The present invention relates to a thermoplastic resin composition and an exterior material thereof, and more particularly, to a conventional ASA-based resin, mechanical properties and processability are equal to or higher than those of conventional ASA-based resins, and have excellent natural coloring quality due to even and low gloss and uniform refractive index control, as well as PVC resin composition. It relates to a low-gloss thermoplastic resin composition capable of reducing appearance defects due to excellent extrusion processability and an exterior material thereof.
background art
[4]
Acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as 'ASA resin') has weather resistance, aging resistance, chemical resistance, rigidity, impact resistance and processability, and has various uses, such as automobiles, miscellaneous goods, and construction materials It is widely used in fields such as
[5]
In the field of exterior materials, customer preference for molded products with excellent matt effect and natural coloring is greatly increasing, but the development of matt ASA resin that can meet this requirement is insufficient.
[6]
Conventionally, low-gloss ASA resins have been implemented by adding crystalline resins such as syndiotactic polystyrene (hereinafter referred to as 'sPS') to ASA resins or using ABS resins having a large particle size of several microns (㎛). In the case of sPS, there were difficulties such as a decrease in colorability and a significant decrease in weather resistance in the case of an ABS resin having a large particle size.
[7]
Notably, when molding as a siding material or decking board material, it is provided through co-extrusion with PVC resin. It is necessary to provide natural colorability and heat resistance while realizing an invisible appearance.
[8]
In the past, an amorphous polymer such as polymethyl methacrylate (hereinafter referred to as 'PMMA') was added to improve colorability, but impact reduction occurred, and in the case of heat-resistant SAN resin to improve heat resistance, colorability was reduced. There are still limitations in being able to identify trade-offs.
[9]
[10]
[Prior art literature]
[11]
[Patent Literature]
[12]
Korean Patent Publication No. 2019-0114898
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[13]
In order to solve the problems of the prior art as described above, the present invention maintains equal or higher mechanical properties, weather resistance and processability compared to the conventional ASA resin, provides even and low gloss and uniform refractive index, so that the natural coloring quality is excellent, It is an object of the present invention to provide a low-gloss thermoplastic resin composition capable of reducing appearance defects due to excellent PVC co-extrusion processability.
[14]
Another object of the present invention is to provide a molded article manufactured from the above thermoplastic resin composition.
[15]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[16]
In order to achieve the above object, the present invention
[17]
A-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle size of 0.33 to 0.5 μm and A-2) an alkyl acrylate rubber having an average particle size of 0.05 to 0.2 μm 10 to 50% by weight of the total weight of the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising;
[18]
B-1) 0 to 30 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 67 to 75 wt% of an aromatic vinyl compound and 25 to 33 wt% of a vinyl cyan compound;
[19]
B-2) 20 to 70 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 70 to 75 wt % of an aromatic vinyl compound and 25 to 30 wt % of a vinyl cyan compound; and
[20]
C) 0.5 to 10% by weight of a polyamide resin having a melting temperature (Tm) of 250 ° C or higher,
[21]
The graft copolymer A-1) and the graft copolymer A-2) provide a thermoplastic resin composition characterized in that the color development coverage value (X) calculated by Equation 1 is 20% or more, respectively.
[22]
[Equation 1]
[23]
X = {A/S} * 100
[24]
(In Equation 1, S is the content (wt%) of the meltable material (sol) after dissolving the graft copolymer in acetone and centrifuging, and A is dissolving the graft copolymer in acetone and centrifuging. Indicates the content (wt%) of the vinyl cyan compound in the subsequent meltable material (sol).
[25]
The sum of the above A-1) graft copolymer and A-2) graft copolymer and the above B-1) aromatic vinyl compound-vinyl cyan compound copolymer and B-2) aromatic vinyl compound-vinyl cyan compound copolymer The weight ratio of the combined contents ((A-1 + A-2): (B-1 + B-2)) may be 1:0.5 to 1:2.
[26]
The thermoplastic resin composition may have a black and white color strength (N) of 100 or more calculated by Equations 3 and 5 below.
