrylate monomer. It is possible to provide a thermoplastic resin composition characterized in that.
[17]
[18]
In addition, the present invention relates to A-1) 3 to 22 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 200 to 400 nm, an aromatic vinyl compound, and a vinyl cyan compound, A-2) An average particle diameter of 50 to 199 17 to 40 wt% of a graft copolymer comprising an acrylate-based rubber of nm, an aromatic vinyl compound and a vinyl cyan compound, B) (meth) acrylic acid alkyl ester compound, α-methyl styrene compound and vinyl cyan compound 30 to 57% by weight of the copolymer and C) 6 to 30% by weight of the polymethacrylate resin (except for α-methyl styrene), and then using an extrusion kneader at 200 to 300°C in 10 to 100 pie specifications to prepare a thermoplastic resin composition, and the prepared thermoplastic resin composition has an average surface impact strength measured 10 times with a specimen thickness of 2.0 mm at a speed of 4.4 m/s according to ISO 6603-2. It provides a method for producing a thermoplastic resin composition, characterized in that J or more and the standard deviation is 6.5 or less.
[19]
[20]
In addition, the present invention provides A-1) 3 to 22 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 200 to 400 nm, an aromatic vinyl compound, and a vinyl cyan compound, A-2) An average particle diameter of 50 to 199 17 to 40 wt% of a graft copolymer comprising an acrylate-based rubber of nm, an aromatic vinyl compound and a vinyl cyan compound, B) (meth) acrylic acid alkyl ester compound, α-methyl styrene compound and vinyl cyan compound 30 to 57% by weight of the copolymer and C) 6 to 30% by weight of the polymethacrylate resin (except for α-methyl styrene), and then using an extrusion kneader at 200 to 300° C. in a standard of 10 to 100 pie to prepare a thermoplastic resin composition, and the prepared thermoplastic resin composition has an average surface impact strength measured 10 times with a specimen thickness of 2.0 mm at a speed of 4.4 m/s in accordance with ISO 6603-2. J or more and the standard deviation is 6.5 or less, and B) the copolymer contains 30 to 55% by weight of a (meth)acrylic acid alkyl ester compound, 25 to 50% by weight of an α-methylstyrene compound, and 10 to 30% by weight of a vinyl cyanide compound. It is possible to provide a method for producing a thermoplastic resin composition comprising the.
[21]
[22]
In addition, the present invention relates to A-1) 3 to 22 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 200 to 400 nm, an aromatic vinyl compound, and a vinyl cyan compound, A-2) An average particle diameter of 50 to 199 17 to 40 wt% of a graft copolymer comprising an acrylate-based rubber of nm, an aromatic vinyl compound and a vinyl cyan compound, B) (meth) acrylic acid alkyl ester compound, α-methyl styrene compound and vinyl cyan compound 30 to 57% by weight of the copolymer and C) 6 to 30% by weight of the polymethacrylate resin (except for α-methyl styrene), and then using an extrusion kneader at 200 to 300°C in 10 to 100 pie specifications to prepare a thermoplastic resin composition, and the prepared thermoplastic resin composition has an average surface impact strength measured 10 times with a specimen thickness of 2.0 mm at a speed of 4.4 m/s according to ISO 6603-2. J or more and the standard deviation is 6.5 or less, and C) the polymethacrylate resin (except α-methyl styrene) comprises 55 wt% or more of a methacrylate monomer. Method for producing a thermoplastic resin composition can provide
[23]
[24]
In addition, the present invention provides a molded article comprising the thermoplastic resin composition.
Effects of the Invention
[25]
According to the present invention, the impact resistance, heat resistance and fluidity are excellent, and the average surface impact strength is high and the standard deviation thereof is low, so that large products can be injection molded, and deep black color can be realized while goniochromism phenomenon occurs There is an effect of providing a thermoplastic resin composition, a method for manufacturing the same, and a molded article manufactured therefrom that satisfy the evaluation of injection appearance quality and vehicle reliability by suppressing the
Modes for carrying out the invention
[26]
Hereinafter, the thermoplastic resin composition of the present disclosure, a method for producing the same, and a molded article prepared therefrom will be described in detail.
[27]
The present inventors adjusted two kinds of ASA resins having different average particle diameters to a predetermined content in order to improve the compatibility between the heat-resistant resin and the MMA-based resin, and a (meth)acrylic acid alkyl ester compound, α-methyl styrene-based compound and vinyl cyanide compound When the copolymer and polymethacrylate resin (except α-methyl styrene) comprising The effect of improving and reducing its standard deviation was confirmed, and based on this, further research was devoted to complete the present invention.
[28]
[29]
The thermoplastic resin composition of the present invention comprises: A-1) 3 to 22 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 200 to 400 nm, an aromatic vinyl compound, and a vinyl cyan compound; A-2) 17 to 40 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 199 nm, an aromatic vinyl compound, and a vinyl cyan compound; B) 30 to 57% by weight of a copolymer comprising a (meth)acrylic acid alkyl ester compound, an α-methyl styrene compound, and a vinyl cyan compound; and C) 6 to 30 wt% of polymethacrylate resin (except α-methyl styrene); and, according to ISO 6603-2, the maximum load energy is 10 with a specimen thickness of 2.0 mm under a speed of 4.4 m/s. It is characterized in that the average surface impact strength measured twice is 22 J/mm or more and the standard deviation is 6.5 or less. In this case, it has excellent impact resistance, heat resistance and fluidity, so large products can be injection molded, and deep black color can be realized, and the occurrence of goniochromism is suppressed to satisfy the evaluation of injection appearance quality and vehicle reliability. has the effect of
[30]
[31]
Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each configuration.
[32]
[33]
A-1) A graft copolymer comprising an acrylate-based rubber having an average particle diameter of 200 to 400 nm, an aromatic vinyl compound, and a vinyl cyan compound
[34]
The acrylate rubber of the graft copolymer has, for example, an average particle diameter of 200 to 400 nm, preferably 220 to 350 nm, more preferably 250 to 330 nm. It can impart gloss, impact strength and surface properties.
