The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded product including the same, and more particularly, has excellent mechanical properties such as impact strength, tensile strength, and flexural strength, surface hardness, transparency, and colorability, particularly when bending. It relates to a thermoplastic resin composition having excellent non-whitening properties that does not cause whitening, a method for preparing the same, and a molded product including the same.
background art
[4]
Acrylate-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 in the automobile, miscellaneous goods, and construction materials fields. It is widely used in etc.
[5]
On the other hand, as the demand for emotional quality and its level increase in the market, substrates such as acrylonitrile-butadiene-styrene resin, polyvinyl chloride resin, polyethylene terephthalate resin, and iron plate are finished with ASA resin, resulting in a luxurious appearance. , Research is being conducted to realize excellent colorability and weatherability.
[6]
However, due to the nature of ASA resin, whitening occurs on the surface of the product during processing processes such as cutting, bending, and molding depending on the shape of the product during the finishing process at room temperature, and the original color disappears and the aesthetics are impaired. . Since this phenomenon is caused by voids caused by cracks inside the ASA resin, in order to improve it, we have tried to solve it through softening of the resin, such as by increasing the rubber content, but the use is limited due to mechanical properties different from those of the existing ASA resin. there was.
[7]
Accordingly, there is a need to develop a thermoplastic resin composition having mechanical properties and surface hardness similar to those of conventional ASA resins, excellent transparency and colorability, and no whitening.
[8]
[9]
[Prior art literature]
[10]
[Patent Literature]
[11]
Japanese Patent Registration No. 1995-033470
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[12]
In order to solve the problems of the prior art as described above, the present substrate has excellent mechanical properties such as impact strength, tensile strength, flexural strength, surface hardness, transparency and colorability, and especially has non-whitening properties that do not cause whitening during bending. It is an object to provide an excellent thermoplastic resin composition.
[13]
In addition, an object of the present description is to provide a method for producing the above thermoplastic resin composition.
[14]
In addition, an object of the present substrate is to provide a molded article manufactured from the above thermoplastic resin composition.
[15]
[16]
All of the above and other objects of the present disclosure can be achieved by the present disclosure described below.
means of solving the problem
[17]
In order to achieve the above object, the present substrate includes (A) 35 to 85% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle diameter of 50 to 120 nm; And (B) 15 to 65% by weight of a polymethacrylate resin; and provides a thermoplastic resin composition, characterized in that the alkyl acrylate coverage value (X) calculated by Equation 1 below is 70% or more.
[18]
[Equation 1]
[19]
X = {(G-Y)/Y} * 100
[20]
(In Equation 1, G represents the gel content (% by weight) with respect to the total weight of the thermoplastic resin composition, and Y represents the content (% by weight) of alkyl acrylate in the gel with respect to the total weight of the thermoplastic resin composition.)
[21]
[22]
In addition, the substrate includes (A) 35 to 85% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle diameter of 50 to 120 nm; and (B) 15 to 65% by weight of a polymethacrylate resin, wherein the (B) polymethacrylate resin has a weight average molecular weight of 50,000 to 150,000 g/mol. there is.
[23]
[24]
In addition, the substrate includes (A) 35 to 85% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle diameter of 50 to 120 nm; And (B) 15 to 65% by weight of a polymethacrylate resin; a thermoplastic resin composition comprising a total light transmittance (Tt) of 75% or more as measured with a specimen thickness of 3T in accordance with ASTM D1003 can provide.
[25]
[26]
In addition, the substrate is (A) 35 to 85% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle diameter of 50 to 120 nm and (B) polymethacrylate Including 15 to 65% by weight of resin and kneading and extruding under conditions of 200 to 300 ° C. and 100 to 500 rpm, characterized in that the alkyl acrylate coverage value (X) calculated by Equation 1 below is 70% or more It provides a method for producing a thermoplastic resin composition.
[27]
[Equation 1]
[28]
X = {(G-Y)/Y} * 100
[29]
(In Equation 1, G represents the gel content (% by weight) with respect to the total weight of the thermoplastic resin composition, and Y represents the content (% by weight) of alkyl acrylate in the gel with respect to the total weight of the thermoplastic resin composition.)
