Title of Invention: Thermoplastic resin composition and exterior material thereof
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0091648 dated July 23, 2020, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
The present invention relates to a thermoplastic resin composition and its exterior material, and more particularly, to a low-gloss thermoplastic resin composition that has mechanical properties and processability equal to or greater than that of a conventional ASA-based resin, and has excellent sensitivity quality by improving low gloss and surface texture, and its It's about exterior materials.
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 the case of ASA resins in the field of exterior materials, the need for developing low-gloss ASA resins that can satisfy the demand for sensible resins away from the artificial feeling of plastic is increasing.
[6]
As the low-gloss ASA resin, a crystalline resin such as nylon has conventionally been used to achieve low gloss, but there is a limit to improvement in surface texture and emotional quality.
[7]
[Prior art literature]
[8]
[Patent Literature]
[9]
KR 2009-0095764 A
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 superior mechanical properties and processability compared to the conventional ASA resin, while improving uniform and low gloss and surface texture, resulting in emotional quality such as softness, luxury and naturalness. An object of the present invention is to provide this excellent low-gloss thermoplastic resin composition and an exterior material thereof.
[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 styrene-based resin 90 comprising an acrylate rubber having a DLS average particle diameter of 0.25 to 0.32 μm or a TEM average particle diameter of 0.2 to 0.27 μm based on the total weight of the styrene-based resin in an amount of 5 to 30% by weight. to 99.5% by weight; And it provides a thermoplastic resin composition comprising 0.5 to 10% by weight of a polyamide resin.
[13]
In addition, the present invention includes 90 to 99.5% by weight of a styrene-based resin comprising 5 to 30% by weight of an acrylate rubber based on the total weight of the styrene-based resin; and 0.5 to 10% by weight of a polyamide resin,
[14]
It is possible to provide a thermoplastic resin composition, characterized in that the reduced volume (reduced volume) calculated by the following formula 1 is 15 to 40.
[15]
[Equation 1]
[16]
Converted volume = [1/6Π(R A ) 3 (A/A+B+C) + 1/6Π(R B ) 3 (B/A+B+C) + 1/6Π(R C ) 3 (C /A+B+C)] / [1/6(R C ) 3 ]
[17]
Here, R A is the average particle diameter (nm) of the rubber having the largest average particle diameter among the rubbers included in the resin composition, and RB is the average particle diameter of the rubber having the average particle diameter of the middle size among the rubbers included in the resin composition ( nm), and R C is the average particle diameter (nm) of the rubber having the smallest average particle diameter among the rubbers included in the resin composition. In addition, A is the weight % of the graft polymer having the largest average particle diameter among the rubbers included in the resin composition, and B is the weight % of the graft polymer having the average particle diameter of the middle size among the rubbers included in the resin composition, wherein C is the weight % of the graft polymer having the smallest average particle diameter among rubbers included in the resin composition.
[18]
B has a value of "0" when the resin composition of the present disclosure does not include a rubber having an average particle size of medium size.
[19]
For reference, the volume may be defined by Equation 2 below.
[20]
[Equation 2]
[21]
Volume = 4/3Πr 3 = 1/6ΠR 3
[22]
(In Equation 2, r is the radius, and R is the diameter.)
[23]
The styrene-based resin preferably includes at least two selected from the group consisting of a first styrene-based resin, a second styrene-based resin, and a third styrene-based resin, and the first styrene-based resin preferably has an average particle diameter of 0.25 to 0.32. It is an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising 30 to 50 wt% of acrylate rubber having an average particle diameter of 0.2 to 0.27 μm or TEM, and the second styrene-based resin is preferably an aromatic vinyl compound- It is a vinyl cyanide compound copolymer, and the third sterene-based resin is preferably i) an acrylate-aromatic vinyl containing 45 to 65 wt% of an acrylate rubber having a DLS average particle diameter of 0.05 to 0.2 μm or a TEM average particle diameter of 0.04 to 0.14 μm. Compound-vinyl cyan compound graft copolymer, ii) acrylate-aromatic vinyl compound-vinyl cyan compound containing 45 to 65 wt% of an acrylate rubber having a DLS average particle diameter of 0.33 to 0.5 μm or a TEM average particle diameter of 0.28 to 0.45 μm It may be at least one selected from the group consisting of a graft copolymer, iii) a heat-resistant styrene-based resin, and iv) an aromatic vinyl compound-vinyl cyan compound-methacrylate copolymer.
[24]
The styrenic resin preferably includes 20 to 50% by weight of the first styrene-based resin, 10 to 60% by weight of the second styrene-based resin, and 1 to 30% by weight of the third styrene-based resin, based on the total weight of the thermoplastic resin composition. can
[25]
The thermoplastic resin composition may preferably have a reduced volume of 15 to 40.
[26]
The thermoplastic resin composition may include, for example, 0.1 to 5 parts by weight of an inorganic pigment in a total of 100 parts by weight of the thermoplastic resin composition.
[27]
Preferably, the thermoplastic resin composition may have an average surface roughness (Ra) of 2.2 or less by measuring 5 points using an optical profiler system.
[28]
The thermoplastic resin composition may be a matte thermoplastic resin composition having a 60° film gloss of 15 or less.
[29]
The first styrenic resin is preferably 30 to 50% by weight of an acrylate rubber having a DLS average particle diameter of 0.25 to 0.32 μm or a TEM average particle diameter of 0.2 to 0.27 μm, an aromatic vinyl compound 40 to 60% by weight, and a vinyl cyanide compound 8 to 18 It may be an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising wt%.
[30]
The second styrene-based resin may preferably be an aromatic vinyl compound-vinyl cyan compound copolymer comprising 65 to 80 wt% of an aromatic vinyl compound and 20 to 35 wt% of a vinyl cyan compound.
