Title of Invention: Thermoplastic resin composition, manufacturing method thereof, and molded article containing the same
technology field
[One]
[Mutual Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2021-0009295 dated 2021.01.22, and all contents disclosed in the literature of the Korean patent application are included as part of this specification.
[3]
The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article including the same, and more particularly, has excellent mechanical properties such as impact strength, tensile strength, elongation, transparency, colorability, and workability, and particularly has excellent whitening properties during bending. It relates to a thermoplastic resin composition with excellent non-whitening properties that does not occur, a method for producing the same, and a molded article including the same.
background art
[4]
Polyvinyl chloride resin (hereinafter referred to as 'PVC resin') and polyethylene terephthalate resin (hereinafter referred to as 'PET resin') have excellent moldability and a simpler manufacturing process compared to painting and painting, so they are used for indoor furniture or interior decoration. It is a material widely used as a decorative sheet. However, in the case of PVC resin, there is a problem of harmfulness due to the large amount of plasticizer injected for flexibility and hydrogen chloride gas generated during combustion during work. .
[5]
Acrylate-styrene-acrylonitrile copolymer (hereinafter referred to as 'ASA resin') containing an alkyl acrylate compound has weather resistance, aging resistance, chemical resistance, rigidity, impact resistance and processability, and has various uses. Therefore, it is widely used in the fields of automobiles, miscellaneous goods, and construction materials, and the scale of its use is continuously increasing.
[6]
On the other hand, as the market demand for emotional quality and its level increase, substrates such as acrylonitrile-butadiene-styrene resin, PVC resin, PET resin, and steel plate are finished with the ASA resin composition, resulting in a luxurious appearance and excellent colorability. And research is being conducted to implement weather resistance.
[7]
However, due to the characteristics of ASA resin, when finishing at room temperature, 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 of the base material, which causes the original color to disappear and the aesthetic appearance to be impaired. do. Since this phenomenon is caused by voids caused by cracks existing inside the ASA resin, in order to improve it, conventionally, we tried to solve it through softening of the resin, such as by increasing the rubber content, but due to the mechanical properties different from the ASA resin composition of the ASA resin, it is not suitable for use. There were limitations.
[8]
Accordingly, there is a need to develop a thermoplastic resin composition having mechanical properties and surface hardness similar to those of conventional ASA resin compositions, excellent transparency and colorability, and no whitening.
[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 is a thermoplastic with excellent mechanical properties such as impact strength, tensile strength, elongation, transparency, colorability and processability, and in particular, non-whitening properties that do not cause whitening during bending. It aims at providing a 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, the object of this 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 75% 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 40 to 120 nm; and (B) 25 to 65% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 50,000 to 180,000 g/mol, and the alkyl acrylate coverage value (X) calculated by Equation 1 below is 70 It provides a thermoplastic resin composition characterized in that % or more.
[18]
[Equation 1]
[19]
X = {(GY)/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 75% 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 40 to 120 nm; and (B) 25 to 65% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 50,000 to 180,000 g/mol, wherein the (A) graft copolymer comprises 20 to 60% by weight of an alkyl acrylate rubber % and an aromatic vinyl compound-vinyl cyan compound copolymer of 40 to 60% by weight.
[23]
[24]
In addition, the substrate is (A) 35 to 75% 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 40 to 120 nm and (B) a weight average molecular weight of 50,000 to 180,000 g/mol of an aromatic vinyl compound-vinyl cyan compound copolymer at 25 to 65% by weight and kneading and extruding under conditions of 200 to 300 ° C. and 100 to 500 rpm, calculated by Equation 1 below: It provides a method for producing a thermoplastic resin composition characterized in that the alkyl acrylate coverage value (X) is 70% or more.
[25]
[Equation 1]
[26]
X = {(GY)/Y} * 100
[27]
(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.)
[28]
[29]
In addition, the substrate is (A) 35 to 75% 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 40 to 120 nm and (B) a weight average molecular weight of 50,000 to 180,000 g/mol of an aromatic vinyl compound-vinyl cyan compound copolymer of 25 to 65% by weight and kneading and extruding under conditions of 200 to 300 ° C. and 100 to 500 rpm, The synthesis may provide a method for producing a thermoplastic resin composition comprising 20 to 60% by weight of an alkyl acrylate rubber and 60 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound.
[30]
[31]
In addition, the present substrate provides a molded article comprising the thermoplastic resin composition.
Effects of the Invention
[32]
According to the present invention, a thermoplastic resin composition having excellent mechanical properties such as impact strength, tensile strength, elongation, transparency, colorability, and processability, and excellent non-whitening properties, in particular, preventing whitening during bending, and a method for preparing the same, including the same There is an effect of providing a molded product that does.
Brief description of the drawing
[33]
1 is a photograph taken after T-die extruded films prepared in Example 2 and Comparative Example 4 after impact with a falling ball.
Mode for Carrying Out the Invention
[34]
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.
[35]
The present inventors have formulated an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and an aromatic vinyl compound-vinyl cyan compound copolymer containing rubber having a predetermined average particle diameter in a predetermined ratio, and the alkyl acrylate coverage When the value is adjusted within a predetermined range, mechanical properties, transparency, and colorability are improved, and it is confirmed that the non-whitening property is excellent in that whitening does not occur due to processing processes such as cutting, bending, or molding. The present invention has been completed.
[36]
[37]
The thermoplastic resin composition of the present disclosure includes (A) 35 to 75% 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 40 to 120 nm; and (B) 25 to 65% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 50,000 to 180,000 g/mol, and the alkyl acrylate coverage value (X) calculated by Equation 1 below is 70 It is characterized by more than %.
[38]
[Equation 1]
[39]
X = {(GY)/Y} * 100
[40]
(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.)