[30]
[31]
In addition, the substrate is (A) 35 to 85% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle diameter of 50 to 120 nm and (B) polymethacrylate kneading and extruding under conditions of 200 to 300 ° C. and 100 to 500 rpm including 15 to 65% by weight of the resin, wherein the (B) polymethacrylate resin has a weight average molecular weight of 50,000 to 150,000 g/mol A method for producing a characterized thermoplastic resin composition can be provided.
[32]
[33]
In addition, the substrate is (A) 35 to 85% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle diameter of 50 to 120 nm and (B) polymethacrylate Kneading and extruding under conditions of 200 to 300 ° C. and 100 to 500 rpm including 15 to 65% by weight of the resin, and the light transmittance (Tt) measured with a specimen thickness of 3T according to ASTM D1003 It is possible to provide a method for producing a thermoplastic resin composition characterized in that 75% or more.
[34]
[35]
In addition, the present substrate provides a molded article comprising the thermoplastic resin composition.
Effects of the Invention
[36]
According to the present invention, a thermoplastic resin composition having excellent mechanical properties such as impact strength, tensile strength, and flexural strength, surface hardness, transparency, and colorability, and excellent non-whitening property that does not cause whitening during bending, and a manufacturing method thereof, and There is an effect of providing a molded article comprising the same.
Brief description of the drawing
[37]
1 is a photograph of a whitening phenomenon on a curved surface by folding 0.15 T extruded sheet specimens prepared in Examples 1, 2, 4, and 5 and Comparative Examples 2 to 5 of the present invention by hand.
Mode for Carrying Out the Invention
[38]
Hereinafter, the thermoplastic resin composition of the present disclosure, a method for preparing the same, and a molded product including the same will be described in detail.
[39]
The present inventors have formulated an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing rubber having a predetermined average particle diameter and a polymethacrylate resin in a predetermined ratio, and the alkyl acrylate coverage value in a predetermined range When adjusted within, it was confirmed that the mechanical properties, surface hardness, transparency and colorability were improved compared to the conventional ASA-based resin, and the non-whitening property was excellent in that whitening did not occur, and based on this, further research was conducted to complete the present invention.
[40]
[41]
The thermoplastic resin composition of the present disclosure includes (A) 35 to 85% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle diameter of 50 to 120 nm; And (B) 15 to 65% by weight of a polymethacrylate resin; characterized in that the alkyl acrylate coverage value (X) calculated by Equation 1 below is 70% or more. In this case, mechanical properties such as impact strength, tensile strength, and flexural strength, surface hardness, transparency, and colorability are excellent, and in particular, non-whitening properties that do not cause whitening during bending are excellent.
[42]
[Equation 1]
[43]
X = {(G-Y)/Y} * 100
[44]
(In Equation 1, G represents the gel content (% by weight) with respect to the total weight of the thermoplastic resin composition, and Y represents the content (% by weight) of alkyl acrylate in the gel with respect to the total weight of the thermoplastic resin composition.)
[45]
[46]
Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each component.
[47]
[48]
(A) Alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
[49]
The (A) alkyl acrylate rubber of the graft copolymer may have an average particle diameter of, for example, 50 to 120 nm, preferably 60 to 120 nm, and even more preferably 80 to 110 nm, within this range. Excellent impact strength, light resistance and gloss can be imparted to the prepared thermoplastic resin composition.
[50]
In the present description, the average particle diameter can be measured using dynamic light scattering, and in detail, intensity in Gaussian mode using a particle meter (product name: Nicomp 380, manufacturer: PSS) ) value. At this time, as a specific measurement example, the sample is 1,000 to 5,000 times 0.1 g of latex having a total solid content of 35 to 50% by weight with distilled water.
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5,000 character limit. Use the arrows to translate more.It is prepared by dilution, and the measurement method is auto-dilution and measured with a flow cell. It can be measured at 632.8 nm and channel width 10 μsec.