[31]
The second styrenic resin is preferably a) 10 to 60 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 90,000 to 160,000 g/mol, and b) a weight average based on the total weight of the thermoplastic resin composition It may contain 0 to 40% by weight of an aromatic vinyl compound having a molecular weight of more than 160,000 g/mol and 200,000 g/mol or less of a vinyl cyanide copolymer, and in this case, mechanical properties and processability, etc. are equal or more and uniform and low gloss and surface texture It has an excellent effect on emotional quality such as softness, luxury and naturalness.
[32]
The i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer preferably contains 45 to 65 wt% of an acrylate rubber having a DLS average particle diameter of 0.05 to 0.2 μm or a TEM average particle diameter of 0.04 to 0.14 μm, aromatic vinyl compound 25 to 45% by weight and 8 to 18% by weight of a vinyl cyan compound, wherein the ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer preferably has a DLS average particle diameter of 0.33 to 0.5 μm or a TEM average 40 to 60 wt% of an acrylate rubber having a particle diameter of 0.28 to 0.45 μm, 25 to 45 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyan compound, wherein iii) the heat-resistant styrene-based resin is preferably α -Methylstyrene 63 to 73% by weight , styrene 0 to 10% by weight and 25 to 33% by weight of a vinyl cyan compound, wherein the iv) aromatic vinyl compound-vinyl cyan compound-methacrylate copolymer is preferably 65 to 85 wt% of a methacrylate-based monomer, 10 to 30 wt% of an aromatic vinyl compound, and 5 to 10 wt% of a vinyl cyanide compound may be included.
[33]
The i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is preferably included in an amount of 1 to 20 wt%, and the ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is preferably is included in an amount of 1 to 20% by weight, iii) the heat-resistant styrene-based resin is preferably included in an amount of 1 to 25% by weight, and the iv) aromatic vinyl compound-vinyl cyan compound-methacrylate copolymer is preferably It may be included in 5 to 30% by weight.
[34]
The polyamide resin may be preferably polyamide 6, polyamide 6.6, or a mixture thereof.
[35]
In addition, the present invention provides an exterior material comprising the thermoplastic resin composition.
[36]
The facing material may preferably be a siding material, a roofing material or a decking material.
Effects of the Invention
[37]
According to the present invention, a low-gloss thermoplastic resin composition with superior emotional qualities such as softness, luxury and naturalness with improved surface texture and even low gloss and improved surface texture while having mechanical properties and processability equal to or greater than that of conventional ASA resins, and an exterior material thereof has the effect of
Brief description of the drawing
[38]
1 is a photograph taken by the film extruder used in Examples.
Modes for carrying out the invention
[39]
Hereinafter, the thermoplastic resin composition of the present disclosure and its packaging material will be described in detail.
[40]
As a result of the present inventors' continuous efforts to improve the emotional quality of the low-gloss ASA resin composition containing the ASA resin and the polyamide resin, when a medium-diameter ASA resin in a predetermined particle size range is added in a predetermined amount, mechanical properties compared to the conventional ASA resin composition , weather resistance and workability, etc. are not deteriorated, and the gloss is low and even, and the surface texture is natural and luxurious unlike the plastic feeling, and based on this, further research was completed to complete the present invention.
[41]
The thermoplastic resin composition of the present invention contains 90 to 99.5% by weight of a styrene-based resin comprising 5 to 30% by weight of an acrylate rubber having a DLS average particle diameter of 0.25 to 0.32 μm or a TEM average particle diameter of 0.2 to 0.27 μm, based on the total weight of the styrene-based resin. ; and 0.5 to 10% by weight of polyamide resin, and in this case, mechanical properties and processability are equal or higher than that of conventional ASA-based resins, and smoothness, luxury and naturalness due to the improvement of even and low gloss and surface texture There is an advantage of providing a low-gloss thermoplastic resin composition excellent in emotional quality such as, and an exterior material thereof.
[42]
The acrylate rubber having an average DLS particle diameter of 0.25 to 0.32 μm or a TEM average particle diameter of 0.2 to 0.27 μm is preferably 10 to 25% by weight, more preferably 10 to 20% by weight, more preferably based on the total weight of the styrenic resin. may be included in an amount of 12 to 18% by weight, most preferably 14 to 16% by weight, and within this range, mechanical properties, processability, and colorability are satisfied, and the sensibility quality such as low gloss and softness and luxury is excellent. have.
[43]
Hereinafter, each component constituting the thermoplastic resin composition of the present disclosure will be described in detail as follows.
[44]
< Styrene-based resin>
[45]
The styrene-based resin of the present disclosure may include two or more selected from the group consisting of a first styrene-based resin, a second styrene-based resin, and a third styrene-based resin, and more preferably a first styrene-based resin. , the second styrene-based resin and the third styrene-based resin may be included.
[46]
In the present description, 'styrene-based resin' follows the definition of a styrene-based resin commonly recognized in the technical field to which the present invention belongs, and may mean, for example, a resin including units derived from an aromatic vinyl compound.
[47]
The styrenic resin is preferably 90 to 99% by weight, more preferably 90 to 97% by weight, still more preferably 90 to 65% by weight, and most preferably 94 to 95% by weight, and weather resistance within this range is , aging resistance, chemical resistance, rigidity, impact resistance and workability are all excellent effects.