[27]
[Equation 3]
[28]
Monochrome color index (N) = ∑ (absorption value of sample sample)/∑ (absorption value of standard sample) Ⅹ 100
[29]
(In Equation 3, the absorption value of the sample is the calculated absorption value of the solid sample calculated by the Kubelka-Munk equation represented by Equation 5 below, and ∑ is the integral value in the entire spectrum of 400 to 700 nm)
[30]
[Equation 5]
[31]
Calculated absorption value of solid sample = (1-R) 2 / 2R
[32]
(In Equation 5, R uses the value of the reflection coefficient measured by the method of CIE Lab with X-lite Color-eye 7000A.)
[33]
The thermoplastic resin composition may have a color strength (C) of 110 or more calculated by Equations 4 and 5 below.
[34]
[Equation 4]
[35]
Color development index (C) = λmax (absorption value of sample sample) / λmax (absorption value of standard sample) Ⅹ 100
[36]
(In Equation 4, the absorption value is the solid sample absorption value calculated by the Kubelka-Munk equation represented by Equation 5 above, and λmax is the highest absorption wavelength over the entire spectrum)
[37]
A weight ratio (A-1 : A-2) of the A-1) graft copolymer and the A-2) graft copolymer may be 1:0.54 to 1:1.50.
[38]
The A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises 30 to 60% by weight of an acrylate rubber having an average particle diameter of 0.33 to 0.5 μm, 20 to 50% by weight of an aromatic vinyl compound, and 10 to 50% by weight of a vinyl cyan compound. 30% by weight, and the A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises 30 to 60% by weight of acrylate rubber having an average particle diameter of 0.05 to 0.2 μm and 20 to 60% by weight of an aromatic vinyl compound 50% by weight and 10 to 30% by weight of a vinyl cyan compound.
[39]
The B-1) aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of 100,000 to 150,000 g/mol, and the B-2) aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight greater than 150,000 g/mol It may be less than 200,000 g / mol.
[40]
Based on the total weight of the thermoplastic resin composition, the B-1) aromatic vinyl compound-vinyl cyan compound copolymer is included in 10 to 30% by weight, and the B-2) aromatic vinyl compound-vinyl cyan compound copolymer is 30 to 60% by weight.
[41]
A-1) graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, and B-2) aromatic vinyl compound-vinyl cyan compound copolymer comprising The thermoplastic resin composition, characterized in that the color development coverage value (Xa1 + Xa2 + Xb1 + Xb2) calculated by the following Equation 6-1 is 20 to 33%.
[42]
[Equation 6-1]
[43]
Xa1 + Xa2 + Xb1 + Xb2 = {(Aa1/Sa1) + (Aa2/Sa2) + (Ab1/Sb1) + (Ab2/Sb2)} * 100
[44]
(In Equation 6-1, Sa1, Sa2, Sb1, and Sb2 are A-1) graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, B-2) The aromatic vinyl compound-vinyl cyan compound copolymer is dissolved in acetone and centrifuged, respectively, and is the content (or weight %) of the meltable material (sol), Aa1, Aa2, Ab1, and Ab2 are A-1 ) Graft copolymer, A-2) Graft copolymer, B-1) Aromatic vinyl compound-vinyl cyan compound copolymer, B-2) Dissolving the aromatic vinyl compound-vinyl cyan compound copolymer in acetone and centrifuging It represents the content (or weight %) of the vinyl cyanide compound in the meltable material (sol) after
[45]
Furthermore, 0.1 to 5 parts by weight of the pigment or dye (D) may be included based on 100 parts by weight of the thermoplastic resin composition.
[46]
The weight ratio (D:C) of the pigment or dye (D) and the polyamide resin (C) may be greater than 1:1 and less than 1:10.