[51]
[52]
The (A) graft copolymer is, for example, 35 to 85% by weight, preferably 40 to 80% by weight, more preferably 50 to 80% by weight, more preferably 50 to 80% by weight, based on the total weight of components (A) and (B) It may be 60 to 80% by weight, more preferably 60 to 75% by weight, and within this range, mechanical properties such as impact strength, tensile strength, and flexural strength, glossiness, and surface hardness are excellent.
[53]
The (A) graft copolymer comprises, for example, (a-1) 20 to 60% by weight of an alkyl acrylate rubber and (a-2) 40 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer, , preferably (a-1) 30 to 50% by weight of an alkyl acrylate rubber and (a-2) 50 to 70% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer, more preferably (a -1) 40 to 50% by weight of an alkyl acrylate rubber and (a-2) 50 to 60% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer, and within this range, mechanical properties, glossiness and surface hardness has an excellent effect.
[54]
The alkyl acrylate rubber may be prepared by, for example, emulsion polymerization of an alkyl acrylate, and as a specific example, it may be prepared by emulsion polymerization by mixing an alkyl acrylate, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte, and a solvent, In this case, since the grafting efficiency is excellent, physical properties such as impact resistance are excellent.
[55]
In the present description, a polymer comprising a certain compound means a polymer polymerized including the compound, and a unit in the polymer is derived from the compound.
[56]
[57]
The (a-1) alkyl acrylate rubber may further include, for example, an aromatic vinyl compound, and in this case, chemical resistance and impact resistance are further excellent. The content of the aromatic vinyl compound contained in the (a-1) alkyl acrylate rubber is, for example, 0.1 to 35% by weight, preferably 1 to 30% by weight, more preferably 1 to 30% by weight, based on 100% by weight of the total acrylate rubber. It may be 7 to 30% by weight, more preferably 10 to 20% by weight, and within this range, mechanical properties, glossiness and surface hardness are excellent without deterioration of physical properties.
[58]
The (a-2) copolymer may further include, for example, an alkyl acrylate, and in this case, an excellent physical property balance of impact resistance, weather resistance, processability, and non-whitening properties is obtained.
[59]
The (a-2) copolymer may contain, for example, 55 to 85% by weight of an aromatic vinyl compound, 10 to 30% by weight of a vinyl cyan compound, and 0.1 to 35% by weight of an alkyl acrylate, based on 100% by weight of the copolymer (a-2). It is composed of, preferably 60 to 80% by weight of an aromatic vinyl compound, 15 to 25% by weight of a vinyl cyan compound and 1 to 25% by weight of an alkyl acrylate, more preferably 65 to 80% by weight of an aromatic vinyl compound 75% by weight, 15 to 22% by weight of a vinyl cyan compound, and 5 to 20% by weight of an alkyl acrylate, and within this range, impact resistance and weather resistance are more excellent.
[60]
[61]
The (A) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, glossiness and surface hardness are excellent.
[62]
The alkyl acrylate may be, for example, an alkyl acrylate having 1 to 15 carbon atoms in an alkyl group, preferably methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, or octyl acrylate. may be one or more selected from the group consisting of acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate and lauryl acrylate, more preferably an alkyl acryl having 2 to 8 carbon atoms acrylate, more preferably butyl acrylate or ethylhexyl acrylate, and even more preferably butyl acrylate.
[63]
Examples of the aromatic vinyl compound include styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brobo styrene, and ρ-bromethane. It may be at least one selected from the group consisting of parent styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, preferably It may be at least one selected from the group consisting of styrene and α-methyl styrene, more preferably styrene, and in this case, the fluidity is appropriate, resulting in excellent workability and excellent mechanical properties such as impact resistance.
[64]
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.
[65]
The emulsion polymerization is not particularly limited when the emulsion polymerization method is commonly performed in the art.
[66]
[67]
The (A) graft copolymer has, for example, a graft rate calculated by Equation 3 below of 60 to 150%, preferably 62 to 140%, more preferably 65 to 130%, still more preferably 65 to 100% It may be, and within this range, there are advantages of excellent gloss, colorability and transparency.