[48]
The first styrene-based resin is preferably an acrylate-aromatic vinyl compound-vinyl cyan compound graft comprising 30 to 50 wt% of an acrylate rubber having a DLS average particle diameter of 0.25 to 0.32 μm or a TEM average particle diameter of 0.2 to 0.27 μm. a copolymer, wherein the second styrene-based resin is an aromatic vinyl compound-vinyl cyan compound copolymer, and the third styrene-based resin is i) an acrylate rubber having a DLS average particle diameter of 0.05 to 0.2 μm or a TEM average particle diameter of 0.04 to 0.14 μm. 40 to 60 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, ii) 40 to 60 weight of an acrylate rubber having a DLS average particle diameter of 0.33 to 0.5 μm or a TEM average particle diameter of 0.28 to 0.45 μm % containing at least one selected from the group consisting of acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, iii) heat-resistant styrene-based resin, and iv) aromatic vinyl compound-vinyl cyan compound-methacrylate copolymer have.
[49]
In addition, the styrene-based resin is preferably 20 to 50% by weight of the first styrene-based resin, 10 to 60% by weight of the second styrene-based resin, and 1 to 30% by weight of the third styrene-based resin, based on the total weight of the thermoplastic resin composition. may include
[50]
first styrene-based resin
[51]
The first styrenic resin of the present substrate preferably contains 30 to 50% by weight, more preferably 35 to 45% by weight, and still more preferably 37 to 42% by weight of acrylate rubber having an average particle diameter of 0.25 to 0.32 μm. It is an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, and within this range, mechanical properties and processability are equal or higher than that of conventional ASA-based resins, and smoothness, luxury and There is an advantage of excellent emotional quality such as naturalness.
[52]
The acrylate rubber preferably has a DLS average particle diameter of 0.25 to 0.32 μm, more preferably 0.25 to 0.30 μm, still more preferably 0.26 to 0.30 μm, and most preferably 0.26 to 0.29 μm, and is evenly distributed within this range. Low gloss and improved surface texture have an excellent effect on emotional qualities such as softness, luxury and naturalness.
[53]
The acrylate rubber preferably has a TEM average particle diameter of 0.2 to 0.27 μm, and within this range, there is an excellent effect in emotional quality such as softness, luxury, and naturalness due to the improvement of uniform low gloss and surface texture.
[54]
The first styrenic resin is preferably 25 to 50% by weight, more preferably 25 to 45% by weight, even more preferably 30 to 45% by weight, most preferably 30 to 42% by weight based on the total weight of the thermoplastic resin composition. % by weight, and within this range, mechanical properties and processability are equal to or greater than that of conventional ASA-based resins, and there is an advantage in that it has excellent emotional qualities such as softness, luxury and naturalness due to the improvement of even and low gloss and surface texture.
[55]
The first styrene-based resin is preferably an acrylate comprising 30 to 50 wt% of an acrylate rubber having an average particle diameter of 0.25 to 0.32 μm, 40 to 60 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyanide compound- It may be an aromatic vinyl compound-vinyl cyan compound graft copolymer, and in this case, while satisfying mechanical properties and processability, even and low gloss and improvement of surface texture have an excellent effect in emotional quality such as softness, luxury and naturalness.
[56]
In this description, the average particle diameter means the DLS average particle diameter unless otherwise defined.
[57]
The aromatic vinyl compound is preferably 40 to 55 wt%, more preferably 40 to 50 wt%, still more preferably 45 to 50 wt%, based on the total weight of the acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer. % by weight, and has excellent processability and mechanical properties within this range.
[58]
The vinyl cyan compound is preferably 10 to 18 wt %, more preferably 10 to 15 wt %, more preferably 11 to 13 wt %, based on the total weight of the acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer. % by weight, and has excellent processability and mechanical properties within this range.
[59]
Second Styrenic Resin
[60]
The second styrene-based resin of the present disclosure is preferably an aromatic vinyl compound-vinyl cyan compound copolymer, and in this case, mechanical properties and processability are excellent.
[61]
The second styrenic resin may preferably be an aromatic vinyl compound-vinyl cyan compound copolymer comprising 65 to 80 wt% of an aromatic vinyl compound and 20 to 35 wt% of a vinyl cyan compound, and mechanical properties within this range and excellent workability.
[62]
The second styrenic resin is preferably 20 to 60% by weight, more preferably 30 to 60% by weight, still more preferably 40 to 60% by weight, most preferably 41 to 56% by weight, within this range It has excellent mechanical properties and processability.
[63]
The second styrenic resin is preferably a) 10 to 60 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 90,000 to 160,000 g/mol, and b) a weight average based on the total weight of the thermoplastic resin composition An aromatic vinyl compound having a molecular weight of more than 160,000 g/mol to 200,000 g/mol or less may contain 0 to 40 wt% of the vinyl cyan compound copolymer, and there is an excellent effect in tensile strength and impact strength within this range.
[64]
As a more specific example, the second styrenic resin may include a) 10 to 30% by weight, preferably 15 to 25% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer, and b) an aromatic vinyl compound, based on the total weight of the thermoplastic resin composition. -The vinyl cyanide compound copolymer may contain 25 to 45 wt%, preferably 30 to 40 wt%, and within this range, there is an excellent effect in processability, tensile strength and impact strength.
[65]
The aromatic vinyl compound-vinyl cyan compound copolymer may be preferably a styrene-acrylonitrile copolymer, and in this case, there are advantages of excellent mechanical strength and processability.
[66]
The second styrenic resin may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, and in this case, it has excellent processability and fluidity.
[67]
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.
[68]
Third Styrenic Resin
[69]
The third sterene-based resin of the present disclosure is preferably i) an acrylate-aromatic vinyl compound-vinyl containing 45 to 65% by weight of an acrylate rubber having a DLS average particle diameter of 0.05 to 0.2 μm or a TEM average particle diameter of 0.04 to 0.14 μm. A cyanide compound graft copolymer, ii) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising 45 to 65 wt% of an acrylate rubber having a DLS average particle diameter of 0.33 to 0.5 μm or a TEM average particle diameter of 0.28 to 0.45 μm It may be at least one selected from the group consisting of a copolymer, iii) a heat-resistant styrene-based resin, and iv) an aromatic vinyl compound-vinyl cyan compound-methacrylate copolymer.
