Title of Invention: Thermoplastic resin composition and molded article thereof
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0122542 dated on September 22, 2020 and Korean Patent Application No. 10-2021-0064033 filed again on May 18, 2021 based thereon. All content disclosed in the literature of the application is incorporated as a part of this specification.
[3]
The present invention relates to a thermoplastic resin composition and a molded article thereof, and more particularly, has excellent processability at a low temperature of less than 200 ° C compared to conventional ASA resin, and surface defects such as flow marks or peeling occur even during co-extrusion with PVC resin The present invention relates to a thermoplastic resin composition and a molded article thereof, which have low energy consumption, excellent processing stability due to low viscosity change even with changes in extrusion RPM, and excellent heat resistance.
background
[4]
The acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as 'ASA resin') has weather resistance, aging resistance, chemical resistance, rigidity, impact resistance, and processability. It is widely used in the field.
[5]
In particular, with respect to construction materials, ASA resin is widely used for PVC co-extrusion, and specific uses include window profiles, decking boards, roofing, siding, and the like.
[6]
In the case of conventional ASA resins, extrusion or injection processing is basically performed at a processing temperature of 200 to 240 ° C, whereas in the case of PVC resins, the PVC resin is easily carbonized at a high temperature of 200 ° C. There is a limitation that co-extrusion processing of PVC resin must be made. However, since the viscosity of the ASA resin rapidly increases at a low temperature of less than 200 ℃, the ASA resin layer is not properly covered on the PVC resin layer during co-extrusion with the PVC resin, resulting in flow marks or partial ASA Surface defects such as peeling that the resin is not covered may occur. In addition, there is a disadvantage in that the viscosity of the ASA resin rapidly changes according to the change in the RPM of the extruder, so that the processing window is narrow.
[7]
Problems such as flow marks and peeling can be solved by increasing the temperature of the extruder die or the extruder barrel, or by increasing the extrusion RPM of the ASA resin to control the shear heat of the ASA, but raising the extrusion temperature requires a lot of energy and However, increasing the RPM of the ASA resin has a disadvantage in that the torque applied to the extruder increases and the load applied to the machine increases.
[8]
Therefore, the low viscosity even at low processing temperature does not cause surface defects such as flow marks or peeling during coextrusion processing with PVC resin. There is a need for development, etc.
[9]
[10]
[Prior art literature]
[11]
[Patent Literature]
[12]
KR 2009-0095764 A
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[13]
In order to solve the problems of the prior art as described above, the present invention has excellent processability at a low temperature of less than 200 ℃ compared to the conventional ASA resin, and does not cause surface defects such as flow marks or peeling even during co-extrusion with PVC resin. An object of the present invention is to provide a thermoplastic resin composition and a molded article thereof having a small consumption, a small viscosity change even with a change in extrusion RPM, and excellent processing stability, and also excellent heat resistance.
[14]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[15]
In order to achieve the above object, the present invention provides (A) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-1) comprising an acrylate rubber having an average particle diameter of 50 to 150 nm and an average particle diameter 10 to 70% by weight of a graft copolymer including an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-2) containing an acrylate rubber having a thickness of 300 to 600 nm; and (B) a high molecular weight aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 160,000 to 200,000 g/mol (B-1) and a low molecular weight having a weight average molecular weight of 80,000 g/mol or more and less than 160,000 g/mol An aromatic vinyl compound-vinyl cyan compound copolymer (B-2) containing 30 to 90 wt% of a non-graft copolymer, and the extrusion RPM is changed from 20 to 60 under the conditions of a barrel temperature of 190 ° C and a die temperature of 200 ° C. When the pressure gradient of the thermoplastic resin composition applied to the single screw extruder for sheet molding is 130 or less, it provides a thermoplastic resin composition.
[16]
In addition, the present invention provides (A) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-1) comprising an acrylate rubber having an average particle diameter of 50 to 150 nm and an average particle diameter of 300 to 600 nm 10 to 70% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-2) containing acrylate rubber; and (B) a high molecular weight aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 160,000 to 200,000 g/mol (B-1) and a low molecular weight having a weight average molecular weight of 80,000 g/mol or more and less than 160,000 g/mol An aromatic vinyl compound-vinyl cyan compound copolymer (B-2) containing 30 to 90 wt% of a non-graft copolymer, and under conditions of barrel temperature of 190 ° C, die temperature of 200 ° C, and extrusion RPM of 50, T for 1 minute and 30 seconds. - It is possible to provide a thermoplastic resin composition, characterized in that the discharge rate calculated as the discharge amount of the thermoplastic resin composition discharged through the die is 18 g / min or more.
[17]
In addition, the present invention provides (A) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-1) comprising an acrylate rubber having an average particle diameter of 50 to 150 nm and an average particle diameter of 300 to 600 nm 10 to 70% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-2) containing acrylate rubber; and (B) a high molecular weight aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 160,000 to 200,000 g/mol (B-1) and a low molecular weight having a weight average molecular weight of 80,000 g/mol or more and less than 160,000 g/mol An aromatic vinyl compound-vinyl cyan compound copolymer (B-2) 30 to 90 wt % of a non-grafted copolymer; 100 parts by weight of a base resin, 0.1 to 10 parts by weight of a polyamide resin, and 0.1 to 5 inorganic pigments It is possible to provide a thermoplastic resin composition comprising parts by weight.
[18]
Preferably, the thermoplastic resin composition may not include a thermoplastic resin having a glass transition temperature of 125° C. or higher.
[19]
In addition, the present invention can provide a molded article comprising the thermoplastic resin composition of the present invention.
Effects of the Invention
[20]
According to the present invention, compared to conventional ASA resins, it has excellent processability at a low temperature of less than 200 ° C. Even when co-extruded with PVC resins, surface defects such as flow marks or peeling do not occur, energy consumption is small, and even when extrusion RPM changes There is an effect of providing a thermoplastic resin composition excellent in processing stability and heat resistance as well as a molded article thereof due to a small change in viscosity.
Brief description of the drawing
[21]
1 schematically shows the definition, calculation method and meaning of the degree of asymmetry Rsk according to the present invention. and, geometrically, it is possible to evaluate which of the peaks and valleys on the surface constitutes the majority of the surface. In particular, the upper figure of FIG. 1 is a graph showing the expression and meaning of the root mean square deviation (Rq), where Z means the peak height, and ℓ means the average section length (sampling length). In addition, the lower figure of FIG. 1 is a graph showing the formula for calculating the asymmetry Rsk and its meaning. As the asymmetry Rsk becomes larger than 0, the peak distribution increases with respect to the mean line. This means that the distribution of The present invention makes it a gist that when the asymmetry Rsk is adjusted within a predetermined range, a rough feeling away from the plastic feeling is realized on the surface of the product.