[41]
In this case, mechanical properties such as impact strength, tensile strength, elongation, transparency, colorability, and processability are excellent, and in particular, there is an advantage in that whitening does not occur during bending.
[42]
[43]
Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each component.
[44]
[45]
(A) Alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
[46]
The (A) alkyl acrylate rubber of the graft copolymer has an average particle diameter of, for example, 40 to 120 nm, preferably 50 to 120 nm, more preferably 60 to 120 nm, still more preferably 70 to 120 nm, More preferably, it may be 80 to 110 nm, and excellent impact strength, light resistance and gloss can be imparted to the finally prepared thermoplastic resin composition within this range.
[47]
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, 0.1 g of latex having a total solid content of 35 to 50% by weight is prepared by diluting 1,000 to 5,000 times with distilled water as a sample, the measurement method is auto-dilution and measurement is performed with a flow cell, and the measurement mode is dynamic light scattering. Method (Dynamic light scattering) / 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.
[48]
[49]
The (A) graft copolymer is, for example, 35 to 75% by weight, preferably 45 to 65% by weight, more preferably 55 to 65% by weight, based on the total weight of components (A) and (B). Within the range, mechanical properties such as impact strength, tensile strength, and flexural strength, glossiness, and surface hardness have excellent effects.
[50]
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 mechanical properties, glossiness and surface hardness within this range has an excellent effect.
[51]
In the present description, a polymer comprising a certain compound means a polymer including the compound, and a unit in the polymer is derived from the compound.
[52]
[53]
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 32% by weight, more preferably 1 to 32% by weight, based on 100% by weight of the total acrylate rubber. It may be 5 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.
[54]
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.
[55]
The (a-2) copolymer is, 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 60 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 22% by weight of an alkyl acrylate, and within this range, impact resistance and weather resistance are more excellent.
[56]
[57]
The (A) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, glossiness and surface hardness are excellent.
[58]
The emulsion polymerization is not particularly limited when the emulsion polymerization method is commonly performed in the art.
[59]
[60]
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 at least one 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, ethylhexyl acrylate or a mixture thereof, and more preferably butyl acrylate.
[61]
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.
[62]
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.
[63]
The (A) graft copolymer has, for example, a graft rate calculated by Equation 3 below of 60% or more, preferably 60 to 150%, more preferably 65 to 140%, still more preferably 65 to 130%, More preferably, it may be 65 to 120%, and within this range, there are advantages of excellent gloss, colorability and transparency.
[64]
[Equation 3]
[65]
Graft rate (%) = [weight of grafted monomer (g) / rubbery weight (g)] * 100
[66]
(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 rubbery component in the graft copolymer powder.)
[67]
The weight of the insoluble material (gel) was (A) 0.5 g of the graft copolymer dry powder was added to 50 ml of acetone, stirred at room temperature for 12 hours, centrifuged, and collected only insoluble matter not dissolved in acetone for 12 hours It is the weight measured after drying, and the rubbery weight (g) is the theoretical weight (g) of the rubbery component added into 0.5g of (A) graft copolymer dry powder.
[68]
As a specific measurement example, the weight 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 increasing the weight of 12 at 210 rpm with an orbital shaker (equipment name: Lab companion SKC-6075) at room temperature. After stirring for a period of time, centrifugation was performed at 0 ° C and 18,000 rpm for 3 hours using a centrifuge (Supra R30, Hanil Scientific Co., Ltd.) to collect insoluble matter not dissolved in acetone. 12 GW) at 85 ° C. for 12 hours by forced circulation drying method, and then the weight is measured.
[69]
[70]
(B) aromatic vinyl compound-vinyl cyan compound copolymer
[71]
The amount of the (B) aromatic vinyl compound-vinyl cyan compound copolymer is, for example, 25 to 65% by weight, preferably 35 to 55% by weight, more preferably 40 to 65% by weight, based on the total weight of the components (A) and (B). 50% by weight, and within this range, 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.
[72]
[73]
The (B) aromatic vinyl compound-vinyl cyan compound copolymer may have, for example, a weight average molecular weight of 50,000 to 180,000 g/mol, preferably 60,000 to 180,000 g/mol, more preferably 100,000 to 180,000 g/mol, Within this range, weather resistance is more excellent, and there is an effect of excellent tensile strength and impact strength.
[74]
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, 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 method according to OECD TG 118 conditions.
[75]
[76]
The (B) aromatic vinyl compound-vinyl cyan compound copolymer comprises, for example, 55 to 85 wt% of an aromatic vinyl compound and 15 to 45 wt% of a vinyl cyan compound, preferably 60 to 80 wt% of an aromatic vinyl compound. And 20 to 40% by weight of a vinyl cyan compound, more preferably 65 to 75% by weight of an aromatic vinyl compound and 25 to 35% by weight of a vinyl cyan compound, in which case processability and gloss are improved. It has the advantage of being excellent and having excellent non-whitening properties.
[77]
The (B) aromatic vinyl compound-vinyl cyan compound copolymer is preferably a styrene-acrylonitrile copolymer (SAN resin), an α-methylstyrene-acrylonitrile copolymer (heat-resistant SAN resin), or a mixture thereof, More preferably, it is a styrene-acrylonitrile copolymer (SAN resin), and in this case, there is an effect of excellent transparency while having excellent calender processability and extrusion processability.
[78]
[79]
The types of the aromatic vinyl compound and the vinyl cyan compound included in the (B) aromatic vinyl compound-vinyl cyan compound copolymer are the same as the types of the aromatic vinyl compound and vinyl cyan compound included in the graft copolymer (A) of the present description. It may be within a category.
[80]
[81]
The (B) aromatic vinyl compound-vinyl cyan compound copolymer may be prepared by solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, preferably bulk polymerization, in which case excellent effects such as heat resistance and fluidity are obtained. have.