[47]
[48]
In addition, the present invention A-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle diameter of 0.33 to 0.5 μm and A-2) an average particle diameter of 0.05 to 0.2 μm 10 to 50% by weight of the total weight of the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including the alkyl acrylate rubber;
[49]
B-1) Aromatic composition comprising 67 to 75% by weight of an aromatic vinyl compound and 25 to 33% by weight of a vinyl cyan compound
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5,000 character limit. Use the arrows to translate more.0 to 30% by weight of a vinyl compound-vinyl cyan compound copolymer;
[50]
B-2) 20 to 70 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 70 to 75 wt % of an aromatic vinyl compound and 25 to 30 wt % of a vinyl cyan compound; and
[51]
C) A thermoplastic resin composition containing 0.5 to 10% by weight of a polyamide resin having a melting temperature (Tm) of 250 °C or higher is provided.
[52]
[53]
In addition, the present invention provides an exterior material comprising the thermoplastic resin composition described above.
[54]
The facing material may be a siding material, a roofing material or a decking board material.
Effects of the Invention
[55]
According to the present invention, compared to conventional ASA resins, mechanical properties and processability are equivalent or better, and natural coloring quality is excellent due to even and low gloss and uniform refractive index control, as well as low-gloss thermoplastic that can reduce appearance defects due to excellent PVC co-extrusion processability. There is an effect of providing a resin composition and a molded article thereof.
[56]
Therefore, the thermoplastic resin composition and molded article according to the present invention can be widely used in the fields of siding materials, roofing materials, or decking board materials that require them. Specifically, it can be applied as a sliding door or window material.
Mode for Carrying Out the Invention
[57]
Hereinafter, the thermoplastic resin composition of the present disclosure and its packaging material will be described in detail.
[58]
The present inventors have formulated an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, an aromatic vinyl compound-vinyl cyan compound copolymer, and a polyamide resin containing an acrylate-based rubber having a predetermined average particle diameter in a predetermined ratio, , If the color development coverage value of the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is adjusted within a predetermined range, ASA resin and polyamide can be obtained without lowering mechanical properties and processability compared to conventional ASA resin compositions. It was confirmed that the compatibility between the resins was improved, the color development was excellent, and the improved gloss and colorability were provided, and based on this, further research was conducted to complete the present invention.
[59]
[60]
The thermoplastic resin composition of the present invention includes A-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle size of 0.33 to 0.5 μm and A-2) an average particle size of 0.05 to 0.2 10 to 50% by weight of the total weight of the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including the alkyl acrylate rubber having a thickness of ㎛; B-1) 0 to 30 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 67 to 75 wt% of an aromatic vinyl compound and 25 to 33 wt% of a vinyl cyan compound; B-2) 20 to 70 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 70 to 75 wt % of an aromatic vinyl compound and 25 to 30 wt % of a vinyl cyan compound; and C) 0.5 to 10% by weight of a polyamide resin having a melting temperature (Tm) of 250 °C or higher.
[61]
In this case, it is a low-gloss thermoplastic resin that has equal or better mechanical properties and processability compared to conventional ASA-based resins, has excellent natural coloring quality due to even and low gloss and uniform refractive index control, and has excellent PVC co-extrusion processability to reduce appearance defects. It is advantageous to provide a composition and a molded article thereof.
[62]
[63]
Hereinafter, each component constituting the thermoplastic resin composition of the present substrate will be described in detail.
[64]
[65]
A-1) Acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.33 to 0.5 μm
[66]
The A-1) acrylate rubber of the graft copolymer may preferably have an average particle diameter of 0.33 to 0.5 μm, more preferably 0.38 to 0.5 μm, and still more preferably 0.4 to 0.5 μm, Within this range, there is an effect of excellent weather resistance and excellent mechanical properties such as fluidity, tensile strength and impact strength.
[67]
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 (TS 35-50 wt%) 1,000-5,000 times with distilled water, and the measurement method is auto-dilution and measured with a flow cell, and the measurement mode is a dynamic light scattering method ( dynamic light scattering) method / Intensity 300KHz / Intensity-weight Gaussian Analysis, and the setting value can be measured at a temperature of 23 ° C, a measurement wavelength of 632.8 nm, and a channel width of 10 μsec.