Modes for carrying out the invention
[22]
Hereinafter, the thermoplastic resin composition of the present disclosure and a molded article thereof will be described in detail.
[23]
The present inventors mix two or more types of acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymers having different average particle diameters of rubber in a predetermined ratio, and a predetermined high molecular weight aromatic vinyl polymer excluding heat-resistant aromatic vinyl polymer, and When a predetermined low molecular weight aromatic vinyl polymer is mixed in a predetermined content range to set the pressure gradient value or discharge rate value applied to the extruder of the thermoplastic resin composition to a predetermined value, co-extrusion with PVC resin at a low temperature of less than 200 ° C. It was confirmed that the surface defects such as flow marks or peeling did not occur even during the operation, and the energy consumption and heat resistance were excellent, and based on this, further research was conducted to complete the present invention.
[24]
[25]
The thermoplastic resin composition of the present invention includes (A) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-1) comprising an acrylate rubber having an average particle diameter of 50 to 150 nm and an average particle diameter of 300 to 600 10 to 70% by weight of a graft copolymer including an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-2) containing an acrylate rubber of nm; and (B) a high molecular weight aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 160,000 to 200,000 g/mol (B-1) and a low molecular weight having a weight average molecular weight of 80,000 g/mol or more and less than 160,000 g/mol An aromatic vinyl compound-vinyl cyan compound copolymer (B-2) containing 30 to 90 wt% of a non-graft copolymer, and the extrusion RPM is changed from 20 to 60 under the conditions of a barrel temperature of 190 ° C and a die temperature of 200 ° C. It is characterized in that the pressure gradient of the thermoplastic resin composition applied to the single screw extruder for sheet molding is 130 or less. There is an advantage of providing a thermoplastic resin composition and a molded article thereof which are excellent in economic feasibility because there is no surface defect such as peeling or the energy consumption and the input amount of the ASA resin is reduced, and also excellent in heat resistance.
[26]
In addition, the thermoplastic resin composition of the present invention comprises (A) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-1) containing an acrylate rubber having an average particle diameter of 50 to 150 nm and an average particle diameter of 300 10 to 70 wt% of a graft copolymer comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-2) containing an acrylate rubber having a thickness of 600 nm; and (B) a high molecular weight aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 160,000 to 200,000 g/mol (B-1) and a low molecular weight having a weight average molecular weight of 80,000 g/mol or more and less than 160,000 g/mol An aromatic vinyl compound-vinyl cyan compound copolymer (B-2) containing 30 to 90 wt% of a non-graft copolymer, and under conditions of barrel temperature of 190 ° C, die temperature of 200 ° C, and extrusion RPM of 50, T for 1 minute and 30 seconds. - It is characterized in that the discharge rate calculated by the discharge amount of the thermoplastic resin composition discharged through the die is 18 g/min or more. A thermoplastic resin composition with excellent processing stability and excellent heat resistance as it can effectively cover PVC resin without significant change in viscosity in a wide processing window, which does not cause surface defects such as flow marks or peeling, and has low energy consumption. There is an advantage of providing a molded article thereof.
[27]
In addition, the thermoplastic resin composition of the present invention comprises (A) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-1) containing an acrylate rubber having an average particle diameter of 50 to 150 nm and an average particle diameter of 300 10 to 70 wt% of a graft copolymer comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-2) containing an acrylate rubber having a thickness of 600 nm; and (B) a high molecular weight aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 160,000 to 200,000 g/mol (B-1) and a low molecular weight having a weight average molecular weight of 80,000 g/mol or more and less than 160,000 g/mol 100 parts by weight of a base resin, 0.1 to 10 parts by weight of a polyamide resin, and 0.1 to 5 parts by weight of an inorganic pigment, including 30 to 90% by weight of a non-grafted copolymer including an aromatic vinyl compound-vinylcyanide copolymer (B-2) It is characterized in that it contains a part, and in this case, it has excellent processability at a low temperature of less than 200 ° C compared to the conventional ASA resin, so that surface defects such as flow marks or peeling do not occur even during coextrusion with PVC resin, and in a wide processing window There is an advantage of providing a thermoplastic resin composition and a molded article thereof, which can effectively cover the PVC resin without a significant change in viscosity and thus have excellent processing stability and also excellent heat resistance.
[28]
[29]
In this description, unless otherwise defined, the molding temperature means the highest temperature among the temperatures set in the temperature control zone of the barrel, that is, zones in the extrusion or injection apparatus (or process), and generally refers to the temperature in the barrel. and the temperature of the adjacent zone.
[30]
In the present description, unless otherwise defined, the barrel temperature means a molding temperature, and the barrel part means a zone in which the temperature is directly controlled by a heating device in the barrel, and although not limited thereto, it usually consists of a plurality of temperature control zones. At this time, the temperature of the barrel part is sequentially described from the temperature control zone or the first temperature control zone adjacent to the inlet (hopper) into which the thermoplastic resin composition is put, to the temperature control zone or the last temperature control zone adjacent to the die.
[31]
In this description, unless otherwise defined, the die temperature refers to the temperature set at the die nozzle, that is, the temperature of the die nozzle during extrusion or injection, and the die part refers to a region where the temperature is directly controlled by a heating device in the die, and is limited Although not normally, it consists of a plurality of temperature control zones. At this time, the temperature of the die part is sequentially described from the temperature control zone or the first temperature control zone adjacent to the barrel to the last temperature control zone or the nozzle of the die.
[32]
[33]
Hereinafter, each component constituting the thermoplastic resin composition of the present disclosure will be described in detail as follows.
[34]
[35]
(A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
[36]
The acrylate rubber of the (A-1) graft copolymer may have, for example, an average particle diameter of 50 to 150 nm, preferably 50 to 130 nm, more preferably 100 to 130 nm, and the thermoplastic finally manufactured within this range. Excellent impact strength and appearance quality can be imparted to the resin composition.
[37]
In the present description, the average particle diameter can be measured using dynamic light scattering, and in detail, the intensity value in Gaussian mode using Nicomp 380 equipment (product name, manufacturer: PSS). can be measured with 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 significantly deviate from the Intensity Setpoint 300kHz, and putting it in a glass tube, and measure it. 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.
[38]
[39]
The (A-1) graft copolymer may be, for example, 5 to 30% by weight, preferably 10 to 25% by weight, more preferably 10 to 20% by weight, based on the total weight of the thermoplastic resin composition, in this range It has excellent co-extrusion workability, mechanical properties such as impact strength, tensile strength, and elongation, as well as excellent appearance quality and surface hardness.
[40]
The (A-1) graft copolymer may include, for example, 40 to 60% by weight of an acrylate rubber, 20 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, within this range It has an excellent effect of appearance quality and surface hardness.