[82]
The solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization are not particularly limited when the solution polymerization and bulk polymerization methods are commonly performed in the art.
[83]
[84]
thermoplastic resin composition
[85]
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 70 to 140%, still more preferably may be 70 to 135%, more preferably 75 to 130%, particularly preferably 80 to 130%, particularly preferably 85 to 110%, and within this range, transparency and colorability are excellent, especially bending It has an excellent effect of non-whitening property that does not cause whitening during processing.
[86]
[Equation 1]
[87]
X = {(GY)/Y} * 100
[88]
(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.)
[89]
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.
[90]
The alkyl acrylate content in the gel can be measured using 1 NMR analyzer or FT-IR.
[91]
[92]
The gel content was 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 not dissolved in acetone, drying it for 12 hours, measuring the weight, and using Equation 2 below: yield As a specific measurement example, 1 g of the thermoplastic resin composition was added to 30 g of acetone, stirred at 210 rpm with a stirrer (Orbital Shaker, equipment name: Lab companion SKC-6075) for 12 hours at room temperature, and centrifuged (Supra R30, Hanil Scientific Co.) Centrifuged at 0 ° C and 18,000 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 ° C for 12 hours. After drying, the weight can be measured.
[93]
[Equation 2]
[94]
Gel content (%) = [weight of insoluble matter (gel) (g) / weight of sample (g)] * 100
[95]
[96]
In the present description, the alkyl acrylate coverage value is a parameter measuring 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 is higher, the aromatic vinyl compound-vinyl cyan compound polymer is evenly grafted onto the alkyl acrylate rubber, resulting in a form that uniformly envelops the rubber, resulting in high gloss, excellent tensile strength, colorability, and non-whitening properties. 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.
[97]
[98]
The difference between the alkyl acrylate coverage value and the graft rate is that the alkyl acrylate coverage value is a measure of the degree of dispersion of the aromatic vinyl compound-vinyl cyan compound polymer grafted onto the alkyl acrylate in the thermoplastic resin composition, and the graft rate is an alkyl acrylate In the rate-aromatic vinyl compound-vinyl cyan compound graft copolymer, the degree of grafting of the aromatic vinyl compound-vinyl cyan compound polymer to the alkyl acrylate was calculated.
[99]
In addition, the alkyl acrylate coverage value is calculated from the alkyl acrylate content actually present in the thermoplastic resin composition using 1 NMR analyzer or FT-IR, and the graft rate is calculated from the content of the rubber component added during polymerization. There is a difference.
[100]
[101]
The thermoplastic resin composition, for example, has 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 to 9 kgf cm / cm, more preferably Preferably 4 to 8.5 kgf cm / cm, more preferably 4.5 to 8 kgf cm / cm, and within this range, there is an excellent effect of physical property balance and non-whitening characteristics within this range.
[102]
In the present description, room temperature may be a point within the range of 20 ± 5 °C.
[103]
[104]
The thermoplastic resin composition is, for example, when a weight of 1 kg is dropped vertically onto an extruded film having a thickness of 0.15 mm X 10 cm X 10 cm from a height of 25 cm using a Gardner impact tester, The haze difference (Δhaze) measured in accordance with ASTM D1003 for the haze before and after impact in the impact part impacted by the weight is 10 or less, preferably 7 or less, more preferably 5 or less, still more preferably 0.1 to 0.1 5, more preferably 0.1 to 4.5, particularly preferably 0.1 to 4, and in this case, the non-whitening property against impact (hit) from the outside is excellent, so that the appearance quality is excellent.
[105]
[106]
The thermoplastic resin composition, for example, after preparing a sheet having a thickness of 0.15 mm using a T-die extruder, cutting the prepared sheet into a length of 100 cm, and then reducing the thickness of the portion excluding 2 to 3 cm from both ends at 10 or more places. The measured thickness deviation calculated as the difference between the maximum thickness and the minimum thickness is 0.05 mm or less, preferably 0.03 mm or less, more preferably 0.001 to 0.03 mm, in this case, the physical property balance and non-whitening property are excellent, and the extrusion moldability is excellent. This has an excellent effect.
[107]
A specific example of extruding a sheet with the T-die extruder is an extrusion screw speed of 100 to 200 rpm, an extrusion temperature of 200 to 300 ° C, a three-axis roll temperature of 80 to 90 ° C, and a roll rotation speed of 1 to 5 using the T-die extruder. Sheets with a thickness of 0.15 mm can be produced under m/min.
[108]
For example, the T-die extruder may use Korea EM's ST32HS (Twin screw, 32Τ, L/D = 44).
[109]
In this substrate, the thickness can be measured with Mitutoyo's ABSOLUTE ID-C1012BS.
[110]
[111]
The thermoplastic resin composition has excellent T-die extrusion processability, for example, using a T-die extruder at an extrusion screw speed of 150 to 200 rpm, an extrusion temperature of 200 to 300 ° C, a three-axis roll temperature of 80 to 90 ° C and a roll rotation speed When extruding at 2 to 4 m/min, the sheet can be extruded without tearing, and in this case, the physical property balance and non-whitening property are excellent, and the extrusion processability is excellent even at high roll rotation speed.
[112]
The T-die extrusion processability is a specific measurement example, using a T-die extruder (Korea EM ST32HS, Twin screw, 32Τ, L / D = 44) at an extrusion screw speed of 150 to 200 rpm and an extrusion temperature of 200 to 300 ° C. , It is possible to manufacture a sheet having a thickness of 0.15 mm by extruding at a roll temperature of 80 to 90 ° C. and a roll rotation speed of 2 to 4 m / min on three axes.