[68]
[Equation 3]
[69]
Graft rate (%) = [weight of grafted monomer (g) / rubbery weight (g)] * 100
[70]
(The weight (g) of the grafted monomer in Equation 3 is the weight obtained by subtracting the weight (g) of rubber from the weight (g) of the insoluble material (gel) after dissolving the graft copolymer in acetone and centrifuging, The rubbery weight (g) is the weight (g) of the theoretically added rubber component in the graft copolymer powder.)
[71]
The weight (g) of the insoluble material (gel) was determined by (A) adding 0.5 g of graft copolymer dry powder to 50 ml of acetone, stirring at room temperature for 12 hours, centrifuging it, and collecting only the insoluble matter not dissolved in acetone. It is the weight measured after drying for 12 hours, and the rubber weight (g) is the weight (g) of the theoretical rubber component added in 0.5 g of (A) graft copolymer dry powder.
[72]
As a specific measurement example, the weight (g) of the insoluble material (gel) was measured by adding 0.5 g of dry powder of the graft copolymer to 50 ml of acetone, and then using a stirrer (Orbital Shaker, equipment name: Lab companion SKC-6075) at room temperature to 210 It was stirred at rpm for 12 hours and centrifuged for 3 hours at 18,000 rpm at 0 ° C using a centrifuge (Supra R30, Hanil Scientific Co., Ltd.) to collect only the insoluble matter that was not dissolved in acetone, and then collected in an oven (Forced Convection Oven; equipment name: Lab). companion OF-12GW) at 85 ℃ for 12 hours by forced circulation drying method, and then weighed.
[73]
[74]
(B) polymethacrylate resin
[75]
The (B) polymethacrylate resin is for example 15 to 65% by weight, preferably 20 to 60% by weight, more preferably 20 to 50% by weight, based on the total weight of components (A) and (B). It may be preferably 20 to 40% by weight, and even more preferably 25 to 40% by weight, and within this range, mechanical properties such as impact strength, tensile strength, flexural strength, surface hardness, transparency and colorability are excellent, In particular, it has excellent non-whitening properties that do not cause whitening during bending.
[76]
[77]
The (B) polymethacrylate resin has, for example, a weight average molecular weight of 50,000 to 150,000 g/mol, preferably 60,000 to 140,000 g/mol, more preferably 70,000 to 130,000 g/mol, still more preferably 80,000 to 120,000 It may be g / mol, and within this range, there is an effect of having excellent weather resistance and excellent tensile strength and impact strength.
[78]
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, the solvent is THF, the column temperature is 40 ℃, the flow rate is 0.3 ml / min, the sample concentration is 20 mg / ml, and the injection amount is 5 μl, and the column model is 1xPLgel 10㎛ MiniMix-B (250x4.6mm ) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), measuring device Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature 35℃, data Treatment can be measured by Agilent ChemStation S/W, and test methods (Mn, Mw and PDI) according to OECD TG 118 conditions.
[79]
[80]
The (B) polymethacrylate resin preferably contains 55% by weight or more of the methacrylate monomer, more preferably 60% by weight or more, and even more preferably 65% by weight or more, within this range.
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5,000 character limit. Use the arrows to translate more.Weather resistance is greatly improved, and gloss and colorability are excellent.
[81]
The methacrylate monomer may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in an alkyl group, preferably methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, It may be at least one selected from the group consisting of 2-ethylhexyl methacrylate and lauryl methacrylate, more preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, and more preferably methyl methacrylate.
[82]
The (B) polymethacrylate resin is preferably at least one selected from the group consisting of polymethyl methacrylate resin and methyl methacrylate-styrene-acrylonitrile copolymer, more preferably polymethyl methacrylate It is a late resin or a methyl methacrylate-styrene-acrylonitrile copolymer, more preferably a polymethyl methacrylate resin, and within this range, there are advantages of better weather resistance, excellent transparency and colorability.
[83]
[84]
The methyl methacrylate-styrene-acrylonitrile copolymer includes, for example, 65 to 85% by weight of methyl methacrylate, 5 to 30% by weight of styrene, and 5 to 10% by weight of acrylonitrile, preferably It may include 70 to 80% by weight of methyl methacrylate, 15 to 25% by weight of styrene, and 5 to 10% by weight of acrylonitrile, and within this range, there are advantages in that weather resistance is better and transparency and colorability are excellent.