[41]
As a preferred example, the (A-1) graft copolymer may include 45 to 55% by weight of an acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, within this range It has an excellent effect on appearance quality and surface hardness.
[42]
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.
[43]
[44]
The (A-1) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, the appearance quality and surface hardness are excellent.
[45]
The acrylate 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 acryl late or ethylhexyl acrylate.
[46]
The aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, and is preferably styrene.
[47]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, preferably acrylonitrile.
[48]
[49]
The emulsion polymerization is not particularly limited if the emulsion graft polymerization method commonly carried out in the art to which the present invention belongs.
[50]
[51]
(A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
[52]
The acrylate rubber of the (A-2) graft copolymer may have, for example, an average particle diameter of 300 to 600 nm, preferably 350 to 600 nm, and even more preferably 350 to 550 nm, and the tensile strength within this range, There is an excellent effect of mechanical strength such as elongation and impact strength.
[53]
[54]
The (A-2) graft copolymer may be, for example, 15 to 35 wt%, preferably 20 to 30 wt%, more preferably 20 to 25 wt%, based on the total weight of the thermoplastic resin composition, in this range It has excellent co-extrusion workability, mechanical properties such as impact strength, tensile strength, and elongation, as well as excellent appearance quality and surface hardness.
[55]
The (A-2) graft copolymer may include, for example, 40 to 60% by weight of acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, within this range. There is an excellent effect of mechanical strength such as tensile strength, elongation and impact strength.
[56]
As a preferred example, the (A-1) graft copolymer may include 45 to 55% by weight of an acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, within this range It has excellent mechanical strength such as tensile strength, elongation and impact strength.
[57]
[58]
The graft copolymer (A-2) may be prepared by, for example, emulsion polymerization, and in this case, mechanical strength such as tensile strength, elongation and impact strength is excellent.
[59]
The emulsion polymerization is not particularly limited if the emulsion graft polymerization method commonly carried out in the art to which the present invention belongs.
[60]
[61]
The acrylate 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 acryl late or ethylhexyl acrylate.
[62]
The aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, and is preferably styrene.
[63]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, preferably acrylonitrile.
[64]
[65]
The (A-1) graft copolymer and the (A-2) graft copolymer have, for example, a total weight of 10 to 70% by weight, preferably 20 to 50% by weight, more preferably 30 to 40% by weight. It may be a weight %, and there is an advantage of excellent low-temperature processability within this range and excellent appearance quality.
[66]
[67]
The (A-1) graft copolymer may preferably be included in a smaller amount than the (A-2) graft copolymer, and more preferably the (A-1) graft copolymer and the (A-1) graft copolymer. -2) The graft copolymer may have a weight ratio of 1:1.2 to 1:2.5, more preferably 1:1.4 to 1:2.5, even more preferably 1:1.5 to 1:2, within this range. It has the advantage of excellent low-temperature processability and excellent appearance quality.
[68]
In the present description, the weight ratio of A and B means the weight ratio of A:B.
[69]
[70]
B-1) High molecular weight aromatic vinyl compound-vinyl cyan compound copolymer
[71]
B-1) high molecular weight aromatic vinyl compound-vinyl cyan compound copolymer of the present description may preferably be an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 160,000 to 200,000 g/mol, more preferably An aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 160,000 to 190,000 g/mol, more preferably an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 160,000 to 180,000 g/mol, even more preferably is an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 160,000 to 170,000 g/mol, and has excellent mechanical strength such as impact strength and excellent heat resistance within this range.
[72]
[73]
The B-1) high molecular weight aromatic vinyl compound-vinyl cyan compound copolymer is preferably based on the total weight of (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) non-graft copolymer. It is included in an amount of 20 to 55% by weight, more preferably 25 to 50% by weight, and in this case, there is an advantage of excellent heat resistance without impairing excellent low-temperature processability.
[74]
[75]
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: 5 μl, 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.
[76]
[77]
The B-1) high molecular weight aromatic vinyl compound-vinyl cyan compound copolymer comprises, for example, 65 to 80 wt % of an aromatic vinyl compound and 20 to 35 wt % of a vinyl cyan compound, preferably 67 to 35 wt % of an aromatic vinyl compound 80% by weight and 20 to 33% by weight of a vinyl cyanide compound, and more preferably 70 to 75% by weight of an aromatic vinyl compound and 25 to 30% by weight of a vinyl cyanide compound, within this range, mechanical It has the advantage of being excellent in strength and low-temperature processability.
[78]
The aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, and is preferably styrene.
[79]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, preferably acrylonitrile.
[80]
[81]
The B-1) high molecular weight aromatic vinyl polymer may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization, preferably by bulk polymerization, and in this case, excellent in heat resistance and fluidity It works.
[82]
The suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are not particularly limited in the case of solution polymerization and bulk polymerization methods commonly performed in the art to which the present invention pertains, respectively.
[83]
[84]
B-2) Low molecular weight aromatic vinyl compound-vinyl cyan compound copolymer
[85]
B-2) low molecular weight aromatic vinyl compound-vinyl cyan compound copolymer of the present description may preferably be an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 80,000 g/mol or more and less than 160,000 g/mol, More preferably, an aromatic vinyl compound having a weight average molecular weight of 80,000 to 110,000 g/mol-vinyl cyan compound copolymer (B-2a), an aromatic vinyl compound having a weight average molecular weight of greater than 110,000 g/mol to 110,000 g/mol or less-vinyl At least one selected from the group consisting of a cyanide compound copolymer (B-2b) and an aromatic vinyl compound having a weight average molecular weight of greater than 110,000 g/mol to less than 160,000 g/mol-vinyl cyan compound copolymer (B-2c), and more Preferably, an aromatic vinyl compound having a weight average molecular weight of 80,000 to 110,000 g/mol - vinyl cyanide copolymer (B-2a) or an aromatic vinyl compound having a weight average molecular weight of greater than 110,000 g/mol to less than 160,000 g/mol - vinyl cyan It is a compound copolymer (B-2c) and has excellent processability at a low temperature of less than 200 ° C within this range. This has excellent advantages.
[86]
[87]
The B-2) low molecular weight aromatic vinyl compound-vinyl cyan compound copolymer is preferably based on the total weight of (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) non-graft copolymer. It is contained in an amount of 5 to 30% by weight, more preferably 5 to 35% by weight, and has excellent effects in chemical resistance, impact strength, tensile strength, and low temperature workability within this range.
[88]
The B-2a) aromatic vinyl compound-vinyl cyan compound copolymer is preferably 10 based on the total weight of (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) non-graft copolymer. to 30% by weight, more preferably 10 to 25% by weight, more preferably 10 to 20% by weight, there is an excellent effect of chemical resistance, impact strength, tensile strength, low temperature workability within this range.