[35]
In the present description, the average particle diameter can be measured using a dynamic light scattering method, and in detail, the intensity (intensity) in Gaussian mode using a particle measuring instrument (product name: Nicomp 380, manufacturer: PSS) ) as a value. At this time, as a specific example of measurement, the sample is prepared by diluting 0.1 g of Latex (TSC 35-50wt%) 1,000-5,000 times with deionized or distilled water, that is, diluting it appropriately so as not to greatly deviate from the Intensity Setpoint 300kHz, and putting it in a glass tube, and prepare and measure The method is auto-dilution and measured with a flow cell, the measurement mode is dynamic light scattering method/Intensity 300KHz/Intensity-weight Gaussian Analysis, and the setting value is temperature 23℃, measuring wavelength 632.8nm, channel width It can measure as 10 microseconds.
[36]
[37]
The A-1) graft copolymer is, for example, 3 to 22% by weight, preferably 5 to 20% by weight, more preferably 7 to 15% by weight, within this range, it has excellent impact resistance, heat resistance and fluidity, and particularly As the average surface impact strength is high and its standard deviation is reduced, large-sized products can be injection molded, and a deep black color can be realized, and the occurrence of goniochromism is suppressed to improve the quality of injection molding and the reliability of automobiles. has a satisfactory effect.
[38]
[39]
In the present description, the phenomenon of goniochromism refers to a phenomenon in which a rainbow or pearlescent color appears in pellets or injection specimens due to poor compatibility between resins. When the above phenomenon is expressed, there is a problem in that the colorability of the dye or pigment is lowered, so that the color of the exterior of the injection product is non-uniform, and the blackness (L) value is increased compared to the coloring of the pigment or dye, so that it is difficult to express high blackness.
[40]
[41]
The A-1) graft copolymer is, for example, 30 to 60% by weight of an acrylate-based rubber, 20 to 60% by weight of an aromatic vinyl compound, and 5 to 20% by weight of a vinyl cyanide compound. The impact property and surface impact strength and standard deviation thereof are improved, and the quality of the appearance of injection is excellent.
[42]
As a preferred example, the A-1) graft copolymer may include 35 to 55% by weight of an acrylate-based rubber, 35 to 55% by weight of an aromatic vinyl compound, and 7 to 17% by weight of a vinyl cyanide compound, within this range In this case, the impact strength and standard deviation thereof are improved, and the quality of the appearance of the injection is excellent.
[43]
In the present description, a polymer including a certain compound means a polymer polymerized including the compound, and a unit in the polymerized polymer is derived from the compound.
[44]
[45]
The A-1) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, it has excellent impact resistance, chemical resistance, weather resistance and colorability.
[46]
The emulsion polymerization is not particularly limited if the emulsion graft polymerization method is commonly carried out in the art to which the present invention belongs.
[47]
[48]
The acrylate of the present invention may be, for example, at least one selected from the group consisting of alkyl acrylates having 2 to 8 carbon atoms in the alkyl group, preferably an alkyl acrylate having 4 to 8 carbon atoms in the alkyl group, more preferably butyl acrylate or ethylhexyl acrylate.
[49]
The aromatic vinyl compound of the present invention is, for example, styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brobo styrene, ρ -bromostyrene, m-bromostyrene, ο-chlorostyrene, ρ-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene and vinylnaphthalene may be at least one selected from the group consisting of, Preferably, it may be styrene.
[50]
The vinyl cyan compound of the present invention may be, for example, at least one selected from the group consisting of acrylonitrile, methnitrolonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, and is preferably acrylonitrile.
[51]
[52]
A-2) A graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 199 nm, an aromatic vinyl compound, and a vinyl cyan compound
[53]
The acrylate rubber of the graft copolymer has, for example, an average particle diameter of 50 to 199 nm, preferably 70 to 180 nm, and more preferably 90 to 150 nm. It can impart gloss, impact strength and surface properties.
[54]
[55]
The A-2) graft copolymer is, for example, 17 to 40% by weight, preferably 20 to 35% by weight, more preferably 25 to 30% by weight, and has excellent impact resistance, heat resistance and fluidity within this range, and particularly It has high average surface impact strength and its standard deviation is reduced so that large-sized products can be injection molded, and deep black color can be realized while suppressing the occurrence of goniochromism, which satisfies the evaluation of injection appearance quality and vehicle reliability. It works.
[56]
[57]
The A-2) graft copolymer is, for example, comprising 30 to 60% by weight of an acrylate-based rubber, 20 to 60% by weight of an aromatic vinyl compound, and 5 to 20% by weight of a vinyl cyanide compound, and within this range, high It has excellent black expression and has the effect of stabilizing the physical properties by reducing the standard deviation of impact strength.
[58]
As a preferred example, the (A-2) graft copolymer may include 35 to 55 wt% of an acrylate-based rubber, 35 to 55 wt% of an aromatic vinyl compound, and 7 to 17 wt% of a vinyl cyanide compound, within this range It has the effect of stabilizing the physical properties as the standard deviation of the surface impact strength is reduced and the high black expression is excellent in the interior.
[59]
[60]
The A-2) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, it has excellent impact resistance, chemical resistance, weather resistance and colorability.
[61]
The emulsion polymerization is not particularly limited if the emulsion graft polymerization method is commonly carried out in the art to which the present invention belongs.
[62]
[63]
The A-1) graft copolymer may be included in an amount equal to or less than that of the A-2) graft copolymer, for example, and preferably, the A-1) graft copolymer and A-2) graft The copolymer may have a weight ratio of 1:1 to 1:7.5, more preferably 1:1 to 1:7, still more preferably 1:2 to 1:4, even more preferably 1:2 to 1:3. And within this range, the surface impact strength and its standard deviation are improved, so it can be applied to large injection molded products and has the advantage of high black expression.
[64]
In the present description, the weight ratio of A and B means the weight ratio of A:B.