[70]
The third styrenic resin is preferably 1 to 20% by weight, more preferably 3 to 20% by weight, more preferably 5 to 20% by weight based on the total weight of the thermoplastic resin composition, and mechanical properties within this range , processability, heat resistance and surface texture are excellent.
[71]
i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
[72]
The i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer preferably contains 45 to 65 wt% of an acrylate rubber having a DLS average particle diameter of 0.05 to 0.2 μm or a TEM average particle diameter of 0.04 to 0.14 μm, and an aromatic vinyl compound 25 to 45% by weight and 8 to 18% by weight of a vinyl cyanide compound, and has excellent effects in weather resistance, fluidity, processability, colorability, tensile strength and impact strength within this range.
[73]
As a preferred example, the i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises 45 to 65 wt% of an acrylate rubber, 30 to 40 wt% of an aromatic vinyl compound and 10 to 20 wt% of a vinyl cyanide compound It can be made, and within this range, there is an excellent effect of weather resistance, fluidity, tensile strength and impact strength.
[74]
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.
[75]
The i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, chemical resistance, weather resistance, fluidity, tensile strength and impact strength are excellent.
[76]
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.
[77]
In the present description, 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 acrylate or ethylhexyl acrylate.
[78]
In the present description, 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 preferably styrene.
[79]
In the present description, the vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methnitrolonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, and is preferably acrylonitrile.
[80]
The acrylate rubber of i) the graft copolymer preferably has an average particle diameter of 0.05 to 0.2 μm, more preferably 0.05 to 0.15 μm, still more preferably 0.08 to 0.15 μm, and most preferably 0.08 to 0.12 μm, Within this range, excellent weather resistance, colorability, impact strength, chemical resistance and processability can be imparted to the finally manufactured thermoplastic resin composition.
[81]
In this description, the DSL average particle diameter can be measured using a dynamic light scattering method, and in detail, the Nicomp 380 equipment (product name, manufacturer: PSS) is used to Gaussian mode intensity (intensity) value can be measured. At this time, as a specific measurement example, the sample is prepared by diluting 0.1 g of Latex (TSC 35-50 wt%) 1,000-5,000 times with distilled water, the measurement method is auto-dilution and measurement with a flow cell, and the measurement mode is dynamic It can be done by dynamic light scattering method/Intensity 300KHz/Intensity-weight Gaussian Analysis.
[82]
In addition, in the present description, the DLS average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, specifically, a scattering intensity average particle diameter.
[83]
In the present description, the TEM average particle diameter may be measured using a transmission electron microscope (TEM) analysis, and as a specific example, it means a value obtained by numerically measuring and averaging particle sizes on a TEM high-magnification image. In this case, specific measurement examples are as follows:
[84]
- Sample preparation: thermoplastic resin or thermoplastic resin composition prepared by extrusion kneading machine
[85]
- Sample pretreatment: Trimming (23℃) → Hydrazine treatment (72℃, 5 days) → Sectioning (-120℃) → OsO 4 vapor staining 2 hours
[86]
- Analysis instrument: TEM (Jeol, JEM-1400)
[87]
- Analysis conditions: Acc. Volt 120KV, SPOT Size 1 (X 10K, X 25K, X 50K)
[88]
- Size (average particle diameter) measurement: average of diameters with the top 10% in diameter size
[89]
The i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer may be included in an amount of preferably 3 to 15% by weight, more preferably 5 to 13% by weight, within this range, weather resistance, fluidity, and tensile strength. It has excellent strength, impact strength and colorability.
[90]
ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
[91]
The ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer preferably contains 40 to 60 wt% of an acrylate rubber having a DLS average particle diameter of 0.33 to 0.5 μm or a TEM average particle diameter of 0.28 to 0.45 μm, aromatic vinyl compound 25 to 45% by weight and 10 to 20% by weight of the vinyl cyanide compound, and has excellent effects in weather resistance, fluidity, tensile strength and impact strength within this range.
[92]
ii) The acrylate rubber of the graft copolymer may preferably have a DLS average particle diameter of 0.35 to 0.5 μm, more preferably 0.35 to 0.45 μm, still more preferably 0.38 to 0.45 μm, most preferably 0.38 to 0.42 μm And within this range, it has good weather resistance and excellent mechanical strength such as fluidity, tensile strength and impact strength.
[93]
As a preferred example, the ii) 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, and weather resistance, within this range, It has excellent fluidity, tensile strength and impact strength.
[94]
The ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer may be included in an amount of preferably 5 to 15% by weight, more preferably 10 to 15% by weight, within this range, weather resistance, fluidity, and tensile strength. It has excellent strength and impact strength.
[95]
The ii) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, it has excellent effects in weather resistance, fluidity, tensile strength and impact strength.
[96]
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.
[97]
iii) Heat-resistant styrenic resin
[98]
The iii) heat-resistant styrene-based resin may preferably be an α-methylstyrene-vinyl cyan compound copolymer, and in this case, mechanical properties and heat resistance are excellent.
[99]
The iii) heat-resistant styrene-based resin preferably includes 63 to 73 wt% of α-methylstyrene , 0 to 10 wt% of styrene, and 25 to 33 wt% of a vinyl cyanide compound, and mechanical properties and heat resistance within this range and the like have excellent advantages.
[100]
The iii) heat-resistant styrene-based resin is preferably 1 to 20% by weight, more preferably 5 to 17% by weight, even more preferably 5 to 15% by weight, within this range, mechanical properties and heat resistance, etc. This has excellent advantages.