[89]
The B-2b) aromatic vinyl compound-vinyl cyan compound copolymer is preferably 10 based on the total weight of the (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) non-graft copolymer. to 30% by weight, more preferably 10 to 25% by weight, more preferably 10 to 20% by weight, there is an excellent effect of chemical resistance, impact strength, tensile strength, low temperature workability within this range.
[90]
The B-2c) aromatic vinyl compound-vinyl cyan compound copolymer is preferably 10 based on the total weight of (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) non-graft copolymer. to 40% by weight, more preferably 20 to 40% by weight, more preferably 20 to 35% by weight, there is an excellent effect in chemical resistance, impact strength, tensile strength and low temperature workability within this range.
[91]
[92]
The B-2) low molecular weight aromatic vinyl compound-vinyl cyan compound copolymer preferably comprises 65 to 80 wt % of an aromatic vinyl compound and 20 to 35 wt % of a vinyl cyan compound, more preferably an aromatic vinyl compound 67 to 80% by weight and 20 to 33% by weight of a vinyl cyan compound, and more preferably 70 to 75% by weight of an aromatic vinyl compound and 25 to 30% by weight of a vinyl cyan compound, and within this range In chemical resistance, impact strength, tensile strength, and workability are excellent.
[93]
The aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, and is preferably styrene.
[94]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, preferably acrylonitrile.
[95]
[96]
The B-2) low molecular weight aromatic vinyl polymer may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, and is preferably prepared by bulk polymerization, in which case it has excellent heat resistance and fluidity. .
[97]
The suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are not particularly limited in the case of solution polymerization and bulk polymerization methods commonly performed in the art to which the present invention pertains, respectively.
[98]
[99]
The (B) non-grafted copolymer is preferably included in an amount of 30 to 90% by weight based on the total weight of the (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) non-graft copolymer. and more preferably 40 to 80% by weight, more preferably 50 to 70% by weight, even more preferably 50 to 60% by weight, and within this range, both low-temperature processability and heat resistance are excellent. .
[100]
[101]
polyamide resin
[102]
The polyamide resin of the present disclosure is preferably 0.1 to 10 parts by weight, based on a total of 100 parts by weight of (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) non-graft copolymer, more Preferably it is 1 to 10 parts by weight, more preferably 3 to 9 parts by weight, and most preferably 4 to 7 parts by weight. There is an advantage.
[103]
[104]
The polyamide resin preferably has a relative viscosity (96% sulfuric acid solution) of 2.5 or less, a specific example of 2.0 to 2.5, and a preferred example of 2.2 to 2.5, and within this range, mechanical properties, weather resistance, processability, etc. are equal or higher. It has an excellent matte property while maintaining it.
[105]
In the present description, the relative viscosity can be measured with a Ubbelohde viscometer by the ISO 307 sulfuric acid method. Specifically, a solution prepared by dissolving 1 g of a sample to be measured in 100 ml of an aqueous solution of sulfuric acid having a concentration of 96% by weight is measured using a Brookfield rotational viscometer (Brookfield). rotational viscometer) can be used to measure at 20 °C.
[106]
[107]
Specific examples of the polyamide resin include polyamide 6, polyamide 66 (PA 6.6), polyamide 46, polyamide ll, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66, polyamide 6/612 , polyamide MXD6, polyamide 6/MXD6, polyamide 66/MXD6, polyamide 6T, polyamide 6I, polyamide 6/6T, polyamide 6/6I, polyamide 66/6T, polyamide 66/6I, poly Amide 6/6T/6I, Polyamide 66/6T/6I, Polyamide 9T, Polyamide 9I, Polyamide 6/9T, Polyamide 6/9I, Polyamide 66/9T, Polyamide 6/12/9T, Poly It may be at least one selected from the group consisting of amide 66/12/9T, polyamide 6/12/9I and polyamide 66/12/6I, preferably polyamide 6, polyamide 12, and polyamide 66 It is at least one selected from the group consisting of polyamide 66, and in this case, mechanical properties, weather resistance, processability, etc. are maintained at the same or higher level, while excellent matting properties are obtained.
[108]
[109]
The production method of the polyamide resin is not particularly limited if it is a polymerization method commonly carried out in the art to which the present invention belongs, and may be commercially purchased and used if it meets the definition of polyamide according to the present invention.
[110]
[111]
inorganic pigment
[112]
The inorganic pigment of the present disclosure is preferably 0.1 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, based on a total of 100 parts by weight of (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) non-graft copolymer It may be included in an amount of 0.1 to 2 parts by weight, more preferably 0.1 to 1 parts by weight, and still more preferably 0.3 to 0.8 parts by weight, and there is an excellent effect of weather resistance and hiding power within this range.
[113]
The inorganic pigment may be, for example, at least one selected from the group consisting of a metal compound such as Ti, Pb, Fe, Cr, and carbon black, and the metal compound is preferably a metal oxide or a metal hydroxide. Examples include TiO 2 , zinc oxide (Zinc Oxide) as a white inorganic pigment; carbon black, graphite as black inorganic pigments; IOR, Cadmium Red, Red Lead (Pb3O4) as red inorganic pigment; Chrome Yellow, Zinc Chromate, Cadmium Y. as yellow inorganic pigments; and at least one selected from the group consisting of Chrome Green and Zinc Green as the green inorganic pigment, and the most preferred inorganic pigment may be TiO 2 which is a white inorganic pigment .
[114]
[115]
additive
[116]
The thermoplastic resin composition of the present invention may preferably include a lubricant, an antioxidant and a UV stabilizer.
[117]
Preferably, the lubricant may be included in an amount of 0.1 to 3 parts by weight based on a total of 100 parts by weight of (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) non-graft copolymer, and more Preferably it may be included in an amount of 0.3 to 1 part by weight, more preferably 0.3 to 0.8 part by weight, and within this range, there is an advantage in that both impact strength and fluidity are excellent while implementing a rough feeling on the surface.
[118]
The lubricant is preferably at least one selected from the group consisting of an ester lubricant, a metal salt lubricant, a carboxylic acid lubricant, a hydrocarbon lubricant, and an amide lubricant, more preferably an amide lubricant, and more preferably It is a steramide-based lubricant, and most preferably is alkylene bis (steramide) having 1 to 10 carbon atoms in the alkylene, and in this case, there is an advantage in that both the impact strength and the fluidity are excellent while realizing a rough feeling on the surface.
[119]
In the present disclosure, the steramide-based lubricant may include steramide and a steramide substituent in which at least one of hydrogen is substituted with another substituent.
[120]
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.
[121]
The antioxidant is preferably at least one selected from the group consisting of phenolic antioxidants and phosphorus antioxidants, and more preferably a mixture of phenolic antioxidants and phosphorus antioxidants.
