Title of Invention: Thermoplastic resin composition and molded article comprising same
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0078393 dated June 26, 2020 and Korean Patent Application No. 10-2021-0025196, filed again on February 25, 2021 based thereon, All content disclosed in the literature of the application is incorporated as a part of this specification.
[3]
The present invention relates to a thermoplastic resin composition and a molded article comprising the same, and more particularly, to a thermoplastic resin composition that is excellent in impact resistance, fluidity and heat resistance, and does not increase processing cost, thereby providing economic advantages and realizing high blackness; It relates to a molded article including the same.
background
[4]
Acrylonitrile-Styrene-Acrylate (ASA) resin improves weather resistance and chemical resistance, which are the biggest drawbacks of conventional ABS (Acrylonitrile-Butadiene-Styrene) resins, and has impact resistance, fluidity, and heat resistance. It is widely used in various applications such as electronics, office equipment, home appliances, toys, and stationery.
[5]
Recently, automobile manufacturers have improved the cost competitiveness of parts by using ASA resin, which has excellent impact resistance, fluidity, heat resistance, weather resistance, and chemical resistance, which can omit the painting process. Efforts are being made to implement
[6]
However, the heat-resistant ASA resin used for conventional automotive exterior materials has poor compatibility with dyes, so there is a limitation in realizing high black color.
[7]
Accordingly, there is a need to develop ASA resins that are excellent in impact resistance, fluidity and heat resistance, as well as high black color, which can satisfy the needs of automobile manufacturers.
[8]
[Prior art literature]
[9]
[Patent Literature]
[10]
Korean Patent Publication No. 2015-0123709
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[11]
In order to solve the problems of the prior art as described above, the present invention provides a thermoplastic resin composition that has excellent impact resistance, fluidity and heat resistance, and does not increase the processing cost, thereby providing economic advantages and realizing high blackness, and a molded article including the same is intended to provide
[12]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[13]
In order to achieve the above object, the present invention is (A) two or more types of acrylic graft resins having different average particle diameters; (B) a first copolymer comprising an alkyl-substituted styrene, (meth)acrylate and a vinyl cyan compound; (C) a second copolymer comprising an alkyl unsubstituted styrene, (meth)acrylate and a vinyl cyan compound; and (D) a (meth)acrylate polymer, but provides a thermoplastic resin composition comprising 40 to 59% by weight of (meth)acrylate based on the total weight of the thermoplastic resin composition.
[14]
In addition, the present invention provides a molded article comprising the thermoplastic resin composition.
Effects of the Invention
[15]
According to the present invention, there is an effect of providing a thermoplastic resin composition that is excellent in impact resistance, fluidity, heat resistance, etc., does not increase processing cost, and can realize high black color while providing economic advantages, and a molded article including the same.
Modes for carrying out the invention
[16]
Hereinafter, the thermoplastic resin composition of the present disclosure and a molded article including the same will be described in detail.
[17]
As a result of the present inventors' efforts to improve the blackness of the ASA resin, alkyl-substituted styrene-(meth)acrylate-vinyl in a composition including the ASA resin and polymethylmethacrylate resin (hereinafter referred to as 'PMMA resin') When the cyanide compound copolymer and the alkyl unsubstituted styrene-(meth)acrylate-vinyl cyan compound copolymer are added, heat resistance and fluidity are improved, and in particular, while reducing the content of PMMA resin, the total weight of (meth)acrylate in the composition Heat resistance, impact resistance, fluidity and blackness are all improved by increasing , based on this, further devoted to research and completed the present invention.
[18]
[19]
The thermoplastic resin composition of the present invention includes (A) two or more types of acrylic graft resins having different average particle diameters; (B) a first copolymer comprising an alkyl-substituted styrene, (meth)acrylate and a vinyl cyan compound; (C) a second copolymer comprising an alkyl unsubstituted styrene, (meth)acrylate and a vinyl cyan compound; and (D) a (meth)acrylate polymer, but comprising 40 to 59% by weight of (meth)acrylate based on the total weight of the thermoplastic resin composition, and in this case, it has excellent impact resistance, fluidity and heat resistance, , there is an advantage that high black color can be realized while providing economic advantages by not increasing the processing cost.
[20]
[21]
Hereinafter, the thermoplastic resin composition of the present disclosure will be described in detail for each component.