[65]
[66]
B) a copolymer comprising an (meth)acrylic acid alkyl ester compound, an α-methyl styrene compound, and a vinyl cyan compound
[67]
The B) copolymer is, for example, 30 to 60% by weight, preferably 35 to 55% by weight, more preferably 42 to 54% by weight, even more preferably 45 to 50% by weight, within this range impact resistance, Excellent heat resistance and fluidity, and particularly high average surface impact strength, while reducing its standard deviation, enables injection molding of large-sized products, and enables deep black color realization and suppresses the occurrence of goniochromism, resulting in injection appearance quality and vehicle reliability evaluation.
[68]
[69]
The B) copolymer is, for example, comprising 30 to 55% by weight of a (meth)acrylic acid alkyl ester compound, 25 to 50% by weight of an α-methyl styrenic compound, and 10 to 30% by weight of a vinyl cyanide compound, and within this range In C), which will be described later, compatibility with polymethacrylate resins (except for α-methyl styrene) is improved, so that goniochromism does not occur, resulting in excellent injection appearance quality.
[70]
The B) copolymer may preferably include 35 to 50% by weight of a (meth)acrylic acid alkyl ester compound, 30 to 45% by weight of an α-methyl styrene compound, and 12 to 27% by weight of a vinyl cyanide compound, C), which will be described later, has improved compatibility with polymethacrylate resins (except α-methyl styrene) to prevent goniochromism from occurring, and thus has an excellent injection appearance.
[71]
The copolymer B) more preferably comprises 40 to 45 wt% of (meth)acrylic acid alkyl ester compound, 35 to 40 wt% of α-methyl styrene-based compound, and 17 to 22 wt% of vinyl cyanide compound. , C) to be described later, compatibility with polymethacrylate resins (except α-methyl styrene) is improved to prevent goniochromism from occurring, so that the appearance of injection is excellent.
[72]
[73]
The B) copolymer may have, for example, a weight average molecular weight of 50,000 to 200,000 g/mol, preferably 70,000 to 150,000 g/mol, more preferably 80,000 to 120,000 g/mol, and surface impact strength within this range It is excellent and has the effect of securing injection moldability.
[74]
In the present description, unless otherwise defined, the weight average molecular weight may be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as the eluent. ) can be measured as a relative value for a standard PS (standard polystyrene) sample. At this time, as a specific example of measurement, solvent: THF, column temperature: 40°C, flow rate: 0.3ml/min, sample concentration: 20mg/ml, injection amount: 5μl, column model: 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing: Agilent ChemStation S/W, test method (Mn, Mw and PDI): It can be measured under OECD TG 118 conditions.
[75]
[76]
The B) (meth)acrylic acid alkyl ester polymer is, for example, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid decyl ester And (meth) may be at least one selected from the group consisting of acrylic acid lauryl ester, preferably methyl methacrylate (meth) acrylic acid methyl ester.
[77]
The α-methyl styrene-based compound may be, for example, at least one selected from the group consisting of α-methyl styrene and derivatives thereof, and in this case, excellent heat resistance is obtained.
[78]
Preferably, the derivative of α-methyl styrene may be a compound in which one or two or more of its hydrogens are substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms or a halogen group, and more preferably an aromatic ring thereof It may be a compound in which one or two or more of the hydrogens are substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogen group, or the like.
[79]
The type of the vinyl cyan compound included in the copolymer B) may be within the same scope as the types of the aromatic vinyl compound and the vinyl cyan compound included in the A-1) graft copolymer of the present disclosure.
[80]
[81]
The B) copolymer may be prepared by, for example, solution polymerization, block polymerization, emulsion polymerization or suspension polymerization, preferably block polymerization, and the solution polymerization, block polymerization, emulsion polymerization and suspension polymerization are each of the present invention In the case of emulsion polymerization and suspension polymerization methods commonly carried out in the art, it is not particularly limited.
[82]
[83]
C) Polymethacrylate resin (except α-methyl styrene)
[84]
C) the polymethacrylate resin (except for α-methyl styrene) is, for example, 6 to 30% by weight, preferably 8 to 25% by weight, more preferably 9 to 22% by weight, even more preferably It may be 10 to 16% by weight, and within this range, the high blackness is excellent and the melt flow index is excellent, so that the injection of a large product is easy.
[85]
C) the polymethacrylate resin (with the exception of α-methyl styrene) preferably contains at least 55% by weight of methacrylate monomer, preferably at least 60% by weight, and most preferably at least 65% by weight, Within this range, the high blackness is excellent and the melt flow index is excellent, so the injection of large products is easy.
[86]
[87]
The methacrylate monomer may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2 -It may be at least one selected from the group consisting of ethylhexyl methacrylate and lauryl methacrylate, preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, more preferably methyl methacrylate. It may be a acrylate.
[88]
[89]
C) the polymethacrylate resin (except for α-methyl styrene) is preferably a methylmethacrylate-styrene-acrylonitrile copolymer, or a polymethylmethacrylate resin and methylmethacrylate-styrene-acryl It may be mixed with a ronitrile copolymer, and within this range, high blackness is excellent and the melt flow index is excellent, so that injection of large products is easy.
[90]
[91]
For example, in the case of using a mixture of methyl methacrylate-styrene-acrylonitrile copolymer and polymethyl methacrylate as the C) polymethacrylate resin (except for α-methyl styrene), methyl methacrylate -Styrene-acrylonitrile copolymer may be included in an amount equal to or greater than that of polymethyl methacrylate resin, and preferably, the methyl methacrylate-styrene-acrylonitrile copolymer is contained in an amount greater than polymethyl methacrylate. In this case, there is an excellent effect of fluidity, surface impact strength, and standard deviation thereof.