[68]
In addition, in the present description, the 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.
[69]
[70]
The A-1) graft copolymer is, for example, 50 to 90% by weight, preferably 50 to 80% by weight, more preferably 50 to 90% by weight, based on the total weight of the A-1) and A-2) graft copolymers 70% by weight, and within this range, there is an excellent effect on weather resistance, fluidity, tensile strength and impact strength.
[71]
[72]
The A-1) graft copolymer comprises, for example, 40 to 60% by weight of the acrylate rubber, 20 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound, preferably the acrylic 40 to 60% by weight of late rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound, more preferably 45 to 55% by weight of the acrylate rubber, 30 to 45% by weight of an aromatic vinyl compound 40% by weight and 10 to 20% by weight of a vinyl cyan compound, and within this range, excellent effects in weather resistance, fluidity, tensile strength and impact strength are obtained.
[73]
In the present description, a polymer comprising a certain compound means a polymer polymerized including the compound, and a unit in the polymerized polymer is derived from the compound.
[74]
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 an alkyl group, preferably an alkyl acrylate having 4 to 8 carbon atoms in an alkyl group, and more preferably butyl acrylate or ethylhexyl acrylate.
[75]
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 is preferably styrene.
[76]
In the present description, the vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethylacrylonitrile, and isopropylacrylonitrile, and is preferably acrylonitrile.
[77]
[78]
The A-1) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, excellent chemical resistance, weather resistance, fluidity, tensile strength and impact strength are obtained.
[79]
The emulsion polymerization is not particularly limited when the emulsion polymerization method is commonly performed in the art.
[80]
[81]
The A-1) graft copolymer preferably has a color coverage value (X) calculated by Equation 1 below of 20% or more, preferably 20 to 30%, more preferably 25 to 30%, , Within this range, mechanical properties such as impact strength, tensile strength, and flexural strength, glossiness, and colorability are excellent, and there is an effect of excellent color development and hiding power.
[82]
[Equation 1]
[83]
X = {A/S} * 100
[84]
(In Equation 1, S is the content (wt%) of the meltable material (sol) after dissolving the graft copolymer in acetone and centrifuging, and A is dissolving the graft copolymer in acetone and centrifuging. Indicates the content (wt%) of the vinyl cyan compound in the subsequent meltable material (sol).
[85]
In Equation 1, the content (wt%) of the vinyl cyan compound in the meltable material (sol) after dissolving the graft copolymer in acetone and centrifuging is the vinyl cyanide in the melt collected in the process of obtaining the gel content The compound content (based on 100% by weight of the total graft copolymer introduced) is shown. Here, the gel content represents the content of insoluble matter based on 100% by weight of the total graft copolymer.
[86]
The content of the vinyl cyanide compound in the meltable material (sol) may be measured using an NMR analyzer or FT-IR.
[87]
Specifically, the gel content was determined by adding 1 g of the graft copolymer to 60 ml of acetone, stirring at room temperature for 12 hours, centrifuging it, collecting only the insoluble content not dissolved in acetone, drying for 12 hours, and measuring the weight, It is calculated by Equation 2 below. Specifically, 1 g of the graft copolymer was added to 60 ml of acetone, stirred at 210 rpm with a stirrer (Orbital Shaker, equipment name: Lab companion SKC-6075) for 12 hours at room temperature, and then centrifuged (Supra R30, Hanil Scientific Co., Ltd.) Centrifuged at 0℃ at 18000 rpm for 3 hours using a centrifuge to collect only the insoluble matter that was not dissolved in acetone, and dried in an oven (Forced Convection Oven; equipment name: Lab companion OF-12GW) at 85℃ for 12 hours. After drying, the weight can be measured.