[85]
The methyl methacrylate-styrene-acrylonitrile copolymer may, for example, have a weight average molecular weight of 70,000 to 140,000 g/mol, preferably 70,000 to 90,000 g/mol, greater than 90,000 g/mol to 140,000 g/mol It may be the following or a mixture thereof, and within this range, weather resistance is better, and there is an effect of excellent tensile strength, flexural strength and impact strength.
[86]
[87]
The (B) polymethacrylate resin may be prepared by solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization, and each of the solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization is commonly used in the art. The method of emulsion polymerization and suspension polymerization to be carried out is not particularly limited.
[88]
[89]
thermoplastic resin composition
[90]
The thermoplastic resin composition of the present disclosure preferably has an alkyl acrylate coverage value (X) calculated by Equation 1 below of 70% or more, preferably 70 to 150%, more preferably 75 to 140%, still more preferably It may be 80 to 130%, more preferably 85 to 110%, and within this range, there is an excellent effect of excellent transparency and colorability and excellent non-whitening properties that do not cause whitening during bending, especially during bending.
[91]
[Equation 1]
[92]
X = {(G-Y)/Y} * 100
[93]
(In Equation 1, G represents the gel content (% by weight) with respect to the total weight of the thermoplastic resin composition, and Y represents the content (% by weight) of alkyl acrylate in the gel with respect to the total weight of the thermoplastic resin composition.)
[94]
In Equation 1, the alkyl acrylate content in the gel of the thermoplastic resin composition represents the alkyl acrylate content (based on 100% by weight of the total thermoplastic resin composition charged) among the insolubles collected in the process of obtaining the gel content. Here, the gel content represents the content of the insoluble content based on 100% by weight of the total thermoplastic resin.
[95]
The alkyl acrylate content in the gel can be quantitatively measured through NMR (Nuclear Magnetic Resonance) analysis or FT-IR (Fourier Transform Infrared Spectroscopy) analysis.
[96]
NMR analysis in the present description means analysis by 1H NMR unless otherwise limited.
[97]
In the present description, NMR analysis can be measured using a method commonly practiced in the art, and specific measurement examples are as follows.
[98]
- Device name: Bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable and broadband, with z-gradient) Prodigy Probe
[99]
- Measurement conditions: 1H NMR (zg30): ns=32, d1=5s, TCE-d2, at room temp.
[100]
[101]
In the present description, FT-IR analysis can be measured using a method commonly practiced in the art, and specific measurement examples are as follows.
[102]
- Device name: Agilent Cary 660
[103]
- Measurement conditions: ATR mode
[104]
[105]
The gel content is obtained by adding 1 g of the thermoplastic resin composition to 30 g of acetone, stirring at room temperature for 12 hours, centrifuging it, collecting only the insoluble content that is not dissolved in acetone, drying for 12 hours, measuring the weight, and yield At this time, as a specific measurement example, the gel content was measured by adding 1 g of the thermoplastic resin composition to 30 g of acetone, stirring at 210 rpm with a stirrer (Orbital Shaker, equipment name: Lab companion SKC-6075) for 12 hours at room temperature, and centrifuging it (Hanil Scientific Co., Ltd.) Supra R30) was centrifuged at 0 ° C and 18,000 rpm for 3 hours to collect only the insoluble matter that was not dissolved in acetone, and then placed in an oven (Forced Convection Oven; equipment name: Lab companion OF-12GW) at 85 ° C for 12 hours. Weight can be measured after drying by forced circulation drying method.
[106]
[Equation 2]
[107]
Gel content (%) = [weight of insoluble matter (gel) (g) / weight of sample (g)] * 100
[108]
[109]
In the present description, the alkyl acrylate coverage value is a parameter that can determine the degree of dispersion of the aromatic vinyl compound-vinyl cyan compound polymer grafted to the alkyl acrylate rubber in the thermoplastic resin composition. As this value increases, the aromatic vinyl compound-vinyl cyan compound polymer is evenly grafted onto the alkyl acrylate rubber to enclose the rubber, resulting in high gloss, excellent tensile strength and colorability. In addition, the higher the alkyl acrylate coverage value, the narrower the distance between rubber particles, thereby reducing voids due to cracks generated inside the thermoplastic resin composition, thereby suppressing the whitening phenomenon during bending.