[101]
The alpha-methylstyrene-acrylonitrile copolymer preferably comprises 70 to 75 wt% of alpha-methylstyrene and 25 to 30 wt% of acrylonitrile, and more preferably 60 to 75 wt% of alpha-methylstyrene. %, 0-10 wt% styrene and 20-30 wt% acrylonitrile, or 65-75 wt% alpha-methylstyrene, 0-10 wt% styrene and 25-30 wt% acrylonitrile More preferably, it comprises 60 to 75% by weight of alpha-methylstyrene, 5 to 10% by weight of styrene, and 20 to 30% by weight of acrylonitrile, or 60 to 70% by weight of alpha-methylstyrene, It may include 5 to 10% by weight of styrene and 25 to 30% by weight of acrylonitrile, and within this range, there is an excellent effect of heat resistance and the like.
[102]
The alpha-methylstyrene-acrylonitrile copolymer preferably has a weight average molecular weight of 80,000 to 120,000 g/mol, more preferably 80,000 to 100,000 g/mol, and has excellent mechanical properties and heat resistance within this range. It works.
[103]
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.
[104]
The iii) heat-resistant styrene-based resin may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, and in this case, heat resistance and fluidity are excellent.
[105]
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.
[106]
iv) Aromatic vinyl compound-vinyl cyan compound-methacrylate copolymer
[107]
The iv) aromatic vinyl compound-vinyl cyan compound-methacrylate copolymer preferably contains 65 to 85% by weight of a methacrylate-based monomer, 10 to 30% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinyl cyanide compound. It can be made, and within this range, there is an effect excellent in weather resistance, mechanical properties, colorability and processability.
[108]
The iv) aromatic vinyl compound-vinyl cyan compound-methacrylate copolymer may be included in an amount of preferably 10 to 25% by weight, more preferably 10 to 20% by weight, even more preferably 12 to 18% by weight, Within this range, there are advantages of excellent weather resistance, mechanical properties, colorability and processability.
[109]
In the present description, the methacrylate monomer may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples thereof include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylbutyl methacrylate. , may be at least one selected from the group consisting of 2-ethylhexyl methacrylate and lauryl methacrylate, preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, more preferably methyl methacrylate.
[110]
The iv) aromatic vinyl compound-vinyl cyan compound-methacrylate copolymer preferably has a weight average molecular weight of 70,000 to 200,000 g/mol or 70,000 to 190,000 g/mol, more preferably 100,000 to 150,000 g/mol mol, and more preferably 120,000 to 140,000 g/mol, within this range, weather resistance is better, and fluidity, tensile strength and impact strength are also excellent.
[111]
The iv) aromatic vinyl compound-vinyl cyan compound-methacrylate copolymer may be prepared by, for example, solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and is preferably prepared by solution polymerization or bulk polymerization, Solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization are not particularly limited in the case of polymerization methods commonly carried out in the art to which the present invention belongs.
[112]
polyamide resin
[113]
The polyamide refers to a thermoplastic polymer including an amide bond, and specific examples include polyamide 6, polyamide 66 (PA 6.6), polyamide 46, polyamide ll, polyamide 12, polyamide 610, polyamide 612, polyamide 612 Amide 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, Polyamide 6/6T/6I, Polyamide 66/6T/6I, Polyamide 9T, Polyamide 9I, Polyamide 6/9T, Polyamide 6/9I, Polyamide 66/9T , polyamide 6/12/9T, polyamide 66/12/9T, polyamide 6/12/9I and polyamide 66/12/6I may be at least one selected from the group consisting of, preferably polyamide 6, polyamide 6.6 or a mixture thereof, and more preferably polyamide 66 (PA 6.6).
[114]
The polyamide resin preferably comprises 1 to 10% by weight, more preferably 3 to 10% by weight, still more preferably 5 to 10% by weight, most preferably 5 to 6% by weight, within this range There is an advantage in that the gloss is lowered, the matte effect is large and the physical property balance is excellent.
[115]
The polyamide may have a melting point of, for example, 230 °C or higher, preferably 240 °C or higher, more preferably 250 °C or higher, and even more preferably 260 to 270 °C.
[116]
The polyamide has, for example, a relative viscosity (96% sulfuric acid solution) of 2.0 to 4.0, preferably 2.0 to 3.5, more preferably 2.0 to 3.0, and still more preferably 2.4 to 2.7.
[117]
In the present description, the relative viscosity can be measured with an Ubbelohde viscometer by the ISO 307 sulfuric acid method.
[118]
The method for preparing the polyamide is not particularly limited as long as it is a polymerization method commonly carried out in the art to which the present invention pertains, and may be commercially purchased and used if it meets the definition of polyamide according to the present invention.
[119]
Thermoplastic resin composition
[120]
The thermoplastic resin composition of the present disclosure may preferably have a reduced volume of 15 to 40, more preferably 18 to 40, still more preferably 20 to 35, even more preferably 20 to 30, It has the advantage of providing an exterior material with superior emotional qualities such as softness, luxury, and naturalness through improved surface texture and even and low gloss while having mechanical properties and workability equal to or greater than that of conventional ASA-based resins within the range.
[121]
The thermoplastic resin composition is, for example, 0.1 to 5 parts by weight of the inorganic pigment in 100 parts by weight of the total thermoplastic resin composition, preferably 0.1 to 2 parts by weight, more preferably 0.1 to 1 parts by weight, more preferably 0.3 to 0.6 It may be included in parts by weight, and there is an excellent effect of weather resistance and hiding power within this range.
[122]
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. For example, 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 pigments; Chrome Yellow, Zinc Chromate, Cadmium Y.; 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 .