[92]
[93]
As a specific example, 3 to 15 wt% of methyl methacrylate-styrene-acrylonitrile copolymer and 3 to 15 wt% of polymethyl methacrylate in 100 wt% of the thermoplastic resin composition, preferably methyl methacrylate -Styrene-acrylonitrile copolymer 5 to 12% by weight and polymethyl methacrylate 4 to 11% by weight can be used, and in this case, heat resistance, blackness and surface impact strength and standard deviation thereof are excellent, and the melt flow index is It is excellent and has the effect of easy injection of large products.
[94]
[95]
The methyl methacrylate-styrene-acrylonitrile copolymer comprises, for example, 55 to 82% by weight of methyl methacrylate, 10 to 35% by weight of styrene, and 1 to 20% by weight of acrylonitrile, preferably 60 to 77% by weight of methyl methacrylate, 15 to 30% by weight of styrene and 1 to 15% by weight of acrylonitrile, more preferably 67 to 72% by weight of methylmethacrylate, 20 to 25% by weight of styrene and acrylonitrile It is made by including 5 to 10% by weight, and the melt flow index is improved within this range, so that large products can be easily injection molded and the physical properties are stabilized.
[96]
[97]
The methyl methacrylate-styrene-acrylonitrile copolymer has, for example, a weight average molecular weight of 100,000 to 180,000 g/mol, preferably 110,000 to 160,000 g/mol, more preferably 120,000 g/mol to 140,000 g/mol , and within this range, the surface impact strength is excellent and the injection moldability is secured.
[98]
[99]
The polymethyl methacrylate resin may have, for example, a weight average molecular weight of 35,000 to 200,000 g/mol, preferably 50,000 to 200,000 g/mol, and more preferably 80,000 to 150,000 g/mol, within this range. It has excellent surface impact strength and has the effect of securing injection moldability.
[100]
[101]
The polymethyl methacrylate resin is made of, for example, methyl methacrylate and methyl acrylate, preferably 1 to 15% by weight of methyl acrylate, preferably 2 to 7% by weight. and excellent compatibility with the methyl methacrylate-styrene-acrylonitrile copolymer within this range, there is an advantage in that colorability, melt flow index and mechanical properties are improved.
[102]
[103]
The C) polymethacrylate resin may be prepared by, for example, solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and the solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization are each conventional in the art to which the present invention belongs. It is not particularly limited in the case of emulsion polymerization and suspension polymerization method carried out as
[104]
[105]
The present invention preferably relates to a combination of said B) copolymer and said C) polymethacrylate resin, more preferably said B) copolymer and said methylmethacrylate-styrene-acrylonitrile copolymer in combination. As a result, mechanical properties such as heat resistance, blackness, and impact strength are excellent, and a synergistic effect of excellent surface impact strength and standard deviation thereof is expressed.
[106]
[107]
additive
[108]
The thermoplastic resin composition may include, for example, at least one selected from the group consisting of a lubricant, a heat stabilizer, a UV stabilizer, and a slip agent, and within this range, necessary physical properties without reducing the original properties of the thermoplastic resin composition of the present invention This has a well-implemented effect.
[109]
[110]
The lubricant may include, for example, 0.1 to 3 parts by weight, preferably 0.5 to 2 parts by weight, more preferably 0.5 to 1.5 parts by weight, of the lubricant based on 100 parts by weight of the total thermoplastic resin composition, in which case the impact strength and melt flow index both have an excellent effect.
[111]
[112]
The lubricant may be, for example, at least one selected from the group consisting of ester lubricants, metal salt lubricants, carboxylic acid lubricants, hydrocarbon lubricants and amide lubricants, preferably amide lubricants, and more preferably stera lubricants. It is a mid-type lubricant, and more preferably an alkylene bis (steramide) having 1 to 10 carbon atoms of alkylene, in which case the original effect of the lubricant is well expressed without degrading the mechanical properties and thermal stability of the resin. There is an advantage.
[113]
In the present description, the steramide-based lubricant may include steramide and a steramide substituent in which at least one of hydrogen is substituted with another substituent.
[114]
The ester-based lubricant, metal salt-based lubricant, carboxylic acid-based lubricant, hydrocarbon-based lubricant, and amide-based lubricant are not particularly limited if they are materials commonly used as a corresponding type of lubricant in the technical field to which the present invention belongs.
[115]
[116]
The heat stabilizer may be, for example, 0.1 to 2 parts by weight, preferably 0.2 to 1.5 parts by weight, based on 100 parts by weight of the total thermoplastic resin composition, and the heat resistance is improved within this range.
[117]
The thermal stabilizer may be, for example, at least one selected from the group consisting of a phenol-based thermal stabilizer, a phosphite-based thermal stabilizer, and a thioether-based thermal stabilizer, and preferably a phenol-based thermal stabilizer and a phosphite-based thermal stabilizer.
[118]
The phenolic heat stabilizer is, for example, tetrakis methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate methane, 1,3,5-tris-(4-t-butyl- 3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and 1,3,5-tris-(3, It may be at least one selected from the group consisting of 5-di-t-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)-trione.
[119]
The phosphite-based heat stabilizer is, for example, trisnonylphenylphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol depot Spite, or a mixture thereof.
[120]
The thioether-based heat stabilizer is, for example, dilauryl thiodipropionate, dimyristyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodipropionate, dimethyl thiodipropionate It may be at least one selected from the group consisting of nate, 2-mercaptobenzimidazole, phenothiazine, octadecyl thioglycolate, butyl thioglycolate, octyl thioglycolate, and thiocresol.
[121]
The UV stabilizer may be, for example, 0.1 to 3 parts by weight, preferably 0.5 to 1.5 parts by weight, based on 100 parts by weight of the total thermoplastic resin composition, in which case weather resistance is improved.