[88]
[Equation 2]
[89]
Gel content (% by weight) = [Weight of insoluble content (gel) (g) / weight of sample
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ContributeCrab (g)] x 100
[90]
[91]
In the present description, the color power coverage value (X) is a parameter representing the degree of dispersion of the ungrafted vinyl cyan compound in the graft copolymer and the grafted vinyl cyan compound in the alkyl acrylate rubber. As this value is higher, the vinyl cyan compound is evenly dispersed in an appropriate amount, resulting in low gloss and excellent coloring and coloring properties. However, if the color development coverage value is too large, the hiding power may be reduced, and thus the optimal compatibility may not be exhibited.
[92]
[93]
A-2) Acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.05 to 0.2 μm
[94]
The A-2) acrylate rubber of the graft copolymer may preferably have an average particle diameter of 0.05 to 0.2 μm, more preferably 0.05 to 0.17 μm, still more preferably 0.1 to 0.17 μm, more preferably It is 0.1 to 0.15 μm, and within this range, excellent weather resistance, colorability, impact strength, color development and surface gloss characteristics can be imparted to the final product.
[95]
[96]
The A-2) graft copolymer is 10 to 50% by weight, preferably 9 to 35% by weight, more preferably 12 to 50% by weight, based on the total weight of the A-1) and A-2) graft copolymers 22% by weight, and within this range, there is an excellent effect on weather resistance, fluidity, tensile strength and impact strength.
[97]
[98]
The A-2) graft copolymer may include, for example, 40 to 60% by weight of the acrylate rubber, 20 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound. 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 cyan compound, more preferably 45 to 55% by weight of the acrylate rubber and 30% by weight of an aromatic vinyl compound to 50% by weight and 5 to 20% by weight of a vinyl cyan compound, more preferably 47 to 57% by weight of the acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound It is made including, and within this range, there is an excellent effect in weather resistance, fluidity, tensile strength and impact strength.
[99]
[100]
The A-2) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, weather resistance, fluidity, tensile strength and impact strength are excellent.
[101]
The emulsion polymerization is not particularly limited when the emulsion polymerization method is commonly performed in the art.
[102]
[103]
The A-2) graft copolymer preferably has a color coverage value (X) calculated by Equation 1 of 20% or more, preferably 20 to 30%, more preferably 25 to 30%, , Within this range, mechanical properties such as impact strength, tensile strength, and flexural strength, glossiness, and colorability are excellent, and there is an effect of excellent color development and compatibility.
[104]
In the present disclosure, the color development coverage value is a parameter indicating the content of the ungrafted vinyl cyan compound in the graft copolymer and the grafted vinyl cyan compound in the alkyl acrylate rubber. As this value increases, the vinyl cyan compound is evenly dispersed, resulting in low gloss and excellent color development. However, if the color development coverage value is too large, the hiding power may decrease, so that the optimal color development and hiding power may not be exhibited.
[105]
[106]
A-1) Graft Copolymer and A-2) Blend of Graft Copolymer
[107]
A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 0.33 to 0.5 μm, and A-2) an acrylate rubber having an average particle diameter of 0.05 to 0.2 μm In the case of a mixture of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, the mechanical properties and processability are equivalent or higher than those of conventional ASA-based resins, and the colorability characteristics are greatly improved, resulting in excellent quality reliability.
[108]
Weight ratio of A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-1:A-2) may satisfy a weight ratio of, for example, 1:0.54 to 1:1.50, preferably 1:0.55 to 1:1.30, and more preferably 1:0.56 to 1:1.20, and in this case, workability, elongation, surface quality, and weather resistance And transparency, etc. have excellent effects.
[109]
[110]
B) two aromatic vinyl compound-vinyl cyan compound copolymers having different weight average molecular weights
[111]
In the present disclosure, B) two aromatic vinyl compound-vinyl cyan compound copolymers having different weight average molecular weights, for example, the aromatic vinyl compound-vinyl cyan compound copolymer preferably has B-1) a weight average molecular weight of 100,000 to 150,000 g/mol aromatic vinyl compound-vinyl cyan compound copolymer; And B-2) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of greater than 150,000 g/mol to less than 200,000 g/mol; preferably at least one selected from the group consisting of B-2) use of an aromatic vinyl compound-vinyl cyan compound copolymer alone; or the above B-1) aromatic vinyl compound-vinyl cyan compound copolymer and B-2) aromatic vinyl compound-vinyl cyan compound copolymer. In this case, heat resistance, chemical resistance, impact strength, tensile strength, processability are It has an excellent effect.