[22]
[23]
(A) acrylic graft resin
[24]
(A) the acrylic graft resin of the present base material may include, for example, two or more types of acrylic graft resins having different average particle diameters, and in this case, the impact resistance, colorability, Elongation and heat resistance are improved, and in particular, blackness and impact resistance are excellent at the same time.
[25]
In the present description, unless otherwise defined, the acrylic graft resin may mean a resin obtained by graft polymerization including an acrylate monomer.
[26]
The two or more types means that there are two or more acrylic graft resins having different average particle diameters.
[27]
As a specific example, the (A) acrylic graft resin may include a first acrylic graft resin having an average particle diameter of 400 to 650 nm and a second acrylic graft resin having an average particle diameter of 50 to 160 nm, in which case impact resistance , there is an advantage in that the blackness is improved while maintaining excellent fluidity and heat resistance.
[28]
The first acrylic graft resin may have, for example, an average particle diameter of 300 to 650 nm, preferably 350 to 550 nm, more preferably 400 to 500 nm, even more preferably 450 to 500 nm, and impact resistance within this range. , excellent fluidity and heat resistance, as well as realizing a high level of blackness, has the advantage that it can be applied in high quality to automotive parts such as automotive exterior materials.
[29]
The second acrylic graft resin may have, for example, an average particle diameter of 30 to 250 nm, preferably 40 to 200 nm, more preferably 50 to 150 nm, still more preferably 80 to 130 nm, and impact resistance within this range. , excellent fluidity and heat resistance, as well as realizing a high level of blackness, has the advantage that it can be applied in high quality to automotive parts such as automotive exterior materials.
[30]
In the present description, the average particle diameter may be measured using a dynamic light scattering method, and in detail, may be measured as an intensity value in a Gaussian mode using a Nicomp 380 HPL equipment.
[31]
In addition, the average particle diameter of the present invention may mean an arithmetic average particle diameter in the particle size distribution measured by the dynamic light scattering method, that is, the average particle diameter of scattering intensity (Intensity Distribution). At this time, as a specific example of measurement, the sample is prepared by diluting 0.1 g of Latex (TSC 35-50 wt%) 1,000-5,000 times with distilled water, and the measurement method is auto-dilution and measured with a flow cell, and the measurement mode is dynamic light scattering ( Dynamic light scattering) method/Intensity 300KHz/Intensity-weight Gaussian Analysis can be used, and the setting value can be measured with a temperature of 23℃, a measurement wavelength of 632.8nm, and a channel width of 10μsec.
[32]
The (A) acrylic graft resin is an example of the first acrylic graft resin and the second acrylic graft resin in a weight ratio of 1:1 to 1:30, preferably in a weight ratio of 1:1.5 to 1:20, more Preferably, it may be included in a weight ratio of 1:2 to 1:18, and there is an advantage in that blackness is significantly improved while maintaining excellent impact resistance, fluidity and heat resistance within this range.
[33]
In the present description, the weight ratio of the first acrylic graft resin to the second acrylic graft resin means the weight ratio of the first acrylic graft resin to the second acrylic graft resin.
[34]
The (A) acrylic graft resin may be, for example, 20 to 45 wt%, preferably 25 to 40 wt%, more preferably 31 to 38 wt%, based on 100 wt% of the thermoplastic resin composition, within this range In addition, it has excellent impact resistance, colorability, elongation, fluidity and heat resistance, as well as a high level of blackness.
[35]
The (A) acrylic graft resin may be, for example, an acrylate rubber graft copolymerized with an aromatic vinyl compound and a vinyl cyan compound.
[36]
The average particle diameter of the acrylate rubber may be, for example, 400 to 600 nm, preferably 450 to 500 nm, and within this range, it has excellent impact resistance, fluidity and heat resistance, as well as an advantage of realizing a high level of blackness. .
[37]
As another example, the average particle diameter of the acrylate rubber may be 50 to 250 nm, preferably 70 to 150 nm, and there is an advantage of implementing a high level of blackness as well as excellent impact resistance, fluidity and heat resistance within this range. .
[38]
However, the average particle diameter of the acrylate rubber is smaller than the average particle diameter of the acrylic graft resin.
[39]
The (A) acrylic graft resin may include, for example, 40 to 60% by weight of acrylate rubber, 20 to 50% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, and has impact resistance within this range. , fluidity, heat resistance and blackness are all excellent.
[40]
As a preferred example, the (A) acrylic graft resin may include 45 to 55% by weight of an acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 12 to 17% by weight of a vinyl cyanide compound, within this range There is an advantage of further improving blackness while maintaining excellent impact resistance, fluidity and heat resistance.