[122]
The UV stabilizer may be, for example, a hindered amine light stabilizer (HALS), preferably 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinic nate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis( 1-Octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-N-butyl -3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid Condensation product, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine with 4-tert-octylamino-2,6-di-chloro-1,3, Linear or cyclic condensation product of 5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4 -piperidyl)-1,2,3,4-butane tetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N,N'-bis(2,2,6 ,6-tetramethyl-4-piperidyl) hexamethylene diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine linear or cyclic condensation product, 7,7,9, 9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, and poly[[6-(1) ,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,One selected from the group consisting of 6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino] may be more than
[123]
The UV stabilizer is more preferably bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate), 2 -(2H-benzotriazol-2-yl)-4-(-(1,1,3,3-tetramethylbutyl)phenol (2-(2H-benzotriazol-2-yl)-4-(1,1) ,3,3-tetramethylbutyl)phenol), poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2, 2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino] or their It may be a mixture, more preferably bis (2,2,6,6-tetramethyl-4-piperidyl) sebacade (Bis (2,2,6,6-tetramethyl-4-piperidyl), poly [[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4- piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino], or a mixture thereof, in which case impact strength and There is an advantage of greatly improving the weather resistance without compromising the flowability.
[124]
[125]
The slip agent may be, for example, 0.1 to 3 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the total weight of the thermoplastic resin composition, and friction resistance is improved within this range.
[126]
[127]
In the present description, a lubricant is used to improve moldability (processability) during injection molding, and a slip agent refers to that used to improve surface properties of a finished product after injection molding.
[128]
[129]
The slip agent may be, for example, polyester-modified siloxane, and in this case, there is an advantage of excellent compatibility with the thermoplastic resin composition.
[130]
Specifically, the polyester-modified siloxane has a main chain of polydimethylsiloxane, an organic group of the polydimethylsiloxane is substituted with polyester, polydimethylsiloxane as a main chain, and polyester as a side chain. In this case, compatibility with the thermoplastic resin composition is further improved, and the balance of physical properties of the composition is maintained high while providing an advantage that friction resistance is further improved.
[131]
The polyester-modified siloxane may be a polyester-modified siloxane having a hydroxyl group at the terminal, and in this case, the compatibility with the thermoplastic resin composition is more excellent, and thus the friction resistance can be greatly improved while maintaining a high overall physical property balance.
[132]
The polyester-modified siloxane may have a melting point of, for example, 50 to 55° C., preferably 52 to 55° C., and has the advantage of easy compounding with the thermoplastic resin composition within this range.
[133]
In the present description, the melting point may be measured using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 2920) manufactured by TA. As a specific example of measurement, the melting point is measured by bringing the DSC to equilibrium at a temperature of 0°C, increasing it by 20°C per minute, raising it to 180°C, decreasing it by 20°C per minute, lowering it to -60°C, and increasing it by 10°C per minute. It can be measured by increasing the temperature up to 180°C. Here, the melting point is obtained by taking the top region of the endothermic curve during the second temperature rise.
[134]
[135]
The polyester-modified siloxane may be characterized in the form of pellets, and in this case, compounding with the thermoplastic resin composition is easy, thereby improving productivity.
[136]
[137]
The thermoplastic resin composition may optionally contain at least one selected from the group consisting of dyes, pigments, flame retardants and inorganic fillers, if necessary, in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the thermoplastic resin composition. , more preferably from 0.1 to 2 parts by weight, even more preferably from 0.5 to 1 part by weight, and within this range, the required physical properties are well realized without reducing the original properties of the thermoplastic resin composition of the present base material has the effect of being
[138]
[139]
Thermoplastic resin composition
[140]
The thermoplastic resin composition of the present invention preferably has an average surface impact strength of 22 J or more, more preferably 23 when the maximum load energy is measured 10 times with a specimen thickness of 2.0 mm at a speed of 4.4 m/s according to ISO 6603-2 J or more, more preferably 23 to 27 J, even more preferably 24 to 27 J, wherein the standard deviation thereof is preferably 6.5 or less, more preferably 6 or less, still more preferably 5 or less. , more preferably 3 to 5, has the effect of satisfying the main reliability evaluation required in the automotive exterior material within this range.
[141]
[142]
In addition, the thermoplastic resin composition preferably has a Charpy impact strength (23° C.) of 9 kJ/m 2 or more, more preferably 10 kJ/m 2 to 17 kJ/m , measured with a notched specimen according to ISO 179. 2 , more preferably 12 to 15 kJ/m 2 , and within this range, the physical property balance is excellent and the impact strength required for a large injection molded article is satisfied.
[143]
[144]
In addition, the thermoplastic resin composition preferably has a melt flow index of 5.5 g/10 min or more, more preferably 6 to 10 g/10 min, still more preferably 6 to 10 kg, according to ISO 1133 at 220°C. It may be 9 g/10min, and within this range, the flowability is excellent, and there is an advantage in that injection molding of large products is easy.
[145]
[146]
The thermoplastic resin composition preferably has a heat deflection temperature of 77° C. or higher, more preferably 78 to 85° C., and still more preferably 80 to 85° C., measured under 1.8 MPa in accordance with ISO 75/Be. Within the range, all physical property balances have an excellent effect.
[147]
[148]
The thermoplastic resin composition preferably contains 3 parts by weight of BK56 (Mu-Il-Hwaseong) and 0.5 parts by weight of BK57 (Mu-Il-Hwaseong) as carbon black pigments based on 100 parts by weight of the thermoplastic resin composition, including injection temperature of 240° C. and mold temperature of 60° C. The blackness (L; pigment) measured in SCI mode using a colormeter by preparing a specimen having a size of 100 X 100 X 3 mm is 26.5 or less, more preferably 20 to 26.5, more preferably 22 to It may be 26.2, and within this range, the balance of all properties is excellent, and there is an effect of realizing a deep black color.
[149]
[150]
The thermoplastic resin composition preferably includes 0.6 parts by weight of BK39 (Muil Hwaseong) as a dye with respect to 100 parts by weight thereof, and prepares a specimen having a size of 100 X 100 X 3 mm at an injection temperature of 240 ° C. and a mold temperature of 60 ° C. Blackness (L; dye) measured in SCI mode using a (Colormeter) may be 26 or less, more preferably 20 to 26, still more preferably 23 to 26, and within this range, all physical property balance is excellent It has the effect of realizing a deep black color.