[113]
[114]
The thermoplastic resin composition is, for example, calendered with a roll mill machine, and the thickness of the portion excluding 2 to 3 cm from both ends of a sheet having a total length of 30 cm prepared is measured at 10 or more places, and the difference between the maximum thickness and the minimum thickness The calculated thickness deviation is 0.05 mm or less, preferably 0.04 mm or less, more preferably 0.03 mm or less, still more preferably 0.005 to 0.03 mm, and within this range, the sheet quality and physical property balance are excellent, and the calender It has excellent processability.
[115]
A specific example of the calendering process is a roll mill machine at a temperature of 180 to 220 ° C. for two calendering rolls, a calendering roll speed of 8 to 12 rpm, and a gap of 0.3 mm between the calendering rolls to prepare a sheet having a thickness of 0.3 mm. .
[116]
In the present description, calendering can be performed using, for example, a roll mill machine (MR-LM0820 from Mirae Rpm Co., Ltd.).
[117]
[118]
The thermoplastic resin composition has, for example, a specimen thickness of 3.2 mm measured according to ASTM D638 and a tensile strength of 280 kgf/cm 2 or more, preferably 300 kgf/cm 2 or more, as measured under a crosshead speed of 50 mm/min. It may be preferably 300 to 600 kgf/cm 2 , more preferably 350 to 550 kgf/cm 2 , and within this range, there is an excellent effect of balancing physical properties and non-whitening properties.
[119]
[120]
The thermoplastic resin composition has, for example, an elongation of 47% or more, preferably 52% or more, more preferably 52 to 80%, as measured under a specimen thickness of 3.2 mm and a crosshead speed of 50 mm / min measured according to ASTM D638 , More preferably 55 to 75%, and within this range, there is an excellent effect of physical property balance, processability and non-whitening characteristics.
[121]
[122]
The thermoplastic resin composition optionally includes a heat stabilizer, a light stabilizer, a dye, a pigment, a colorant, a lubricant, a mold release agent, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a flame retardant, a retardant, an anti-drip agent, an anti-friction agent, and 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the total of the (A) graft copolymer and (B) copolymer, at least one selected from the group consisting of antiwear agents, more preferably It may further include 0.1 to 2 parts by weight, more preferably 0.2 to 1.5 parts by weight, and within this range, there is an effect that the necessary physical properties are well implemented without deteriorating the physical properties of the thermoplastic resin composition of the present substrate. .
[123]
The thermal stabilizer may preferably include a primary thermal stabilizer and a secondary thermal stabilizer.
[124]
The primary thermal stabilizer may preferably be a phenolic thermal stabilizer, more preferably 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl Acrylate, 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate, 1,6-hexanediolbis-[ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylenebis-[3-(3,5-di-t-butyl-4-hydride) hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) Isocyanurate, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy Ethyl] isocyanurate, tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,2'-methylenebis (4-methyl-6-t-butylphenol ) terephthalate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-bis[1,1-dimethyl- 2-{β-(3-t-butyl-4-hydroxy-5-methyl-phenyl)pripionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane; 2,2-bis[4-(2-3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)ethoxyphenyl]propane, and β-(3,5-di-t-butyl- It may be at least one selected from the group consisting of 4-hydroxyphenyl)propionic acid stearyl esters, more preferably octadecyl 3-(3,5-ditertiary-butyl-4-hydroxyphenyl)propanoate (octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate; IR1076).
[125]
The secondary thermal stabilizer may preferably be a phosphorus-based thermal stabilizer, more preferably bis(dialkylphenyl)pentaerythritol diphosphite ester, phosphite ester, trioctyl phosphite, trilauryl phosphite, tridecyl Phosphite, (octyl)diphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, dis Tearylpentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-hydroxy-phenyl)butane diphosphite, tetra(C12-C15 mixed alkyl )-4,4'-isopropylidenediphenyl diphosphite, tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-t-bunylphenol) diphosphite, tris(mono- and Di-mixed nonylphenyl)phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, phenyl(4,4'-isopropylidenediphenol)pentaerythritol diphosphite, distearylpentaerythritol Diphosphite, tris[4,4'-isopropylidenebis(2-t-butylphenol)] phosphite, di(isodecyl)phenyl phosphite, 4,4'-isopropylidenebis(2-t-butyl phenol)bis(nonylphenyl) phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, 2-[{2,4,8,10-tetra-t-butyldibenz[ d,f][1.3.2]-dioxa-phosphepin-6-yl}oxy]-N,N-bis[2-[{2,4,8,10-tetra-t-butyl-dibenz[ d,f][1.3.2]-dioxaphosphepin-6-yl}oxy]ethyl]-ethanamine, and 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)pro Poxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1.3.It may be at least one selected from the group consisting of 2]-dioxaphosphepines, more preferably tris(2,4-di-tert-butylphenyl) phosphite (Tris(2,4-di-tert-butylphenyl ) phosphite; IF168).
[126]
The lubricant may preferably be at least one selected from the group consisting of aliphatic amide-based lubricants, fatty acid ester-based lubricants, and olefin-based waxes.
[127]
The aliphatic amide-based lubricant is preferably composed of stearamide, oleamide, erucamide, ethylene bis stearamide, and ethylene bis oleamide. It may be one or more selected from the group.
[128]
The fatty acid ester-based lubricant is preferably 1 selected from the group consisting of alcohol or fatty acid ester of polyhydric alcohol, hydrogenated oil, butyl stearate, stearic acid monoglyceride, pentaerythritol tetrastearate, stearyl stearate, ester wax, and alkyl phosphate ester. There may be more than one species.
[129]
The olefin-based wax may be preferably polyethylene wax.
[130]
The light stabilizer may be, for example, at least one selected from the group consisting of a HALS-based UV stabilizer and a benzotriazole-based UV stabilizer, and preferably may be a mixture of a HALS-based UV stabilizer and a benzotriazole-based UV stabilizer.