[112]
The B-1) aromatic vinyl compound-vinyl cyan compound copolymer is preferably used in an amount of 0 to 30% by weight, more preferably 0 to 25% by weight, still more preferably 0 to 20% by weight, based on the total weight of the thermoplastic resin composition. , Specific examples include 1 to 30% by weight, more specific examples 10 to 25% by weight, more specific examples include 15 to 20% by weight, in which case heat resistance, chemical resistance and impact strength, tensile strength, excellent workability It works.
[113]
The B-2) aromatic vinyl compound-vinyl cyan compound copolymer is preferably 30 to 70% by weight, more preferably 30 to 60% by weight, still more preferably 35 to 60% by weight, based on the total weight of the thermoplastic resin composition. In this case, heat resistance, chemical resistance, impact strength, tensile strength, and processability are excellent.
[114]
In the present description, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze) unless otherwise defined, and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent. ), it can be measured as a relative value for a standard PS (standard polystyrene) sample. At this time, as a specific measurement example, solvent: THF, column temperature: 40 ℃, flow rate: 0.3ml / min, sample concentration: 20mg / ml, injection amount: 5μl, column model: 1xPLgel 10 ㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10 ㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10 ㎛ MiniMix-B Guard (50x4.6mm), equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing: Agilent ChemStation S/W, test method (Mn, Mw and PDI): can be measured under OECD TG 118 conditions.
[115]
[116]
The B-1) and B-2) aromatic vinyl compound-vinyl cyan compound copolymers include, for example, 65 to 80% by weight of an aromatic vinyl compound and 20 to 35% by weight of a vinyl cyan compound, preferably aromatic vinyl. 67 to 80% by weight of the compound and 20 to 33% by weight of the vinyl cyan compound, more preferably 70 to 75% by weight of the aromatic vinyl compound and 25 to 30% by weight of the vinyl cyan compound, within this range It has excellent chemical resistance, impact strength, tensile strength, and processability within
[117]
The aromatic vinyl polymers B-1) and B-2) may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, and in this case, excellent effects such as heat resistance and fluidity are obtained.
[118]
The suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are not particularly limited when each of the solution polymerization and bulk polymerization methods commonly performed in the art to which the present invention pertains.
[119]
[120]
Excluding the use of a heat-resistant styrenic resin or a methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer in addition to the above-mentioned B-1) and B-2) aromatic vinyl compound-vinyl cyan compound copolymers in the present description is necessary for coloring and It is preferable to maintain hiding power while sufficiently implementing color development properties, but is not limited thereto.
[121]
[122]
A-1) Graft Copolymer, A-2) Graft Copolymer, and B) Two Types of Aromatic Vinyl Compound-Vinyl Cyan Compound Copolymer Blend with Different Weight Average Molecular Weights
[123]
The thermoplastic resin composition is preferably A-1) a graft copolymer and A-2) 10 to 50% by weight of the total amount of the graft copolymer and B) two aromatic vinyl compounds having different weight average molecular weights - vinyl cyan 50 to 90% by weight of the compound copolymer, more preferably 20 to 50% by weight of the total amount of A-1) graft copolymer and A-2) graft copolymer and B) weight average molecular weight 50 to 80% by weight of two different aromatic vinyl compound-vinyl cyan compound copolymers, more preferably the total amount of A-1) graft copolymer and A-2) graft copolymer
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5,000 character limit. Use the arrows to translate more.30 to 50% by weight and B) 50 to 70% by weight of two aromatic vinyl compound-vinyl cyan compound copolymers having different weight average molecular weights, more preferably A-1) graft copolymer and A- 2) 30 to 45% by weight of the total amount of the graft copolymer and B) 55 to 70% by weight of two aromatic vinyl compound-vinyl cyan compound copolymers having different weight average molecular weights, most preferably A-1 ) 30 to 40% by weight of the total amount of the graft copolymer and A-2) the graft copolymer and B) 60 to 70% by weight of two aromatic vinyl compound-vinyl cyan compound copolymers having different weight average molecular weights , Within this range, there is an effect of giving a feeling that the surface appearance of the coextruded product is improved by improving weatherability, low gloss, and colorability without deteriorating mechanical properties and processability.