[122]
The phenolic antioxidant and the phosphorus antioxidant are preferably 0.1 to 2 parts by weight based on a total of 100 parts by weight of (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) non-graft copolymer, respectively. It may include parts by weight, more preferably 0.1 to 1 parts by weight, more preferably 0.2 to 0.6 parts by weight, respectively, within this range, while implementing a rough feeling on the surface, antioxidant effect has an excellent effect.
[123]
The phenolic antioxidant is preferably tetrakis[ethylene-3-(3,5-di-t-butyl-hydroxyphenyl)propionate](IR-1010), octadecyl 3-(3,5- di-t-butyl-4-hydroxyphenyl)propionate (IR-1076), pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, more preferably octadecyl 3-(3 ,5-di-t-butyl-4-hydroxyphenyl)propionate (IR-1076) has an excellent antioxidant effect while realizing a rough feeling on the surface within this range.
[124]
The phosphorus-based antioxidant is preferably tris (2,4-di-tert-butylphenyl) phosphite (tris (2,4-di-tertbutylphenyl) phosphite), tris (nonylphenyl) phosphite (Tris (nonylphenyl) phosphite; TNPP) and di-(2,4-di-tert-butylphenyl) pentaerythritol diphosphide (Di-(2,4-di-t-butylphenyl) pentaerythritol diphosphite) may be at least one selected from the group consisting of and more preferably tris (2,4-di-tertiary-butylphenyl) phosphite, and within this range, a rough feeling is realized on the surface while having an excellent antioxidative effect.
[125]
[126]
The UV stabilizer is preferably at least one selected from the group consisting of a benzotriazole-based UV stabilizer and a HALS-based UV stabilizer, and more preferably a mixture of a benzotriazole-based UV stabilizer and a HALS-based UV stabilizer.
[127]
The ultraviolet stabilizer is preferably 0.1 to 2 parts by weight of a benzotriazole-based ultraviolet stabilizer based on a total of 100 parts by weight of (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) non-graft copolymer and 0.1 to 2 parts by weight of a HALS-based UV stabilizer, more preferably 0.2 to 1 parts by weight of a benzotriazole-based UV stabilizer, and 0.2 to 1 parts by weight of a HALS-based UV stabilizer, more preferably benzotriazole It may contain 0.3 to 0.8 parts by weight of a sol-based UV stabilizer and 0.3 to 0.8 parts by weight of a HALS-based UV stabilizer, and within this range, a rough feeling is realized on the surface and excellent light resistance is obtained.
[128]
[129]
The benzotriazole-based UV stabilizer may be, for example, a hydroxybenzotriazole-based compound, preferably a 2-(2'-hydroxyphenyl)benzotriazole-based compound, and more preferably a 2-(2'- Hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2' -Hydroxyphenyl)benzotriazole, 2-(2'-hydroxyl-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di -tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3 ',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole Sol, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxy-carbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl -5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxyl -5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole; 2-(3'-tert-Butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2 '-Hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2, 2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol], and 2-[3'-tert-butyl-5'-(2 -Methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole may be at least one selected from the group consisting of an transesterification product of polyethylene glycol, and within this range, while implementing a rough feeling on the surface There is an effect excellent in light resistance.It may be at least one selected from the group consisting of -hydroxyphenyl]-2H-benzotriazole and a transesterification product of polyethylene glycol, and within this range, there is an effect of excellent light resistance while implementing a rough feeling on the surface.It may be at least one selected from the group consisting of -hydroxyphenyl]-2H-benzotriazole and a transesterification product of polyethylene glycol, and within this range, there is an effect of excellent light resistance while implementing a rough feeling on the surface.
[130]
[131]
The HALS-based UV stabilizer is preferably 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethyl-4-pi). Peridyl) 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- Linear or cyclic condensation product of tetramethyl-4-piperidyl)hexamethylene diamine and 4-tert-octylamino-2,6-di-chloro-1,3,5-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- linear or cyclic condensation products of morpholino-2,6-dichloro-1,3,5-triazine, and 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3, 8-diaza-4-oxospiro-[4,5] at least one selected from the group consisting of a reaction product of decane and epichlorohydrin, 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) or a mixture thereof, and within this range, a rough feeling is realized on the surface and excellent light resistance is obtained.
[132]
[133]
The thermoplastic resin composition of the present disclosure may optionally include heat stabilizers, dyes, pigments (except inorganic pigments), colorants, mold release agents, antistatic agents, antibacterial agents, processing aids, metal deactivators, flame retardants, flame retardants, anti-drip agents, if necessary. , at least one selected from the group consisting of anti-friction agents and anti-wear agents, (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) non-graft copolymer based on a total of 100 parts by weight based on 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.5 to 1 parts by weight may further include, within this range, the effect that the corresponding physical properties are well implemented without reducing the desired effect in the present invention within this range there is
[134]
[135]
Thermoplastic resin composition
[136]
The thermoplastic resin composition of the present disclosure is preferably applied to a single screw extruder for sheet molding (die form: T-Die) when the extrusion RPM is changed from 20 to 60 under the conditions of a barrel temperature of 190 ° C. and a die temperature of 200 ° C. may have a pressure gradient of 130 or less, more preferably 100 to 130, and more preferably 110 to 130, and within this range, there is an advantage in that the viscosity change due to shear is small and processing stability is excellent.
[137]
The thermoplastic resin composition is preferably discharged through the T-die of the single screw T-Die extruder for 1 minute and 30 seconds under the conditions of a barrel temperature of 190° C., a die temperature of 200° C., and an extrusion RPM of 50. The discharge calculated as the discharge amount of the thermoplastic resin composition The speed may be 18 g/min or more, more preferably 18 to 19.5 g/min, more preferably 18 to 19.0 g/min, and within this range, processability and economy are excellent.
[138]
[139]
The thermoplastic resin composition may preferably have a capillary viscosity of 2,500 to 3,200 Pa·s at 190° C. and a shear range of 100/s, more preferably 2,600 to 3,100 Pa·s, more preferably 2,700 to 3,000. Pa·s, and within this range, there is an advantage of excellent workability and economical efficiency.
[140]
The thermoplastic resin composition preferably has a storage modulus of 70,000 to 150,000 MPa at a temperature condition of 190 ° C., a strain condition of 0.1% and a frequency condition of 10 rad/s at a frequency condition of 10 rad/s, more preferably 80,000 to 140,000 MPa, more preferably 90,000 to 130,000 MPa, within this range, the adhesion to the PVC resin surface is excellent, so that the ASA resin is well covered on the PVC resin surface, layer separation does not occur, and there is an advantage of excellent processability.