[131]
The HALS-based UV stabilizer is preferably bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate ; UV 770), bis-[N-methyl-2,2,6,6-tetramethyl-4-piperidinyl] sebacate (bis-[N-methyl-2,2,6,6-tetramethyl-4-piperidinyl ] sebacate) and succinic acid dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine (succinic acid dimethyl-1-(2-hydroxyethyl)-4-hydroxy -2,2,6,6-tetramethylpiperidine; Tinuvin 622) may be at least one selected from the group consisting of, more preferably bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; UV 770).
[132]
hydroxy-3',5'-di-t-butylphenyl)benzotriazole; Tinuvin-320), and 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (2-(2H-benzotrizol-2-yl)-4 It may be one or more selected from the group consisting of -(1,1,3,3-tetramethylbutyl)phenol; UV 329), more preferably 2-(2H-benzotriazol-2-yl)-4-(1 ,1,3,3-tetramethylbutyl)phenol (2-(2H-benzotrizol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol; UV 329) .
[133]
[134]
Manufacturing method of thermoplastic resin composition
[135]
The method for producing the thermoplastic resin composition of the present disclosure includes (A) 35 to 75% 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 40 to 120 nm and ( B) kneading and extruding at 200 to 300 ° C. and 100 to 500 rpm conditions including 25 to 65% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 50,000 to 180,000 g / mol, It is characterized in that the alkyl acrylate coverage value (X) calculated by Equation 1 is 70% or more.
[136]
[Equation 1]
[137]
X = {(GY)/Y} * 100
[138]
(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.)
[139]
In this case, mechanical properties such as impact strength, tensile strength, elongation, transparency, colorability, and processability are excellent, and in particular, there is an advantage in that whitening does not occur during bending.
[140]
[141]
The manufacturing method of the thermoplastic resin composition shares all the technical characteristics of the thermoplastic resin composition described above. Therefore, the description of the overlapping part will be omitted.
[142]
[143]
The melt-kneading and extruding step may preferably be carried out using an extrusion kneader at 10 to 199 pi standard at 200 to 300 ° C., more preferably at 20 to 80 pi standard at 210 to 260 ° C. It may be, more preferably carried out in a 25 to 75 pi standard under 220 to 250 ℃, stable extrusion is possible within this range and the kneading effect is excellent. At this time, the temperature is the temperature set in the cylinder, and Pi means the outer diameter of the screw (unit: mm).
[144]
[145]
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.
[146]
[147]
molding
[148]
The molded article of the present substrate is characterized by comprising the thermoplastic resin composition, and in this case, mechanical properties such as impact strength, tensile strength, and flexural strength, surface hardness, transparency, and colorability are excellent, and in particular, whitening does not occur during bending. Since it has excellent non-whitening properties and can provide a high-quality appearance, it can be applied to film or sheet products.
[149]
The molded article may preferably be an injection molded article, a calendered molded article, or a T-die extrusion molded article, and in this case, mechanical properties such as impact strength, tensile strength, flexural strength, surface hardness, transparency and coloration as well as non-whitening properties are all exhibited. It has an excellent effect.
[150]
[151]
The molded article may preferably be a decorative sheet for finishing, a finishing material for outdoor construction materials, or a finishing material for a roof.
[152]
[153]
The manufacturing method of the molded article is preferably (A) 35 to 75% 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 40 to 120 nm and (B) Preparing an extrudate by kneading and extruding at 200 to 300 ° C. and 100 to 500 rpm conditions including 25 to 65% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 50,000 to 180,000 g / mol; And preparing a molded product by injection molding, calendar molding or T-die extrusion molding of the extrudate at a molding temperature of 180 to 300 ° C., including, in this case, mechanical properties such as impact strength, tensile strength, flexural strength, surface It has excellent hardness, transparency, and colorability, and has an excellent effect of non-whitening property, in which whitening does not occur during bending, in particular.
[154]
The extrudate may be, for example, in the form of pellets or plates.
[155]
In the present description, the plate-like form is not particularly limited when it is commonly defined as a plate-like form in the technical field to which the present invention belongs, and may include, for example, a flat form, a sheet form, a film form, and the like.
[156]
[157]
The step of manufacturing the molded article may include, as a preferred example, calendering the manufactured extrudate into a sheet under a calender temperature of 140 to 220 ° C. In this case, a sheet molded article having excellent processability and a uniform surface can be easily manufactured. There is an advantage to being
[158]
In the present substrate, calender molding is to roll an extrudate by a calendering process including calendering rolls, and is not particularly limited in the case of a method commonly used in the art to which the present invention belongs, but preferably sheet raw materials Mixing with a mixer at 130 to 200 ° C., preparing the mixed raw materials into a base sheet at 170 to 200 ° C., and forming the base sheet into a sheet using calendering rolls at 140 to 220 ° C. have. Here, in the base sheet manufacturing step, a mixing roll may be used as an example.
[159]
[160]
As another preferred example, the step of preparing the molded article may include injection molding the manufactured extrudate under conditions of an injection temperature of 200 to 260 °C, an injection pressure of 60 to 100 bar, and a packing pressure of 25 to 55 bar, in which case impact impact There is an advantage in that injection molded products having excellent mechanical properties such as strength can be easily manufactured.
[161]
The injection temperature is preferably 200 to 250 ° C, more preferably 210 to 240 ° C, and within this range, there is an advantage that an injection molded product having excellent mechanical properties such as impact strength can be easily manufactured.
[162]
The injection pressure is preferably 70 to 90 bar, more preferably 75 to 85 bar, and within this range, there is an advantage that an injection-molded product having excellent mechanical properties such as impact strength can be easily manufactured.
[163]
The packing pressure may be preferably 30 to 50 bar, more preferably 35 to 50 bar, and within this range, there is an advantage in that injection molded products having excellent mechanical properties such as impact strength can be easily manufactured.