[151]
[152]
The thermoplastic resin composition preferably has a tensile strength of 44 MPa or more, more preferably 45 MPa or more, more preferably 45 to 55 MPa, even more preferably 46 to MPa, measured in accordance with ISO 527, and , there is an excellent effect of all physical property balance within this range.
[153]
[154]
The thermoplastic resin composition may be one in which the goniochromism phenomenon has not occurred by visually observing the surface of a specimen injection-molded from the thermoplastic resin composition, for example, and in this case, the surface quality is excellent.
[155]
[156]
Hereinafter, a method for producing the thermoplastic resin composition of the present invention and a molded article including the composition will be described. In describing the method for producing the thermoplastic resin composition of the present invention and a molded article including the composition, all of the above-described thermoplastic resin composition is included.
[157]
[158]
Method for producing a thermoplastic resin composition
[159]
The method for producing the thermoplastic resin composition of the present invention is A-1) 3 to 22 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 200 to 400 nm, an aromatic vinyl compound, and a vinyl cyan compound, A-2) 17 to 40 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 199 nm, an aromatic vinyl compound, and a vinyl cyan compound, B) (meth)acrylic acid alkyl ester compound, α-methyl styrene compound, and After mixing 30 to 57 wt% of a copolymer comprising a vinyl cyanide compound and 6 to 30 wt. of C) polymethacrylate resin (except α-methyl styrene), 10 to 100 pie standard at 200 to 300 ° C. To prepare a thermoplastic resin composition using an extrusion kneader; and the thermoplastic resin composition has an average surface impact strength of 22 J/mm or more and a standard deviation of 6.5 or less when the maximum load energy is measured 10 times with a specimen thickness of 2.0 mm at a speed of 4.4 m/s according to ISO 6603-2 do it with In this case, it has excellent impact resistance, heat resistance and fluidity, so that large-sized products can be injection molded, and deep black color can be realized, while suppressing the occurrence of goniochromism, which satisfies the evaluation of injection appearance quality and vehicle reliability. there is
[160]
[161]
The kneading and extrusion may be performed by, for example, a single-screw extruder, a twin-screw extruder, or a Banbury mixer, in which case the composition is uniformly dispersed to have excellent compatibility.
[162]
[163]
The kneading and extrusion may be performed, for example, in a barrel temperature of 200 to 300°C, preferably 210 to 280°C, more preferably 220 to 250°C, in which case the throughput per unit time is appropriate while Sufficient melt-kneading may be possible, and there is an effect that does not cause problems such as thermal decomposition of the resin component.
[164]
[165]
The kneading and extrusion may be performed under the condition that, for example, the number of screw rotations is 100 to 500 rpm, 150 to 400 rpm, 100 to 350 rpm, 200 to 310 rpm, preferably 250 to 350 rpm, in which case the throughput per unit time It has an effect of suppressing excessive cutting while being suitable for excellent process efficiency.
[166]
[167]
molded product
[168]
The molded article of the present substrate may include, for example, the thermoplastic resin composition of the present substrate, and in this case, it has excellent impact resistance, heat resistance and fluidity, so that large products can be injection molded, and deep black color can be realized while goniochromism ( It has the effect of suppressing the occurrence of goniochromism), which satisfies the evaluation of injection exterior quality and vehicle reliability.
[169]
The molded article may be, for example, an automobile exterior material, specifically, a large injection molded article such as a radiator grill.
[170]
[171]
Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such variations and modifications fall within the scope of the appended claims.
[172]
[173]
[Example]
[174]
(A-1) ASA graft copolymer: 40 wt% of butyl acrylate rubber having an average particle diameter of 300 nm, 43.8 wt% of styrene, 16.2 wt% of acrylonitrile
[175]
(A-2) ASA graft copolymer: 50 wt% of butyl acrylate rubber having an average particle diameter of 130 nm, shell-styrene 36.5 wt%, acrylonitrile 13.5 wt%
[176]
(A-3) ASA graft copolymer: 50 wt% of butyl acrylate rubber having an average particle diameter of 450 nm, 36.5 wt% of styrene, 13.5 wt% of acrylonitrile
[177]
(B-1) bulk polymerization type MMA-based heat-resistant SAN resin: methyl methacrylate 45% by weight, α-methyl styrene 36% by weight, acrylonitrile 19% by weight
[178]
(B-2) bulk polymerization type heat-resistant SAN resin: α-methyl styrene 72% by weight, acrylonitrile 28% by weight
[179]
(B-3) Block polymerization PMI heat-resistant resin: Denka's MSNJ
[180]
(C-1) MMA-SAN resin: 71 wt% methacrylate, 22 wt% styrene, 7 wt% acrylonitrile
[181]
(C-2) Suspension polymerization PMMA resin: polymethyl methacrylate resin (weight average molecular weight 101,000 g/mol)
[182]
(D) Lubricant: ethylene bis stearamide (EBA, manufactured by pioneer)
[183]
(E-1) Heat stabilizer: IR1076 (BASF)
[184]
(E-2) Heat stabilizer: IF168 (BASF)
[185]
(F-1) UV Stabilizer: Tin-700 (BASF)
[186]
(F-2) UV Stabilizer: Chimassorb-944 (Global Planning)
[187]
(G) Slip agent: H-Si 6441P (EVONIK)
[188]
[189]
Examples 1 to 6 and Comparative Examples 1 to 11
[190]
Pellets were prepared by kneading and extruding the components and contents shown in Tables 1 to 3, respectively, in an extruder (SM Twin screw extruder, 25Φ) at an extrusion temperature of 240° C., a feed rate of 20 kg/hr, and a screw speed of 300 rpm. Melt index was measured with the prepared pellets. In addition, injection specimens were prepared using the pellets produced under the conditions of an injection temperature of 240° C., a mold temperature of 60° C., and an injection speed of 30 mm/min using an injection machine (ENGEL 120MT).