[141]
[142]
The thermoplastic resin composition may preferably have an asymmetry Rsk (200° C.) of 0 to 0.5, more preferably 0 to 0.4, still more preferably 0 to 0.3, even more preferably 0.05 to 0.2, most preferably It is 0.08 to 0.15, and within this range, mechanical properties and workability, etc. are not deteriorated, and the weather resistance is excellent, and in particular, a rough feeling is implemented on the product surface, thereby having an effect of having a luxurious appearance deviating from the artificial plastic feeling.
[143]
The thermoplastic resin composition may preferably have an asymmetry Rsk (220° C.) of 0.65 to 1.35, more preferably 0.7 to 1.2, still more preferably 0.7 to 1.3, still more preferably 0.7 to 1.0, most preferably It is 0.74 to 0.9, and within this range, mechanical properties and workability, etc. are not deteriorated, and the weather resistance is excellent, and in particular, a rough feeling is implemented on the surface of the product to have an effect of having a luxurious appearance deviating from the artificial plastic feeling.
[144]
[145]
The thermoplastic resin composition may not preferably contain a thermoplastic resin having a glass transition temperature of 125° C. or higher, and more preferably an alpha-methylstyrene-vinyl cyan compound copolymer and a methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer. It may not include at least one selected from the group consisting of coalescing, and more preferably does not include both alpha-methylstyrene-vinyl cyan compound copolymer and methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer, In this case, there is an advantage that the low-temperature workability at less than 200°C does not decrease.
[146]
In the present disclosure, the glass transition temperature (Tg) may be measured by a method conventionally measured in the technical field to which the present invention belongs, and as a specific example, it may be measured by a Differential Scanning Calorimeter (DSC) based on ASTM D 3418.
[147]
In the present description, not only does not include a predetermined thermoplastic resin, but also means that the thermoplastic resin is not included at all, and the injection effect of the thermoplastic resin is very insignificant, so that the effect of the thermoplastic resin composition of the present invention is not affected at all. It also means less than the amount, and specific examples may be less than 3% by weight, less than 2% by weight, less than 1% by weight, less than 0.5% by weight, or less than 0.1% by weight. Described as a specific example, heat-resistant SAN resins such as alpha-methylstyrene-acrylonitrile copolymer not only have high viscosity at low temperatures, but also have severe viscosity changes with RPM, so when added to the thermoplastic resin composition of the present invention, low-temperature processing conditions It may be preferable to exclude in accordance with the above definition in the thermoplastic resin composition of the present invention, since low-temperature processability is reduced by increasing the viscosity in , and processing stability is deteriorated by narrowing to a processing window.
[148]
[149]
The thermoplastic resin composition may preferably be a decking material, and in this case, it has the advantage of greatly satisfying all of the physical properties required for the decking material.
[150]
The thermoplastic resin composition preferably has a heat resistance of 80 °C or higher, more preferably 82 °C or higher, even more preferably 84 °C or higher, as measured under a load of 18.6 kgf in accordance with ASTM D648, and a preferred example is 80 to 90 °C. ℃, a more preferred example may be 82 to 90 ℃, while sufficient heat resistance is secured within this range, there is an excellent effect of low-temperature processability at less than 200 ℃.
[151]
[152]
The thermoplastic resin composition may preferably be a matte thermoplastic resin composition having a film gloss of 15 or less measured at 60° with a gloss meter VG7000, more preferably 10 or less, and still more preferably 8 The following may be a matte thermoplastic resin composition, and within this range, the matte property is excellent and the physical property balance is excellent. Accordingly, the thermoplastic resin composition of the present disclosure may also be referred to as a matte thermoplastic resin composition.
[153]
[154]
The method for producing the thermoplastic resin composition of the present invention preferably includes (A) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-1) comprising an acrylate rubber having an average particle diameter of 50 to 150 nm; 10 to 70 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-2) containing an acrylate rubber having an average particle diameter of 300 to 600 nm; and (B) a high molecular weight aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 160,000 to 200,000 g/mol (B-1) and a low molecular weight having a weight average molecular weight of 80,000 g/mol or more and less than 160,000 g/mol An aromatic vinyl compound-vinyl cyan compound copolymer (B-2) containing 30 to 90 wt% of a non-graft copolymer, and the extrusion RPM is changed from 20 to 60 under the conditions of a barrel temperature of 190 ° C and a die temperature of 200 ° C. When the pressure gradient applied to the single screw extruder for sheet molding is 130 or less, it is characterized in that it comprises the step of preparing pellets using an extrusion kneader under the conditions of 220 to 280 ° C. In this case, 200 compared to the conventional ASA resin Excellent processability at low temperatures below ℃, no surface defects such as flow marks or peeling occur even during coextrusion with PVC resin, and energy consumption is low. There is an advantage of providing a thermoplastic resin composition excellent in this and also excellent in heat resistance.
[155]
The conditions of the barrel temperature of 190 °C and the die temperature of 200 °C may be, for example, barrel temperatures of 50, 190, 190, 190 °C, and die temperatures of 200, 200, and 200 °C.
[156]
[157]
The method for producing the thermoplastic resin composition shares all the technical characteristics of the aforementioned thermoplastic resin composition. Therefore, a description of the overlapping portion will be omitted.
[158]
[159]
The step of preparing the pellets using the extrusion kneader may be carried out preferably under 220 to 290 ℃, more preferably under 250 to 290 ℃, even more preferably under 270 to 290 ℃, wherein the temperature is It means the temperature set in the reader.
[160]
The extrusion kneader is not particularly limited if it is an extrusion kneader commonly used in the art to which the present invention belongs, and may preferably be a twin-screw extrusion kneader.
[161]
[162]

[163]
The molded article of the present base material is characterized by including the thermoplastic resin composition of the present base material, and in this case, it has excellent processability at a low temperature of less than 200 ° C compared to conventional ASA resins, so that flow marks and peeling are not prevented even during coextrusion with PVC resin. There is no surface defect and low energy consumption, and even with a small input amount of ASA resin, PVC resin can be effectively covered, so it is economical and has excellent heat resistance.
[164]
The molded article may preferably be an exterior material, more preferably a co-extrusion extrusion molded article or an injection molded article, and more preferably a co-extrusion molded article with a PVC resin, and specific examples include a siding material, a decking ( decking material, roofing material, sliding door material or window material, most preferred example is decking material.
[165]
[166]
The molded article may be prepared, for example, by co-extruding the thermoplastic resin composition of the present invention at a molding temperature of less than 200 ° C, preferably 180 ° C or higher to less than 200 ° C, more preferably 190 to 199 ° C. And within this range, there is an economic advantage because the surface defect does not occur and the energy consumption is small.