[164]
[165]
As another preferred example, in the step of preparing the molded article, the manufactured extrudate is extruded at an extrusion temperature of 200 to 300 ° C, an extrusion screw speed of 50 to 200 rpm, a three-axis roll temperature of 60 to 100 ° C, and a roll rotation speed of 1 to 5 m / min. In this case, there is an advantage in that a sheet molded article having excellent processability and a uniform surface can be easily manufactured.
[166]
[167]
In describing the thermoplastic resin composition of the present description, its manufacturing method and molded article, it is stated that other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art and are not particularly limited. do.
[168]
[169]
Hereinafter, preferred embodiments are presented to aid understanding of the present description, but the following examples are merely illustrative of the present description, and various changes and modifications are possible within the scope and spirit of the present description. It is obvious to those skilled in the art, It goes without saying that such variations and modifications fall within the scope of the appended claims.
[170]
[171]
[Example]
[172]
Materials used in the following examples and comparative examples are as follows.
[173]
* (A-1) ASA graft copolymer: an ASA graft copolymer having an average particle diameter of 100 nm of alkyl acrylate rubber prepared by emulsion polymerization (core: butyl acrylate 38% by weight, styrene 7% by weight, shell: Butyl acrylate 4% by weight, styrene 40% by weight and acrylonitrile 11% by weight, graft rate 70%)
[174]
* (A-2) ASA graft copolymer: an ASA graft copolymer having an average particle diameter of 50 nm of alkyl acrylate rubber prepared by emulsion polymerization (core: butyl acrylate 38% by weight, styrene 7% by weight, shell: Butyl acrylate 4% by weight, styrene 40% by weight and acrylonitrile 11% by weight, graft rate 70%)
[175]
* (A-3) ASA graft copolymer: an ASA graft copolymer having an average particle diameter of 100 nm of alkyl acrylate rubber prepared by emulsion polymerization (core: butyl acrylate 37% by weight, styrene 3% by weight, shell: Butyl acrylate 12 wt%, styrene 37 wt% and acrylonitrile 11 wt%, graft rate 120%)
[176]
* (A-4) ASA graft copolymer: an ASA graft copolymer having an average particle diameter of 100 nm of alkyl acrylate rubber prepared by emulsion polymerization (core: butyl acrylate 32% by weight, styrene 13% by weight, shell: Butyl acrylate 4% by weight, styrene 40% by weight and acrylonitrile 11% by weight, graft rate 70%)
[177]
* (A-5) ASA graft copolymer: ASA graft copolymer having an average particle diameter of 100 nm of alkyl acrylate rubber prepared by emulsion polymerization (core: butyl acrylate 30% by weight, shell: butyl acrylate 12% by weight %, styrene 47 wt% and acrylonitrile 11 wt%, graft rate 70%)
[178]
* (A-6) ASA graft copolymer: an ASA graft copolymer having an average particle diameter of 150 nm of an alkyl acrylate rubber prepared by emulsion polymerization (core: butyl acrylate 38% by weight, styrene 7% by weight, shell: Butyl acrylate 4% by weight, styrene 40% by weight and acrylonitrile 11% by weight, graft rate 70%)
[179]
* (A-7) ASA graft copolymer: an ASA graft copolymer having an average particle diameter of 30 nm of alkyl acrylate rubber prepared by emulsion polymerization (core: butyl acrylate 38% by weight, styrene 7% by weight, shell: butyl Acrylate 4% by weight, styrene 40% by weight and acrylonitrile 11% by weight, graft rate 70%)
[180]
* (B-1) SAN resin: weight average molecular weight 170,000 g/mol (97HC from LG Chem)
[181]
* (B-2) SAN resin: bulk polymerization acrylonitrile-styrene copolymer (weight average molecular weight 30,000 g/mol. 75% by weight of styrene and 25% by weight of acrylonitrile)
[182]
* (B-3) SAN resin: bulk polymerization acrylonitrile-styrene copolymer (weight average molecular weight 200,000 g/mol, styrene 75 wt% and acrylonitrile 25 wt%)
[183]
[184]
Examples 1 to 7 and Comparative Examples 1 to 8
[185]
In addition to the ingredients and contents listed in Tables 1 and 2 below, Pasflow7501 (Patechfine chemical) 1 part by weight as a lubricant, Irgonox (BASF) 1076 and Irgafos 168 (BASF) 0.5 parts by weight each as an antioxidant, and a UV stabilizer 0.5 parts by weight of each of Tinuvin 770 (BASF) and Sunsorb 329 (Sunfine Global) were introduced into a twin-screw extruder, and melt-kneaded and extruded at 230° C. and 150 rpm to prepare pellets. Afterwards, the manufactured pellets were injected using an injection molding machine (VC 330/80 TECJ PRO from ENGEL) at a molding temperature of 220 °C, an injection pressure of 50 bar, and a holding pressure of 35 bar to prepare specimens for measuring appearance and physical properties, and using this, impact Strength, tensile strength, flexural strength, surface hardness, gloss, light transmittance and haze were measured. Furthermore, the prepared pellets were prepared using a T-die extruder (Korea EM's ST32HS (Twin screw, 32Τ, L/D = 44) at a screw speed of 150 to 200 rpm, a temperature of 200 to 250 ° C, and a roll temperature of 80 ℃, the roll rotation speed of 1.5 m / min to prepare a film with a thickness of 0.15 T was evaluated for non-whitening characteristics according to the impact of falling balls.
[186]
[187]
[Test Example]
[188]
In Examples 1 to 7 and Comparative Examples 1 to 8, the properties of the extruded and extruded specimens were measured by the following method, and the results are shown in Tables 1 and 2 and FIG. 1 below.
[189]
[190]
How to measure
[191]
* Alkyl acrylate coverage value (%): calculated by Equation 1 below.