[191]
[192]
[Test Example]
[193]
The properties of the pellets and injection specimens prepared in Examples 1 to 6 and Comparative Examples 1 to 11 were measured by the following method, and the results are shown in Tables 1 to 3 below.
[194]
* Charpy impact strength (kJ/m 2 ): A notched specimen (thickness 4 mm) was measured at 23° C. according to ISO 179/1eA.
[195]
* Melt flow rate (MFR; g/10min): The prepared pellets were measured under the conditions of 220 °C and 10 kg in accordance with ISO 333.
[196]
* Tensile strength (MPa): It was measured according to ISO 527.
[197]
* Hear deflection temperature (HDT; ℃): measured under 1.8 MPa in accordance with ISO 75/Be.
[198]
* Average multi-axial impact strength (J) and standard deviation of surface impact strength: In accordance with ISO 6603-2, the average value and The standard deviation value was calculated.
[199]
* Blackness (L): The blackness (L) was measured in SCI mode using a colormeter with an injected pigment specimen and a dye specimen having a size of 100 X 100 X 3 mm.
[200]
The lower the blackness (L) value, the higher the blackness was expressed.
[201]
Pigment specimens were prepared by kneading and extruding 3 parts by weight of BK56 (Mu-Il-Hwaseong) and 0.5 parts by weight of BK57 (Mu-Il-Hwaseong) with carbon black pigment based on 100 parts by weight of the thermoplastic resin composition to prepare pellets, followed by an injection temperature of 240° C. and a mold temperature. A pigment specimen was prepared by injection at 60° C. having a size of 100 X 100 X 3 mm.
[202]
The dye specimen was kneaded and extruded 0.6 parts by weight of BK39 (Muil-Hwaseong) as a dye with respect to 100 parts by weight of the thermoplastic resin composition to prepare a dye specimen having a size of 100 X 100 X 3 mm at an injection temperature of 240 ° C and a mold temperature of 60 ° C. .
[203]
* Goniochromism phenomenon: The appearance of extruded pellets and injection specimens of each NP color, pigment and dye was visually observed to determine whether rainbow or pearlescent color occurred. If any one of these occurs, the goniochromism phenomenon is indicated as "occurring", and if it does not occur, it is indicated as "not occurring".
[204]
The NP color is a unique color of a resin that is not colored, meaning that no pigment or dye is applied.
[205]
[206]
[Table 1]
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
(A-1) 10 11 8 5 10 20
(A-2) 28 27 28 35 28 20
(A-3)
(B-1) 47 47 54 50 42 50
(B-2)
(B-3)
(C-1) 15 11 5 10 10 10
(C-2) 4 5 10
(D) EBA 1.0 1.0 1.0 1.0 1.0 1.0
(E-1) IR1076 0.2 0.2 0.2 0.2 0.2 0.2
(E-2) IF168 0.2 0.2 0.2 0.2 0.2 0.2
(F-1) Tin-700 0.3 0.3 0.3 0.3 0.3 0.3
(F-2) Chimasorb-944 0.7 0.7 0.7 0.7 0.7 0.7
(G) H-Si 6441P 1.0 1.0 1.0 1.0 1.0 1.0
Properties
Charpy impact strength 12 12 10 10 9 15
MFR 9 8 8 7 7 6
The tensile strength 48 47 49 45 47 44
HDT 82 82 83 80 81 78
Blackness (pigment) 26.0 26.0 26 26.1 26 26.4
Blackness (dye) 25.7 25.7 25.8 25.9 25.7 26
Average
face impact strength 25 25 25 25 23 25

Standard Deviation of Surface Impact Strength 5 5 6 4 6 4
Goniochromism non-occurring non-occurring non-occurring non-occurring non-occurring non-occurring
[207]
[Table 2]
Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5
(A-1) 10
(A-2) 30.0 30.0 35.0 30.0 28
(A-3) 5.0 5.0 5.0
(B-1) 15.0 50.0 50.0
(B-2) 30.0
(B-3) 15.0
(C-1) 15.0 15.0 11.0 11.0
(C-2) 20.0 20.0 4.0 4.0 62
(D) EBA 1.0 1.0 1.0 1.0 1.0
(E-1) IR1076 0.2 0.2 0.2 0.2 0.2
(E-2) IF168 0.2 0.2 0.2 0.2 0.2
(F-1) Tin-700 0.3 0.3 0.3 0.3 0.3
(F-2) Chimasorb-944 0.7 0.7 0.7 0.7 0.7
(G) H-Si 6441P 1.0 1.0 1.0 1.0 1.0
Properties
Charpy impact strength 10 7 5 10 10
MFR 8 3 9 9 4
The tensile strength 48 48 49 48 47
HDT 83 85 82 83 75
Blackness (pigment) 26.1 26.0 25.8 26.0 25.6
Blackness (dye) 26.9 26.3 25.5 25.7 24.8
Average face impact strength 20 11 18 21 10

Standard Deviation of Surface Impact Strength 14 7 7 7 7
Goniochromism Occur Occur non-occurring non-occurring non-occurring
[208]
[Table 3]
Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11
(A-1) 10 25 8 9 10 10
(A-2) 28 10 20 25 28 28
(A-3)
(B-1) 22 50 64 10 39
(B-2) 47
(B-3)
(C-1) 2 11
(C-2) 40 4 6 56 4 23
(D) EBA 1.0 1.0 1.0 1.0 1.0 1.0
(E-1) IR1076 0.2 0.2 0.2 0.2 0.2 0.2
(E-2) IF168 0.2 0.2 0.2 0.2 0.2 0.2
(F-1) Tin-700 0.3 0.3 0.3 0.3 0.3 0.3
(F-2) Chimasorb-944 0.7 0.7 0.7 0.7 0.7 0.7
(G) H-Si 6441P 1.0 1.0 1.0 1.0 1.0 1.0
Properties
Charpy impact strength 9 13 7 8 13 10
MFR 4 8 12 5 9 6
The tensile strength 47 44 53 48 48 47
HDT 78 79 86 77 84 81
Blackness (pigment) 25.6 26.8 25.9 25.6 26.5 25.8
Blackness (dye) 24.9 26.6 25.6 24.8 27 25.1
Average face impact strength 16 20 16 13 23 20

Standard Deviation of Surface Impact Strength 8 8 10 9 12 8
Goniochromism non-occurring non-occurring non-occurring non-occurring Occur non-occurring
[209]
As shown in Tables 1 to 3, the thermoplastic resin compositions (Examples 1 to 6) according to the present invention are excellent in fluidity, heat resistance, surface impact strength, and standard deviation thereof compared to Comparative Examples 1 to 11, while gonioc There was the effect of realizing high blackness without lomism. In Comparative Examples 1 to 11, it was confirmed that the average surface impact strength was less than 22 J and the standard deviation exceeded 6.5, which did not satisfy the automobile reliability evaluation, making it difficult to apply to automobile applications. Specifically, (B-1) Public In Comparative Examples 1, 2, and 10 containing no or a small amount of coalescence, a goniochromism phenomenon occurred, and in particular, Comparative Examples 1 and 10 increased the standard deviation of the surface impact strength significantly.