[124]
The sum of the above A-1) graft copolymer and A-2) graft copolymer and the above B-1) aromatic vinyl compound-vinyl cyan compound copolymer and B-2) aromatic vinyl compound-vinyl cyan compound copolymer When the weight ratio ((A-1+A-2): (B-1+B-2)) of the combined contents is 1:0.5 to 1:2, the gloss is low, and the colorability and color development characteristics are improved to The surface appearance of the extruded product has a beautiful effect.
[125]
A-1) graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, and B-2) aromatic vinyl compound-vinyl cyan compound copolymer comprising When the color development coverage value (X) calculated by Equation 6 below of the thermoplastic resin composition is 20 to 33%, preferably 25 to 30%, the effect of improving the colorability and color development characteristics to make the surface appearance of the coextruded product beautiful there is.
[126]
[Equation 6]
[127]

[128]
(In Equation 6, Sa1, Sa2, Sb1, and Sb2 are A-1) graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, B- 2) Aromatic vinyl compound-vinyl cyan compound copolymer is dissolved in acetone and centrifuged, respectively, and is the content (or weight %) of the meltable material (sol), and Aa1, Aa2, Ab1, and Ab2 are A-1) graph After dissolving the aromatic vinyl compound-vinyl cyan compound copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, B-2) each in acetone and centrifuging It represents the content (or weight %) of vinyl cyanide compound in the meltable material (sol).

we claim

claims
[Claim 1]
A-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle diameter of 0.33 to 0.5 ㎛ and A-2) an alkyl acrylate rubber having an average particle diameter of 0.05 to 0.2 ㎛ 10 to 50% by weight of the total weight of the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising; B-1) 0 to 30 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 67 to 75 wt% of an aromatic vinyl compound and 25 to 33 wt% of a vinyl cyan compound; B-2) 20 to 70 wt % of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 70 to 75 wt % of an aromatic vinyl compound and 25 to 30 wt % of a vinyl cyan compound; and C) 0.5 to 10% by weight of a polyamide resin having a melting temperature (Tm) of 250° C. or higher, wherein the A-1) graft copolymer and A-2) graft copolymer are calculated by Equation 1 below: A thermoplastic resin composition, characterized in that the color development coverage value (X) is 20% or more, respectively. [Equation 1] X = {A/S} * 100 (In Equation 1, S is the content (wt%) of the meltable material (sol) after dissolving the graft copolymer in acetone and centrifuging, A represents the content (wt%) of the vinyl cyan compound in the meltable material (sol) after dissolving the graft copolymer in acetone and centrifuging.)
[Claim 2]
The method of claim 1, wherein the A-1) graft copolymer and A-2) the combined content of the graft copolymer and the B-1) aromatic vinyl compound-vinyl cyan compound copolymer and B-2) aromatic vinyl compound - A thermoplastic resin composition characterized in that the weight ratio ((A-1+A-2) : (B-1+B-2)) of the combined contents of the vinyl cyan compound copolymer is 1:0.5 to 1:2.
[Claim 3]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a black and white color strength (N) of 100 or more calculated by Equations 3 and 5 below. [Equation 3] Black and white color development index (N) = ∑ (absorption value of sample sample) / ∑ (absorption value of standard sample) Ⅹ 100 (In Equation 3, the absorption value is Kubelka-Munk represented by Equation 5 below) The solid sample absorption value calculated by the equation, and ∑ is the spectral integral value of the entire range of 400 to 700 nm) [Equation 5] Calculated absorption value of the solid sample = (1-R) 2 / 2R (In Equation 5 above, , R uses the reflection coefficient value measured according to the method of CIE Lab with X-lite Color-eye 7000A.)