[123]
The thermoplastic resin composition preferably has an average surface roughness (Ra) of 2.2 or less, more preferably 2.1 or less, measured at 5 points using an optical profiler system, preferably 1.9 to 2.2, and more preferably 1.9 to 2.1. In this range, softness, luxury, and naturalness have excellent effects.
[124]
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 7 or less. It may be a resin composition, and there is an effect of excellent balance of physical properties while excellent matte properties within this range. Accordingly, the thermoplastic resin composition of the present disclosure may also be referred to as a matte thermoplastic resin composition.
[125]
The thermoplastic resin composition may have a weather resistance (ΔE) of 5.0 or less, preferably 4.9 or less, more preferably 4.0 or less, and still more preferably 3.5 or less, as measured by the SAE J1960 method for 2000 hours.
[126]
The thermoplastic resin composition has, for example, a flow index (MI) (220° C., load 10 kg) according to ASTM D1238 of 4 g/10 min or more, preferably 5 g/10 min or more, and more preferably 6 g/10 min or more. and more preferably 9 g/10 min or more, and may be 4 to 15 g/10 min as a specific example.
[127]
The thermoplastic resin composition, for example, has a tensile strength (1/8 inch) according to ASTM 638 of 350 kg/cm 2 or more, preferably 380 kg/cm 2 or more, more preferably 450 kg/cm 2 or more, and still more preferably 470 kg/cm 2 or more, and may be 380 to 490 kg/cm 2 as a specific example.
[128]
The thermoplastic resin composition has an Izod impact strength (1/4 inch) of 6 kg·cm/cm or more, preferably 7 kg·cm/cm or more, according to ASTM 256, as an example, and specifically, 6 to 11 kg·cm /cm.
[129]
The thermoplastic resin composition is optionally a heat stabilizer, a light stabilizer, a dye, a colorant, a mold release agent, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a flame retardant, a flame retardant, an anti-drip agent, a friction-resistant agent and a group consisting of abrasion-resistant agents 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 of one or more selected from There is an advantage in that the necessary physical properties are well realized without having to do it.
[130]
The method for producing the thermoplastic resin composition of the present invention includes, for example, an acrylate rubber having a DLS average particle diameter of 0.25 to 0.32 μm or a TEM average particle diameter of 0.2 to 0.27 μm based on the total weight of the styrene-based resin in an amount of 5 to 30 wt. to 99.5% by weight; and 0.5 to 10% by weight of the polyamide resin, and then mixing to prepare pellets using an extrusion kneader under 220 to 280°C conditions, in this case mechanical properties compared to conventional ASA-based resins and There is an advantage in providing a thermoplastic resin composition that has excellent weather resistance, low gloss, even surface gloss, and low surface roughness value while maintaining processability and the like at the same or higher level, giving an emotionally soft feeling.
[131]
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.
[132]
The step of preparing the pellets using the extrusion kneader is suitable for processing at a temperature higher than the Tm of nylon, so it may be preferably carried out under 220 to 280 ℃, more preferably under 250 to 280 ℃, at this time the temperature is the temperature set in the cylinder.
[133]
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.
[134]
exterior material
[135]
The exterior material of the present substrate is characterized in that it contains the thermoplastic resin composition of the present substrate, and in this case, mechanical properties and processability are equal or higher than that of the conventional ASA resin, and smoothness, luxury and naturalness due to the improvement of even and low gloss and surface texture There is an advantage in that the emotional quality such as sensibility is excellent.
[136]
The exterior material may be, for example, an extrusion-molded article or an injection-molded article, preferably a siding material, a roofing material, or a decking material, and more preferably a sliding door or a window.
[137]
The exterior material may preferably be prepared including the step of extruding or injecting the thermoplastic resin composition of the present base at a molding temperature of 190 to 250 ℃, preferably 210 to 240 ℃, within this range, the product has a matting effect. It has the advantage of being well expressed.
[138]
In describing the thermoplastic resin composition of the present invention, its manufacturing method and the exterior material, 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.
[139]
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.
[140]
[Example]
[141]
Materials used in Examples 1 to 8 and Comparative Examples 1 to 5 below are as follows.
[142]
A-1) Graft copolymer of emulsion polymerization (40 wt% of butyl acrylate polymer-derived units having an average particle diameter of 280 nm, 48 wt% of styrene-derived units, 12 wt% of acrylonitrile-derived units)
[143]
A-2) emulsion polymerization type graft copolymer (units derived from butyl acrylate polymer with an average particle diameter of 100 nm, 50% by weight, styrene-derived units 36% by weight, acrylonitrile-derived units 14% by weight);
[144]
A-3) Graft copolymer of emulsion polymerization (50 wt% of butyl acrylate polymer units having an average particle diameter of 400 nm, 37 wt% of styrene-derived units, 13 wt% of acrylonitrile-derived units)
[145]
B-1) Bulk polymerization method SAN resin (90RF)
[146]
B-2) Bulk polymerization method SAN resin (97HC)
[147]
B-3) Bulk polymerization method SAN resin (200UH)
[148]
C) Bulk polymerization method SAMMA resin (XT500)
[149]
D) PA 6.6
[150]
Examples 1 to 8 and Comparative Examples 1 to 5
[151]
Each of the components and contents described in Table 1 below were prepared into pellets using an extrusion kneader at 36 pie specifications at 280 ° C., and uniformly produced as a film with a thickness of 0.15T through a film extruder, and then as a sample Thus, it was measured according to the following measurement method. At this time, the film extruder uses a single screw extruder for sheet molding (manufactured by Collin, E20T product, 20 pie, L/D: 25), and the temperature condition is 50, 200, 210, 210 ° C. And the die part temperature was set to 220, 220, 230 ℃. The pellets were sufficiently dried in an oven at 80° C. for 3 hours or longer before input into the film extruder to remove the moisture influence, and then put into the inlet of the film extruder to uniformly produce a film with a thickness of 0.15T. The temperature of the used rear end roller was set to 85° C. using water as a medium, and the roller configuration was a type in which only one side of the resin extruded through the T-die is in contact with the roll as shown in FIG. 1 below. Here, the RPM of the film extruder screw was fixed at 100 and the linear speed of the roll was adjusted so that the thickness of the film was 0.15T. Here, the surface roughness value Ra and the film gloss were measured for the surface in contact with the first roll among the extruded film surfaces. For reference, when measuring with a surface that is not in contact with the first roll, a difference in surface roughness may occur.