[192]
[Equation 1]
[193]
X = {(GY)/Y} * 100
[194]
(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.) Here, the gel The content of alkyl acrylate in the mixture was quantitatively measured using a 1 NMR analyzer or FT-IR.
[195]
1 H NMR
[196]
- Device name: Bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable and broadband, with z-gradient) Prodigy Probe
[197]
- Measurement conditions: 1 H NMR (zg30): ns=32, d1=5s, TCE-d2, at room temp.
[198]
FT-IR
[199]
- Device name: Agilent Cary 660
[200]
- Measurement conditions: ATR mode
[201]
The gel content was obtained by adding 1 g of thermoplastic resin composition pellets 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 (Supra R30, Hanil Scientific Co.) Centrifuged at 0 ° C and 18,000 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 ° C for 12 hours. After drying, the weight was measured and calculated by Equation 2 below.
[202]
[Equation 2]
[203]
Gel content (% by weight) = [weight of insoluble matter (gel) (g) / weight of sample (g)] * 100
[204]
* Graft rate (%): 0.5 g of graft copolymer dry powder was added to 50 ml of acetone, stirred at room temperature for 12 hours, centrifuged, and only the insoluble matter not dissolved in acetone was collected, dried for 12 hours, and then weighed So, it was calculated by Equation 3 below.
[205]
[Equation 3]
[206]
Graft rate (%) = [weight of grafted monomer (g) / rubbery weight (g)] * 100
[207]
(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 rubbery component in the graft copolymer powder.)
[208]
Specifically, the weight of the insoluble material (gel) was measured by adding 0.5 g of dry powder of the graft copolymer to 50 ml of acetone, followed by stirring at 210 rpm for 12 hours with an orbital shaker (equipment name: Lab companion SKC-6075) at room temperature. and centrifuged at 0 ° C and 18,000 rpm for 3 hours using a centrifuge (Supra R30, Hanil Scientific Co., Ltd.) to collect only the insoluble matter that was not dissolved in acetone and placed in an oven (Forced Convection Oven; equipment name: Lab companion OF-12GW) After drying at 85 ° C. for 12 hours in a forced circulation drying method, the weight was measured.
[209]
* Izod impact strength (kgf cm/cm): Measured according to ASTM D256 using an injection specimen (thickness of 1/4") at room temperature.
[210]
* Tensile strength (kgf/cm 2 ): Tensile strength was measured with a cross head speed of 50 mm/min and an injection specimen (thickness of 3.2 mm) in accordance with ASTM D638.
[211]
* Elongation (%): Elongation was measured with a crosshead speed of 50 mm/min and an injection specimen (thickness of 3.2 mm) according to ASTM D638.
[212]
* Whitening characteristics according to falling ball impact: Using a Gardner impact tester, a weight of 1 kg is vertically placed on a T-die extruded film with a thickness of 0.15 mm X 10 cm X 10 cm at a height of 25 cm. When dropped, it was evaluated by the following criteria by visually determining whether a whitening phenomenon occurred in the impact part impacted by the weight.
[213]
○: Whitening does not occur, so the non-whitening characteristics are excellent
[214]
X: A large amount of whitening occurs and the non-whitening characteristic is poor
[215]
* Haze difference (Δhaze) according to falling balls: A T-die extruded film with a thickness of 0.15 mm X 10 cm X 10 cm length at a height of 25 cm with a weight of 1 kg using a Gardner impact tester. When dropped vertically, the haze before and after impact at the impact part impacted by the weight was measured according to ASTM D1003 and calculated by Equation 4 below.
[216]
[Equation 4]
[217]
Haze difference (Δhaze) = Haze value after falling ball - Haze value before falling ball
[218]
* Thickness deviation after calendering (mm): Two calendering rolls with a diameter of 30 cm are installed at a distance of 0.3 mm. A sheet having a thickness of 0.3 mm was prepared by calendering the thermoplastic resin composition in the form of an extruded pellet in a state maintained at . The thickness of the portion excluding 2 to 3 cm from both ends of the prepared 30 cm total length sheet was measured at more than 10 locations to obtain a thickness deviation from the difference between the maximum thickness and the minimum thickness. The thickness was measured using Mitutoyo's ABSOLUTE ID-C1012BS.
[219]
* Thickness deviation (mm) after T-die extrusion: Using a T-die extruder (Korea EM ST32HS (Twin screw, 32Τ, L/D = 44), screw speed 150 to 200 rpm, temperature 200 to 250 ° C. , A sheet having a thickness of 0.15 mm was prepared at a roll temperature of 80 ° C and a roll rotation speed of 1.5 m / min on the 3 axis.The prepared sheet was cut into 100 cm in length, and then the thickness of the part excluding 2 to 3 cm from both ends was The thickness deviation was obtained as the difference between the maximum thickness and the minimum thickness by measuring at more than 10. The thickness was measured using Mitutoyo's ABSOLUTE ID-C1012BS.
[220]
* Gloss: measured at 45 ° using a gloss meter in accordance with ASTM D2457.