[110]
[111]
The difference between the alkyl acrylate coverage value and the graph ratio is that the alkyl acrylate coverage value is NMR (nuclear magnetic resonance) analysis or FT-IR (Fourier transform infrared spectroscopy) analysis of the alkyl acrylate content actually present in the thermoplastic resin composition It is quantitatively calculated through, and the graft rate has a difference calculated from the content of the rubber component introduced during polymerization.
[112]
In addition, the graft rate is a parameter that can determine the degree of grafting of the aromatic vinyl compound-vinyl cyan compound polymer to the alkyl acrylate rubber in the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer.
[113]
[114]
The thermoplastic resin composition has a total light transmittance (Tt) of, for example, 75% or more, preferably 80% or more, more preferably 80 to 95%, further It may preferably be 82 to 90%, and within this range, the balance of physical properties is excellent, and transparency, colorability, and non-whitening characteristics are excellent.
[115]
[116]
The thermoplastic resin composition has a haze of, for example, 11% or less, preferably 8% or less, more preferably 6% or less, and still more preferably 0.1 to 6%, as measured by a specimen thickness of 3T in accordance with ASTM D1003, for example. Within this range, the balance of physical properties is excellent, and transparency, colorability, and non-whitening characteristics are excellent.
[117]
[118]
The thermoplastic resin composition has a glossiness of, for example, 120 or more, preferably 125 or more, more preferably 125 to 150, further It may be preferably 133 to 145, and within this range, in this case, the physical property balance group is excellent, and the transparency, colorability, and non-whitening characteristics are excellent.
[119]
[120]
The thermoplastic resin composition is impacted by the weight when a weight of 1 kg is dropped vertically onto an extruded film extruded to a thickness of 0.15 mm from a height of 50 cm using a Gardner impact tester, for example. The haze difference (Δhaze) measured according to ASTM D1003 before and after impact in the affected area is 10 or less, preferably 8 or less, more preferably 5 or less, still more preferably 4 or less, even more preferably may be 3 or less, particularly preferably 0.1 to 3, and within this range, there are advantages in excellent balance of physical properties, excellent appearance quality and non-whitening characteristics.
[121]
[122]
The thermoplastic resin composition has, for example, an Izod impact strength (specimen thickness 1/4 ", room temperature) measured according to ASTM D256 of 3 kgf cm/cm or more, preferably 3.5 kgf cm/cm or more, more preferably may be 3.5 to 10 kgf cm/cm, more preferably 4 to 9 kgf cm/cm, and even more preferably 4.5 to 8.5 kgf cm/cm, and within this range, physical property balance and non-whitening characteristics This has an excellent effect.
[123]
In the present description, room temperature may be a point within the range of 20 ± 5 °C.
[124]
[125]
The thermoplastic resin composition has a tensile strength of, for example, 200 kgf/cm 2 or more, preferably 250 kgf/cm 2 or more, as measured under a specimen thickness of 3.2 mm and a speed of 10 mm/min measured in accordance with ASTM D638, for example. preferably 300 kgf/cm 2 or more, more preferably 300 to 600 kgf/cm 2 , even more preferably 350 to 600 kgf/cm 2 ,
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ContributeWithin this range, there is an excellent effect of physical property balance and non-whitening characteristics.
[126]
[127]
The thermoplastic resin composition has, for example, a flexural strength of 350 kgf/cm 2 or more, preferably 450 kgf/cm, measured under a specimen thickness of 3.2 mm, a span of 64 mm, and a test speed of 10 mm/min in accordance with ASTM D790. 2 or more, more preferably 500 kgf/cm 2 or more, and more preferably 500 to 900 kgf/cm 2 , and within this range, there is an excellent effect of physical property balance and non-whitening properties.