[152]
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.
[153]
[Test Example]
[154]
The properties of the pellets, sheets and specimens prepared in Examples 1 to 8 and Comparative Examples 1 to 5 were measured by the following method, and the results are shown in Table 1 below.
[155]
* Melt index (MI): The prepared pellets were measured by the ASTM D1238 method under the conditions of 220 ℃ / 10 kg.
[156]
* Tensile strength (kg/cm 2 ): Measured by ASTM 638 method.
[157]
* Izod impact strength (kg.cm/cm): The specimen thickness was 1/4" and was measured by ASTM 256 method.
[158]
* Film Gloss: Measured at 60° with a gloss meter VG7000.
[159]
* Reduced volume: It is measured using Equation 1 below.
[160]
[Equation 1]
[161]
Converted volume = [1/6Π(R A ) 3 (A/A+B+C) + 1/6Π(R B ) 3 (B/A+B+C) + 1/6Π(R C ) 3 (C /A+B+C)] / [1/6(R C ) 3 ]
[162]
Here, R A is the average particle diameter (nm) of the rubber having the largest average particle diameter among the rubbers included in the resin composition, and RB is the average particle diameter of the rubber having the average particle diameter of the middle size among the rubbers included in the resin composition ( nm), and R C is the average particle diameter (nm) of the rubber having the smallest average particle diameter among the rubbers included in the resin composition. In addition, A is the weight % of the graft polymer having the largest average particle diameter among the rubbers included in the resin composition, and B is the weight % of the graft polymer having the average particle diameter of the middle size among the rubbers included in the resin composition, wherein C is the weight % of the graft polymer having the smallest average particle diameter among rubbers included in the resin composition. In addition, B has a value of "0" in the case where a rubber having an average particle diameter of an intermediate size is not included in the resin composition of the present disclosure.
[163]
* Surface roughness value (Ra): Optical profiler system (NV-2700, Nanosystem Co., Ltd.) Objective lens: 10x X eyepiece 1x (FOV: 628㎛ x 471㎛), Mode: WSI Envelope and Scan range: ± 5 points were measured under the condition of 30 μm and averaged. When the surface roughness value is low, the hand feels soft to the touch and the gloss is even.
[164]
* Weather resistance: After 2000 hours of measurement by the SAE J1960 method, it was evaluated as ΔE calculated by Equation 2 below. When the ΔE value is low, the weather resistance is excellent.
[165]
[Equation 2]
[166]
△E=√{(LL') 2 + (aa') 2 + (bb') 2 }
[167]
(√: sign of the root)
[168]
[Table 1]
(parts by weight) Example comparative example
One 2 3 4 5 6 7 8 One 2 3 4 5
A-1 38 38 33 33 30 40 39 30
A-2 5 5 14 13 13 8 38
A-3 8 8 25 25 30 38
B-1 41 51 41 20 20 41 50 15 41 41 51 41 41
B-2 36 36 41
B-3 5 15 5 15 5 15 15
C 15 15
B-4
D 6 6 6 6 6 5 6 6 6 6 6 6 6
TiO 2 pigment 0.60 0.60 0.60 0.60 0.60 0.60 0.6 0.6 0.60 0.60 0.60 0.60 0.60
flow index 9.6 11.3 9.0 6.3 5.9 4.3 9.9 5.6 7.9 9.2 9.9 9.50 7.7
The tensile strength 469 487 479 487 477 385 474 479 442 444 450 532 438
impact strength 6.71 6.21 6.74 7.53 8.61 10.1 6.6 8.96 7.11 6.48 6.45 2.81 7.4
Film Gloss 5.7 5.7 4.6 6.4 5.8 7 6.9 5.6 4.3 4.7 5.1 6.1 4.7
surface roughness 1.96 1.91 2.09 2.03 2.13 1.90 1.48 2.04 2.82 2.81 2.94 2.32 3.93
converted volume 22 22 19.2 19.2 30.8 16.5 22 30.8 42.4 42.4 50.7 1.0 64
[169]
As shown in Table 1, the thermoplastic resin composition (see Examples 1 to 8) according to the present invention is a first styrenic polymer according to the present invention, medium-diameter acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer Compared to Comparative Examples 1 to 5 which does not contain It was confirmed that it had a natural, soft and luxurious feel.
[170]
For reference, in the case of Comparative Example 4, which does not follow the present invention, it can be seen that the roughness value is somewhat low, but the impact strength and the like are very poor, so that it can be confirmed that it does not meet the purpose of the present invention at all.
Claims
[Claim 1]
90 to 99.5% by weight of a styrene-based resin comprising 5 to 30% by weight of an acrylate rubber having a DLS average particle diameter of 0.25 to 0.32 μm or a TEM average particle diameter of 0.2 to 0.27 μm, based on the total weight of the styrene-based resin; and 0.5 to 10 wt% of a polyamide resin.