[221]
[222]
[Table 1]
Classification (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
(A-1) ASA 40 50 60 70
(A-2) ASA 50
(A-3) ASA 50
(A-4) ASA 50
(B-1) SAN 60 50 40 30 50 50 50
(A)
Rubber particle size of ASA (nm) 100 100 100 100 50 100 100
(A)
Graft rate of ASA (%) 70 70 70 70 70 120 70
Alkyl acrylate coverage value (%) 90 90 90 90 90 89 123
Properties
Impact strength
(kgf cm/cm) 5 6 6.5 7.5 3.5 5.5 4
Tensile strength (kgf/cm 2 ) 500 450 370 310 450 450 300
Elongation (%) 50 55 65 70 55 55 80
Non-whitening characteristics according to falling ball impact ○ ○ ○ ○ ○ ○ ○
Haze difference
(Δhaze) 4.5 3.5 2.5 2 3 3.5 1.5
Thickness deviation after extrusion
(mm) 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Thickness deviation after calendering (mm) 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Glossiness 105 102 100 95 100 110 100
[223]
[Table 2]
Classification (parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8
(A-1) ASA 30 20 80 50 50
(A-5) ASA 50
(A-6) ASA 50
(A-7) ASA 50
(B-1) SAN 70 80 20 50 50 50
(B-2) SAN 50
(B-3) SAN 50
(A)
Rubber particle size of ASA (nm) 100 100 100 100 150 30 100 100
(A)
Graft rate of ASA (%) 70 70 70 70 70 70 70 70
Alkyl acrylate coverage value (%) 90 90 90 52 90 90 90 90
Properties
Impact strength
(kgf cm/cm) 3.5 2.5 8 8 9 1.5 6 6
Tensile strength
(kgf/cm 2 ) 550 600 250 450 450 450 450 450
Elongation (%) 45 25 100 60 55 55 60 50
Non-whitening characteristics according to falling ball impact X X ○ X X ○ ○ ○
Haze difference
(Δhaze) 15 25 1.5 40 40 2.5 3.5 3.5
Thickness deviation after extrusion
(mm) 0.01 0.01 0.02 0.01 0.01 0.01 0.1 0.1
Thickness deviation after calendering (mm) 0.01 0.01 0.02 0.01 0.01 0.01 0.1 0.1
Glossiness 110 120 90 90 80 105 120 75
[224]
As shown in Tables 1 and 2, Examples 1 to 7 prepared according to the present invention are excellent in mechanical properties such as impact strength, tensile strength, and flexural strength compared to Comparative Examples 1 to 8 outside the scope of the present invention, The haze difference was small, the non-whitening property was excellent, and the thickness deviation after extrusion and calendering was small. and whitening occurred, and (A) Comparative Example 3, which contained an ASA resin exceeding the scope of the present invention, had poor tensile strength and glossiness.
[225]
In addition, (A) Comparative Example 4, in which the graft rate of the ASA resin was high but the alkyl acrylate coverage value was less than the range of the present invention, whitening occurred, the haze difference rapidly increased, and the glossiness decreased.
[226]
In addition, (A) Comparative Example 5 in which the average particle diameter of the rubber contained in the ASA resin exceeded the scope of the present invention, whitening occurred, the difference in height was large and the glossiness was reduced, and (A) the rubber contained in the ASA resin The average particle diameter of Comparative Example 6, which is less than the range of the present invention, has significantly lowered impact strength.
[227]
In addition, (B) Comparative Examples 7 and 8, in which the weight average molecular weight of the aromatic vinyl compound-vinyl cyan compound copolymer was out of the range of the present invention, the sheet thickness deviation increased after T-die extrusion processing and calendering processing, resulting in poor processability. did
[228]
In addition, as shown in FIG. 1, Example 2 according to the present invention was confirmed to have excellent non-whitening properties even with a large impact compared to Comparative Example 4.
claims
[Claim 1]
(A) 35 to 75% 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 40 to 120 nm; and (B) 25 to 65% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 50,000 to 180,000 g/mol, and the alkyl acrylate coverage value (X) calculated by Equation 1 below is 70 A thermoplastic resin composition, characterized in that % or more. [Equation 1] X = {(GY) / 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 (A) graft copolymer comprises 20 to 60% by weight of an alkyl acrylate rubber and 40 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer. .
[Claim 3]
The thermoplastic resin composition according to claim 1, wherein the (A) graft copolymer 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 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.)
[Claim 4]
The thermoplastic resin composition according to claim 1, wherein the copolymer (B) comprises 55 to 85% by weight of an aromatic vinyl compound and 15 to 45% by weight of a vinyl cyan compound.
[Claim 5]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an Izod impact strength (specimen thickness 1/4", normal temperature) of 4.5 kgf cm/cm or more measured according to ASTM D256.
[Claim 6]
The method of claim 1, wherein the thermoplastic resin composition is an extruded film obtained by extruding a weight of 1 kg into a thickness of 0.15 mm X 10 cm X 10 cm at a height of 25 cm using a Gardner impact tester. When dropped vertically upward, 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, characterized in that the thermoplastic resin composition.
[Claim 7]
The method of claim 1, wherein the thermoplastic resin composition is prepared by using a T-die extruder to prepare a sheet having a thickness of 0.15 mm, and then cutting the prepared sheet into a length of 100 cm, and then excluding 2 to 3 cm from both ends of the sheet. A thermoplastic resin composition, characterized in that the thickness deviation calculated as the difference between the maximum thickness and the minimum thickness by measuring the thickness at 10 or more places is 0.05 mm or less.
[Claim 8]
The method of claim 1, wherein the thermoplastic resin composition is calendered with a roll mill machine and then measured at 10 or more thicknesses of a portion excluding 2 to 3 cm from both ends of a sheet having a total length of 30 cm prepared, to determine the maximum thickness and minimum thickness. A thermoplastic resin composition, characterized in that the thickness deviation calculated by the difference in thickness is 0.05 mm or less.
[Claim 9]
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 mold 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 10]
(A) 35 to 75% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle diameter of 40 to 120 nm and (B) a weight average molecular weight of 50,000 to 180,000 g/mol A phosphorus aromatic vinyl compound-vinyl cyan compound copolymer containing 25 to 65% by weight and kneading and extruding under conditions of 200 to 300 ° C. and 100 to 500 rpm, and the alkyl acrylate coverage value calculated by Equation 1 below A method for producing a thermoplastic resin composition, characterized in that (X) is 70% or more. [Equation 1] X = {(GY) / 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 11]
A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 9.
[Claim 12]
12. The molded product according to claim 11, wherein the molded product is an injection molded product, a calendered molded product, or an extrusion molded product.