[167]
As another example, the molded article may be manufactured by extruding or injecting the thermoplastic resin composition of the present invention at a molding temperature of 190 to 250 ° C, preferably at 190 to 230 ° C, more preferably at 190 to 220 ° C. have.
[168]
[169]
In describing the thermoplastic resin composition of the present invention, its manufacturing method and molded article, other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation. do.
[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]
Materials used in Examples 1 to 6 and Comparative Examples 1 to 5 below are as follows.
[175]
A-1) Graft copolymer: butyl acrylate-styrene-acrylonitrile copolymer having an average particle diameter of acrylate rubber of 130 nm (butyl acrylate 50% by weight, styrene 35% by weight, and acrylonitrile 15% by weight)
[176]
A-2) Graft copolymer: butyl acrylate-styrene-acrylonitrile copolymer having an average particle diameter of acrylate rubber of 500 nm (butyl acrylate 50% by weight, styrene 35% by weight, and acrylonitrile 15% by weight)
[177]
B-1) Bulk polymerization type SAN resin (95HCP, manufactured by LG Chem, weight average molecular weight 91,000 g/mol)
[178]
B-2) Bulk polymerization type SAN resin (92HR, manufactured by LG Chem, weight average molecular weight 130,000 g/mol)
[179]
B-3) Bulk polymerization type SAN resin (90HR, manufactured by LG Chem, weight average molecular weight 150,000 g/mol)
[180]
B-4) Bulk polymerization type SAN resin (97HC, manufactured by LG Chem, weight average molecular weight 170,000 g/mol)
[181]
B-5) Bulk polymerization type heat-resistant SAN resin (200UH, manufactured by LG Chem, weight average molecular weight 90,000 g/mol)
[182]
D) Nylon 66
[183]
[184]
Examples 1 to 6 and Comparative Examples 1 to 5
[185]
0.5 parts by weight of EBS (manufactured by pioneer) as a lubricant, and octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (octadecyl) as an antioxidant 0.4 parts by weight of 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate) and Tris(2,4-di-tert.-butylphenyl)phosphite (Tris(2,4-di-tert.-butylphenyl) )phosphite)) 0.4 parts by weight, as a UV stabilizer, 0.6 parts by weight of Tinuvin 329 (manufactured by BASF), a benzotriazole-based UV stabilizer, and 0.6 parts by weight of Tinuvin770 (manufactured by BASF), a HALS-based UV stabilizer, were uniformly mixed, and then this was mixed in a twin-screw extruder. Pellets were prepared by kneading and extrusion at 280 °C. In addition, a sheet of 0.15T was manufactured using a single screw T-die extruder at a barrel temperature of 50, 190, 190, 190 °C and a die temperature of 200, 200, 200 °C with the produced pellets to obtain gloss and surface roughness values. was measured. Furthermore, the prepared pellets were injected at a molding temperature of 220° C. to prepare a specimen for measuring physical properties, and tensile strength and impact strength were measured using this.
[186]
[187]
[Test Example]
[188]
The properties of the pellets, sheets and specimens prepared in Examples 1 to 6 and Comparative Examples 1 to 5 were measured by the following method, and the results are shown in Table 1 below.
[189]
* Heat resistance (°C): Measured under a load of 18.6 kgf according to ASTM D648.
[190]
* Gloss: Measured at 60° with a gloss meter VG7000.
[191]
* Pressure gradient: Single screw extruder for sheet molding (manufactured by Collin, E20T product) when changing the extrusion RPM from 20 to 60 under conditions of barrel temperature 50, 190, 190, 190 ℃ and die temperature 200, 200, 200 ℃ ) was measured by the pressure of the thermoplastic resin composition. As for the pressure gradient, the RPM is first raised to 60, and the resin flows while waiting until the temperature of the internal adapter of the extruder is stabilized. When the temperature is stabilized, the pressure displayed on the extruder is recorded. Since temperature affects the viscosity of the resin, data should be taken after confirming that the temperature is constant. In the same manner, the pressure was recorded while sequentially decreasing the RPM to 20. The slope obtained by drawing a logarithmic trend line on the graph of the pressure change with respect to the obtained RPM was used as the pressure slope value.
[192]
* Discharge rate: It was calculated as the discharge amount of the thermoplastic resin composition discharged through the T-die for 1 minute and 30 seconds under the conditions of barrel temperature 50, 190, 190, 190 ° C, die temperature 200, 200, 200 ° C, and extrusion RPM 50 .
[193]
* Capillary viscosity (Pa·s): A capillary rheometer (GOETTFERT, RG-75) was used, and flow viscosity was measured in a shear range of 10/s to 2000/s at 190 ° C. At this time, the data in the shear range 100/s was used for the analysis result, and the sample was dried in an oven at 80° C. for 3 hours or more before analysis to remove the effect of viscosity due to moisture.
[194]
* Storage modulus (MPa): A Strain Controlled Type Rheometer (TA Instruments, ARES-G2) was used, and the geometry used for measurement at a measurement temperature of 190 ° C was a 25mm parallel plate. Here, the strain condition was 0.1%, and the measurement was carried out in the range of a frequency of 0.1 to 500 rad/s. In this case, the storage modulus data of 10 rad/s was used as the analysis result.
[195]
* Asymmetry Rsk: Referring to FIG. 1 below, an Optical profiler system (Nano View NV-2700, Manufacturer: Nano System) was used as the equipment, and the analysis conditions were 20 times the objective lens × eyepiece in WSI Envelope mode. Scanning was performed over a range of ±40 μm using a 1x lens. Measurements were carried out for 5 points after the sample was flatly fixed on the stage. For the measured values, the average value for 5 points was calculated using the formula to find the root mean square deviation (Rq) shown in the upper figure and the asymmetry Rsk shown in the lower figure.
[196]
Here, the degree of asymmetry (Rsk, 200 ℃) is uniformly extruded to a thickness of 0.15T through a 15-pi film extruder at a barrel temperature of 50, 190, 190, 190 ℃ and a die temperature of 200, 200, 200 ℃ After that, Rsk is measured by the method presented above, and the degree of asymmetry (Rsk, 220 ℃) ​​is 15 pie at the barrel temperature of 50, 200, 210, 210 ℃ and the die part temperature of 220, 220, 230 ℃ of the prepared pellets. It is a value measured by the method presented above after uniformly extruding to a thickness of 0.15T through a film extruder.