[Claim 4]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a color strength (C) of 110 or more calculated by Equations 4 and 5 below. [Equation 4] Color development index (C) = λmax (absorption value of sample sample) / λmax (absorption value of standard sample) Ⅹ 100 (In Equation 4, the absorption value is Kubelka-Munk represented by Equation 5 below The solid sample absorption value calculated by the equation, and λmax is the highest absorption wavelength over the entire spectrum) [Equation 5] Calculated absorption value of the solid sample = (1-R) 2 / 2R (In Equation 5 above, , R uses the reflection coefficient value measured according to the method of CIE Lab with X-lite Color-eye 7000A.)
[Claim 5]
The thermoplastic according to claim 1, wherein the weight ratio (A-1 : A-2) of the A-1) graft copolymer and the A-2) graft copolymer is 1:0.54 to 1:1.50. resin composition.
[Claim 6]
The method of claim 1, wherein the A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises 30 to 60% by weight of an acrylate rubber having an average particle diameter of 0.33 to 0.5 μm and 20 to 50% by weight of an aromatic vinyl compound. and 10 to 30% by weight of a vinyl cyan compound, wherein the A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises 30 to 60% by weight of an acrylate rubber having an average particle diameter of 0.05 to 0.2 μm. A thermoplastic resin composition comprising 20 to 50% by weight of an aromatic vinyl compound and 10 to 30% by weight of a vinyl cyan compound.
[Claim 7]
The method of claim 1, wherein the B-1) aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of 100,000 to 150,000 g/mol, and the B-2) aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight A thermoplastic resin composition, characterized in that greater than 150,000 g / mol to less than 200,000 g / mol.
[Claim 8]
The method of claim 1, based on the total weight of the thermoplastic resin composition, the B-1) aromatic vinyl compound-vinyl cyan compound copolymer is included in 10 to 30% by weight, and the B-2) aromatic vinyl compound-vinyl cyan compound A thermoplastic resin composition, characterized in that the cyan compound copolymer is included in 30 to 60% by weight.
[Claim 9]
The method of claim 1, wherein the A-1) graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, and B-2) aromatic vinyl compound-vinyl cyan The thermoplastic resin composition comprising the compound copolymer has a color coverage value (Xa1 + Xa2 + Xb1 + Xb2) calculated by Equation 6-1 below of 20 to 33%. [Equation 6-1] Xa1 + Xa2 + Xb1 + Xb2 = {(Aa1/Sa1) + (Aa2/Sa2) + (Ab1/Sb1) + (Ab2/Sb2)} * 100 (in Equation 6-1 above) , Sa1, Sa2, Sb1, and Sb2 are A-1) graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, B-2) aromatic vinyl compound- The content (or weight %) of the meltable material (sol) after dissolving the vinyl cyan compound copolymer in acetone and centrifuging, respectively, and Aa1, Aa2, Ab1, and Ab2 are A-1) graft copolymer, A- 2) Graft copolymer, B-1) Aromatic vinyl compound-vinyl cyan compound copolymer, B-2) Meltable material (sol) after dissolving the aromatic vinyl compound-vinyl cyan compound copolymer in acetone and centrifuging represents the content (or weight %) of the vinyl cyanide compound in
[Claim 10]
The thermoplastic resin composition according to claim 1, which comprises 0.1 to 5 parts by weight of the pigment or dye (D) based on 100 parts by weight of the thermoplastic resin composition.
[Claim 11]
The thermoplastic resin composition according to claim 10, wherein a weight ratio (D:C) of the pigment or dye (D) and the polyamide resin (C) is greater than 1:1 and less than 1:10.
[Claim 12]
An exterior material comprising the thermoplastic resin composition according to any one of claims 1 to 11.
[Claim 13]
13. The exterior material according to claim 12, wherein the exterior material is a siding material, a roofing material or a decking board material.