[210]
In addition, Comparative Example 3 including only the ASA resin having an average particle diameter of 130 nm had poor Charpy impact strength, and Comparative Examples 5 to 7 and (C-1) which did not include a combination of (B-1) copolymer and (C-1) copolymer; 9 has lowered heat resistance.
[211]
In addition, (C-2) Comparative Example 11 including the PMMA resin alone had a low surface impact strength and a high standard deviation thereof.
Claims
[Claim 1]
A-1) 3 to 22 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 200 to 400 nm, an aromatic vinyl compound, and a vinyl cyan compound; A-2) 17 to 40 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 199 nm, an aromatic vinyl compound, and a vinyl cyan compound; B) 30 to 57% by weight of a copolymer comprising a (meth)acrylic acid alkyl ester compound, an α-methyl styrene compound, and a vinyl cyan compound; and C) 6 to 30 wt% of polymethacrylate resin (except α-methyl styrene); and, according to ISO 6603-2, the maximum load energy is 10 with a specimen thickness of 2.0 mm under a speed of 4.4 m/s. A thermoplastic resin composition, characterized in that the average surface impact strength measured twice is 22 J or more and the standard deviation is 6.5 or less.
[Claim 2]
The method according to claim 1, wherein the A-1) graft copolymer comprises 30 to 50 wt% of an acrylate rubber, 30 to 60 wt% of an aromatic vinyl compound, and 5 to 20 wt% of a vinyl cyanide compound. Thermoplastic resin composition.
[Claim 3]
The method according to claim 1, wherein the A-2) graft copolymer comprises 30 to 60% by weight of an acrylate rubber, 20 to 60% by weight of an aromatic vinyl compound, and 5 to 20% by weight of a vinyl cyanide compound. Thermoplastic resin composition.
[Claim 4]
The thermoplastic resin composition according to claim 1, wherein the A-1) graft copolymer is included in a smaller amount than the A-2) graft copolymer.
[Claim 5]
The method according to claim 1, wherein the B) copolymer comprises 30 to 55% by weight of a (meth)acrylic acid alkyl ester compound, 25 to 50% by weight of an α-methylstyrene-based compound, and 10 to 30% by weight of a vinyl cyanide compound. Thermoplastic resin composition characterized in that.
[Claim 6]
The thermoplastic resin composition according to claim 1, wherein the B) copolymer has a weight average molecular weight of 50,000 to 200,000 g/mol.
[Claim 7]
The thermoplastic resin composition according to claim 1, wherein C) the polymethacrylate resin (except for α-methyl styrene) comprises 55 wt% or more of a methacrylate monomer.
[Claim 8]
The method according to claim 7, wherein C) the polymethacrylate resin (except for α-methyl styrene) is a methyl methacrylate-styrene-acrylonitrile copolymer, or a methyl methacrylate-styrene-acrylonitrile copolymer. and a mixture of polymethyl methacrylate resin.
[Claim 9]
The method of claim 8, wherein the methyl methacrylate-styrene-acrylonitrile copolymer comprises 55 to 82% by weight of methyl methacrylate, 10 to 35% by weight of styrene, and 1 to 20% by weight of acrylonitrile. Thermoplastic resin composition characterized in that.
[Claim 10]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition comprises at least one selected from the group consisting of a lubricant, a heat stabilizer, a UV stabilizer, and a slip agent.
[Claim 11]
The thermoplastic resin composition according to claim 1, wherein the Charpy impact strength (23°C) measured with a notched specimen according to ISO 179 is 9 kJ/m 2 or more.
[Claim 12]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a melt flow index of 5 g/10 min or more measured at 220°C under 10 kg according to ISO 1133.
[Claim 13]
A-1) 3 to 22 wt% of a graft copolymer comprising an acrylate-based rubber having an average particle diameter of 200 to 400 nm, an aromatic vinyl compound and a vinyl cyan compound, A-2) An acrylate-based rubber having an average particle diameter of 50 to 199 nm 17 to 40% by weight of a graft copolymer comprising rubber, an aromatic vinyl compound, and a vinyl cyan compound, B) a copolymer comprising an (meth)acrylic acid alkyl ester compound, α-methyl styrene compound, and vinyl cyan compound 30 to 57% by weight and C) 6 to 30% by weight of a polymethacrylate resin (except for α-methyl styrene), and then at 200 to 300° C., using an extrusion kneader in a size of 10 to 100 pie, a thermoplastic resin composition manufacturing; And the prepared thermoplastic resin composition has an average surface impact strength of 22 J or more and a standard deviation of 6.5 or less when the maximum load energy is measured 10 times with a specimen thickness of 2.0 mm at a speed of 4.4 m/s in accordance with ISO 6603-2 A method for producing a thermoplastic resin composition.
[Claim 14]
A molded article comprising the thermoplastic resin composition of any one of claims 1 to 12.