[197]
[198]
[Table 1]
(parts by weight) Example comparative example
One 2 3 4 5 6 One 2 3 4 5
A-1 13 13 13 13 15 17 25 13 13 13 13
A-2 23 23 23 23 19 17 15 25 23 23 23
B-1 15 25 58
B-2 20 58
B-3 20 30 20 41 58
B-4 38 43 33 28 40 40
B-5 54 15
D 6 6 6 6 6 6 6 6 6 6 6
TiO 2 pigment 0.6 0.6 0.6 0.5 0.5 0.6 0.6 0.6 0.6 0.6 0.6
RPM 60 326 288 295 292 291 281 370 311 275 282 296
50 310 271 277 273 275 264 346 290 255 266 276
40 289 249 252 248 252 242 310 259 228 242 252
30 248 213 217 209 218 210 264 215 202 210 220
20 189 157 166 157 163 160 193 154 171 167 170
inclination 126.16 119.76 118.2 124.13 117.09 110.33 162.07 144.55 94.92 105.95 114.27
Discharge speed (g/min) 18.1 18.5 18.3 18.4 18.7 18.9 15.9 17.4 19.3 18.7 18.3
Capillary Viscosity (Pa s) 2837 2766 2799 2778 2613 2793 3338 2988 2587 2714 2799
Storage modulus (MPa) 125070 107017 113842 116711 107503 94342 131601 111484 74351 89648 100207
HDT(℃) 84.2 84.6 82.3 82.7 84.9 84.2 89.7 92.9 72.2 75.4 77.3
Asymmetry (Rsk, 200℃) 0.12 0.11 0.08 0.14 0.15 0.12 0.34 0.28 0.14 0.13 0.09
Asymmetry (Rsk, 220℃) 0.79 0.9 0.88 0.84 0.74 0.78 0.91 0.95 0.81 0.88 0.85
Gloss (60°) 8.2 7.8 8 8.2 9.3 8.7 6.5 6.8 7.9 8.1 8.3
[199]
As shown in Table 1, the thermoplastic resin composition according to the present invention (see Examples 1 to 6) has excellent processability even at a low temperature of less than 200 ° C. compared to Comparative Examples 1 to 5, which have different configurations, resulting in flow marks and peeling. It was confirmed that no surface defects such as surface defects occur, energy consumption is small, and viscosity change is small even with changes in extrusion RPM, so processing stability is excellent, and even heat resistance is excellent. Comparative Examples 1 and 2 using the resin have poor processability and economic feasibility due to poor discharge speed, etc., and Comparative Examples 3 to 5 using only low molecular weight SAN resins with different types have poor heat resistance (HDT). there was.
Claims
[Claim 1]
(A) An acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-1) comprising an acrylate rubber having an average particle diameter of 50 to 150 nm and an acrylate rubber having an average particle diameter of 300 to 600 nm 10 to 70 wt% of a graft copolymer comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-2); and (B) a high molecular weight aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 160,000 to 200,000 g/mol (B-1) and a low molecular weight having a weight average molecular weight of 80,000 g/mol or more and less than 160,000 g/mol An aromatic vinyl compound-vinyl cyan compound copolymer (B-2) containing 30 to 90 wt% of a non-graft copolymer, and the extrusion RPM is changed from 20 to 60 under the conditions of a barrel temperature of 190 ° C and a die temperature of 200 ° C. A thermoplastic resin composition, characterized in that the pressure gradient of the thermoplastic resin composition applied to the single screw extruder for sheet molding is 130 or less.
[Claim 2]
According to claim 1, wherein the thermoplastic resin composition is a discharge rate calculated as the discharge amount of the thermoplastic resin composition discharged through the T-die for 1 minute and 30 seconds under the conditions of a barrel temperature of 190 °C, a die temperature of 200 °C, and an extrusion RPM of 50 is 18 g Thermoplastic resin composition, characterized in that /min or more.
[Claim 3]
According to claim 1, wherein the thermoplastic resin composition is (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) based on a total of 100 parts by weight of the non-grafted copolymer polyamide resin 0.1 to 10 A thermoplastic resin composition comprising parts by weight.
[Claim 4]
According to claim 1, wherein the thermoplastic resin composition (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) based on a total of 100 parts by weight of the non-grafted copolymer inorganic pigment 0.1 to 5 weight A thermoplastic resin composition comprising a part.
[Claim 5]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition does not contain a thermoplastic resin having a glass transition temperature of 125°C or higher.
[Claim 6]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a decking material.
[Claim 7]
The thermoplastic resin composition according to claim 1, wherein the weight ratio of the (A-1) graft copolymer and the (A-2) graft copolymer is 1:1.2 to 1:2.5.
[Claim 8]
The method according to claim 1, wherein the (A-1) graft copolymer comprises 40 to 60 wt% of an acrylate-based rubber, 20 to 40 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyanide compound. A thermoplastic resin composition comprising
[Claim 9]
The method according to claim 1, wherein the (A-2) graft copolymer comprises 40 to 60 wt% of an acrylate-based rubber, 25 to 45 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyanide compound. A thermoplastic resin composition comprising
[Claim 10]
The method according to claim 1, wherein the (B-1) high molecular weight aromatic vinyl compound-vinyl cyan compound copolymer and the (B-2) low molecular weight aromatic vinyl compound-vinyl cyan compound copolymer each contain 65 to 80 weight of the aromatic vinyl compound. % and 20 to 35 wt% of a vinyl cyan compound.
[Claim 11]
The method according to claim 1, wherein the low molecular weight aromatic vinyl compound-vinyl cyan compound copolymer (B-2) has a weight average molecular weight of 80,000 to 110,000 g/mol, an aromatic vinyl compound-vinyl cyan compound copolymer (B-2a); Aromatic vinyl compound-vinyl cyan compound copolymer (B-2b) having a weight average molecular weight of more than 110,000 g/mol to 110,000 g/mol or less, and an aromatic vinyl compound having a weight average molecular weight of greater than 110,000 g/mol to less than 160,000 g/mol- A thermoplastic resin composition, characterized in that at least one selected from the group consisting of vinyl cyan compound copolymer (B-2c).
[Claim 12]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a heat resistance of 80°C or higher measured under a load of 18.6 kgf according to ASTM D648.
[Claim 13]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a capillary viscosity of 2,500 to 3,200 Pa·s under a condition of 190°C and a shear range of 100/s.
[Claim 14]
The thermoplastic resin according to claim 1, wherein the thermoplastic resin composition has a storage modulus (geometry is 25 mm parallel plate) of 70,000 to 150,000 MPa at a temperature condition of 190 °C, a strain condition of 0.1%, and a frequency condition of 10 rad/s. composition.
[Claim 15]
The thermoplastic resin composition according to claim 1, wherein the asymmetry Rsk (200°C) of the thermoplastic resin composition is 0 to 0.5, and the asymmetry Rsk (220°C) is 0.65 to 1.35.
[Claim 16]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a matte thermoplastic resin composition having a film gloss of 15 or less measured at 60°.
[Claim 17]
A molded article comprising the thermoplastic resin composition of any one of claims 1 to 16.