[Claim 2]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a reduced volume calculated by the following Equation 1 of 15 to 40. [Equation 1] Converted volume = [1/6Π(R A ) 3 (A/A+B+C) + 1/6Π(R B ) 3 (B/A+B+C) + 1/6Π(R C ) ) 3 (C/A+B+C)] / [1/6(R C ) 3 ] (In Formula 1, R A is the average particle diameter of the rubber having the largest average particle diameter among rubbers included in the resin composition (nm) ), and RB is the average particle diameter (nm) of a rubber having an average particle diameter of a medium size among rubbers included in the resin composition, and R Cis the average particle diameter (nm) of the rubber having the smallest average particle diameter among the rubbers included in the resin composition, wherein A is the weight% of the graft polymer having the largest average particle diameter among the rubbers included in the resin composition, and B is It is the weight % of the graft polymer having an average particle diameter of medium size among the rubbers included in the resin composition, and C is the weight % of the graft polymer having the smallest average particle diameter among the rubbers included in the resin composition.)
[Claim 3]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an average surface roughness (Ra) of 2.2 or less measured at 5 points using an optical profiler system.
[Claim 4]
According to claim 1, wherein the styrene-based resin comprises at least two selected from the group consisting of a first styrene-based resin, a second styrene-based resin, and a third styrene-based resin, the first styrene-based resin has an average particle diameter of 0.25 to An acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising 30 to 50 wt% of an acrylate rubber of 0.32 μm, the second styrene-based resin is an aromatic vinyl compound-vinyl cyan compound copolymer, and the third The sterene-based resin is i) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising 45 to 65 wt% of an acrylate rubber having a DLS average particle diameter of 0.05 to 0.2 μm or a TEM average particle diameter of 0.04 to 0.14 μm, ii ) An acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising 45 to 65 wt% of an acrylate rubber having a DLS average particle diameter of 0.33 to 0.5 μm or a TEM average particle diameter of 0.28 to 0.45 μm, iii) a heat-resistant styrenic resin and iv) at least one selected from the group consisting of methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer.
[Claim 5]
The method of claim 1, wherein the styrene-based resin is 20 to 50% by weight of the first styrene-based resin, 10 to 60% by weight of the second styrene-based resin, and 1 to 30% by weight of the third styrene-based resin, based on the total weight of the thermoplastic resin composition. A thermoplastic resin composition comprising a.
[Claim 6]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises 0.1 to 5 parts by weight of the inorganic pigment in 100 parts by weight of the thermoplastic resin composition.
[Claim 7]
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.
[Claim 8]
5. The method of claim 4, wherein the first styrene-based resin comprises 30 to 50 wt% of an acrylate rubber having a DLS average particle diameter of 0.25 to 0.32 μm or a TEM average particle diameter of 0.2 to 0.27 μm, 40 to 60 wt% of an aromatic vinyl compound, and a vinyl cyan compound 8 A thermoplastic resin composition, characterized in that it is an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising from 18 wt%.
[Claim 9]
The thermoplastic resin composition according to claim 4, wherein the second styrene-based resin is an aromatic vinyl compound-vinyl cyan compound copolymer comprising 65 to 80 wt% of an aromatic vinyl compound and 20 to 35 wt% of a vinyl cyan compound.
[Claim 10]
5. The method according to claim 4, wherein the second styrenic resin comprises a) 10 to 60 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 90,000 to 150,000 g/mol, and b) based on the total weight of the thermoplastic resin composition. A thermoplastic resin composition comprising 0 to 40 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of greater than 150,000 g/mol and less than or equal to 200,000 g/mol.
[Claim 11]
5. The method of claim 4, wherein i) the acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer has a DLS average particle diameter of 0.05 to 0.2 μm or a TEM average particle diameter of 0.04 to 0.14 μm, 45 to 65% by weight of an acrylate rubber, aromatic 25 to 45 wt% of a vinyl compound and 8 to 18 wt% of a vinyl cyan compound, wherein the ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer has a DLS average particle diameter of 0.33 to 0.5 μm or a TEM average 45 to 65% by weight of an acrylate rubber having a particle diameter of 0.28 to 0.45 μm, 25 to 45% by weight of an aromatic vinyl compound, and 8 to 18% by weight of a vinyl cyanide compound, wherein iii) the heat-resistant styrene-based resin is preferably α -Methylstyrene 63 to 73% by weight, styrene 0 to 10% by weight and 25 to 33% by weight of a vinyl cyan compound, wherein the iv) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer is methacrylate A thermoplastic resin composition comprising 60 to 80% by weight of a system monomer, 10 to 30% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinyl cyanide compound.
[Claim 12]
5. The method of claim 4, wherein the i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is included in an amount of 1 to 20 wt%, and wherein the ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is included. The coal is included in an amount of 1 to 20 wt%, the iii) heat-resistant styrene-based resin is included in an amount of 1 to 25 wt%, and the iv) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer is 5 to 30 wt% A thermoplastic resin composition comprising a.
[Claim 13]
According to claim 1, wherein the polyamide resin is polyamide 6, polyamide 66 (PA 6.6), polyamide 46, polyamide ll, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66, poly Amide 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, polyamide 6/6T/6I, polyamide 66/6T/6I, polyamide 9T, polyamide 9I, polyamide 6/9T, polyamide 6/9I, polyamide 66/9T, polyamide 6/12 A thermoplastic resin composition, characterized in that at least one selected from the group consisting of /9T, polyamide 66/12/9T, polyamide 6/12/9I and polyamide 66/12/6I.
[Claim 14]
The exterior material comprising the thermoplastic resin composition of any one of claims 1 to 13.
[Claim 15]
15. The facing material of claim 14, wherein the facing material is a siding material, a roofing material or a decking material.