we claims

[Claim 1]
(A) 35 to 85% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle diameter of 50 to 120 nm; and (B) 15 to 65% by weight of a polymethacrylate resin, wherein the alkyl acrylate coverage value (X) calculated by Equation 1 below is 70% or more. [Equation 1] X = {(G-Y) / Y} * 100 (in Equation 1, G is the gel content (% by weight) with respect to the total weight of the thermoplastic resin composition, Y is the gel content with respect to the total weight of the thermoplastic resin composition Indicates the content (% by weight) of alkyl acrylate.)
[Claim 2]
The thermoplastic resin composition according to claim 1, wherein the polymethacrylate resin (B) has a weight average molecular weight of 50,000 to 150,000 g/mol.
[Claim 3]
The thermoplastic resin composition according to claim 1, wherein (B) the polymethacrylate resin comprises 55% by weight or more of methacrylate monomers.
[Claim 4]
The thermoplastic resin composition according to claim 3, wherein the polymethacrylate resin (B) is at least one selected from the group consisting of polymethyl methacrylate resin and methyl methacrylate-styrene-acrylonitrile copolymer. .
[Claim 5]
The method of claim 4, wherein the methyl methacrylate-styrene-acrylonitrile copolymer comprises 65 to 85% by weight of methyl methacrylate, 5 to 30% by weight of styrene, and 5 to 10% by weight of acrylonitrile. Characterized by a thermoplastic resin composition.
[Claim 6]
The method of claim 1, wherein the (A) graft copolymer comprises (a-1) 20 to 60% by weight of an alkyl acrylate rubber and (a-2) 40 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer. A thermoplastic resin composition comprising
[Claim 7]
The thermoplastic resin composition according to claim 1, wherein the graft copolymer (A) has a graft rate of 60% or more calculated by Equation 3 below. [Equation 3] Graft rate (%) = [weight of grafted monomer (g) / rubbery weight (g)] * 100 (in Equation 3, the weight (g) of grafted monomer is It is the weight obtained by subtracting the rubber weight (g) from the weight (g) of the insoluble material (gel) after being dissolved in acetone and centrifuged, and the rubber weight (g) is the weight (g) of the theoretically added rubber component in the graft copolymer powder to be.)
[Claim 8]
The method of claim 1, wherein the thermoplastic resin composition is a heat stabilizer, a light stabilizer, a dye, a pigment, a colorant, a lubricant, a release agent, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a flame retardant, an inhibitor, an anti-drip agent, and an anti-friction agent. and at least one selected from the group consisting of antiwear agents.
[Claim 9]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a total light transmittance (Tt) of 75% or more as measured with a specimen thickness of 3T in accordance with ASTM D1003.
[Claim 10]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a haze of 11% or less as measured with a specimen thickness of 3T according to ASTM D1003.
[Claim 11]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a glossiness of 120 or more as measured at an incident angle of 45° according to the ASTM D2457 method.
[Claim 12]
According to claim 1, wherein the thermoplastic resin composition using a Gardner impact tester (Gardner impact tester) weight of 1 kg at a height of 50 cm thickness 0.15 mm X 5 cm X 5 cm vertically on the extruded film. When dropped, the thermoplastic resin composition, characterized in that the haze difference (Δhaze) measured according to ASTM D1003 of the haze before and after impact in the impact part impacted by the weight is 10 or less.
[Claim 13]
(A) 35 to 85% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle diameter of 50 to 120 nm and (B) 15 to 65% by weight of a polymethacrylate resin A thermoplastic resin composition comprising the steps of kneading and extruding under conditions of 200 to 300 ° C. and 100 to 500 rpm, characterized in that the alkyl acrylate coverage value (X) calculated by Equation 1 is 70% or more, including manufacturing method. [Equation 1] X = {(G-Y)/Y} * 100 (in Equation 1, G is the gel content (%) with respect to the total weight of the thermoplastic resin composition, Y is the alkyl in the gel with respect to the total weight of the thermoplastic resin composition Represents the content (wt%) of acrylate.)
[Claim 14]
A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 12.