[41]
In the present description, a resin including a certain compound means a polymer polymerized including the compound, and a unit in the polymerized polymer is derived from the compound.
[42]
The acrylate rubber may be, for example, an alkyl acrylate rubber.
[43]
The alkyl acrylate may be, for example, an acrylate having 1 to 10 carbon atoms in the alkyl group, preferably an alkyl acrylate having 4 to 10 carbon atoms in the alkyl group, more preferably butyl acrylate, In this case, there is an advantage of realizing a high level of blackness while having excellent intrinsic weather resistance and chemical resistance.
[44]
The aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methylstyrene, 2,4-dimethyl styrene, vinyltoluene, t-butylstyrene and chlorostyrene, preferably styrene, In this case, excellent effects are provided in fluidity and mechanical properties.
[45]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, preferably acrylonitrile.
[46]
The (A) acrylic graft resin may be, for example, an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, preferably a butyl acrylate-styrene-acrylonitrile graft copolymer.
[47]
[48]
(B) the first copolymer
[49]
The (B) first copolymer of the present disclosure may include, for example, an alkyl-substituted styrene, (meth)acrylate and a vinyl cyan compound, in which case blackness is greatly improved.
[50]
As a specific example, the (B) first copolymer may be a copolymer of a monomer mixture including an alkyl-substituted styrene, (meth)acrylate, and a vinyl cyan compound.
[51]
The alkyl-substituted styrene is one in which at least one hydrogen of styrene is replaced with an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms.
[52]
The alkyl-substituted styrene may be, for example, at least one selected from the group consisting of α-methylstyrene, p-methylstyrene and 2,4-dimethylstyrene, and may preferably be α-methylstyrene, in this case, The desired effect is well expressed.
[53]
The (meth) acrylate may be, for example, an alkyl (meth) acrylate, preferably methyl methacrylate, in this case, by improving the stability of the composition of the present invention, impact resistance, fluidity, Both heat resistance and blackness have excellent effects.
[54]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and 2-chloroacrylonitrile, in which case the desired effect of the present invention is well expressed. .
[55]
In the (B) first copolymer, the alkyl-substituted styrene is, for example, 25 to 50% by weight, preferably 30 to 45% by weight, more preferably 30 to 40% by weight, based on 100% by weight of the first copolymer. More preferably, it may be 35 to 40 wt%, and within this range, impact resistance, fluidity, heat resistance and blackness are all excellent effects.
[56]
In the (B) first copolymer, (meth)acrylate is, for example, 40 to 60% by weight, preferably 40 to 55% by weight, more preferably 40 to 50% by weight based on 100% by weight of the first copolymer. In this range, it is excellent in impact resistance, fluidity and heat resistance, and it does not increase the processing cost, thereby providing economic advantages while implementing high blackness.
[57]
In the present description, unless otherwise defined, the processing cost may mean a cost used in a thermoplastic resin composition manufacturing process such as a painting process.
[58]
In the (B) first copolymer, the vinyl cyanide compound may be, for example, 10 to 30% by weight, preferably 15 to 30% by weight, more preferably 17 to 22% by weight based on 100% by weight of the first copolymer. And within this range, impact resistance, fluidity, heat resistance and blackness are all excellent effects.
[59]
The (B) first copolymer may be, for example, 10 to 30% by weight, preferably 15 to 22% by weight, based on 100% by weight of the thermoplastic resin composition, and within this range, impact resistance, fluidity, heat resistance and blackness All of them have great advantages.
[60]
The (B) first copolymer may be an α-methylstyrene-methylmethacrylate-acrylonitrile copolymer as the most preferred example, and in this case, the desired effect of the present invention is best expressed.
[61]
The (B) first copolymer may have, for example, a glass transition temperature of 90 to 130° C., preferably 100 to 125° C., and more preferably 110 to 122° C., and has excellent heat resistance within this range, particularly for automobiles. It has the advantage that it can be applied with high quality to fields requiring high heat resistance, such as exterior materials.
[62]
In the present disclosure, the glass transition temperature (Tg) may be measured using a differential scanning calorimetry (DSC), and as a specific example, it may be measured using a differential scanning calorimeter manufactured by TA Instruments.
[63]
The (B) first copolymer has, for example, a weight average molecular weight of 70,000 to 150,000 g/mol, preferably 70,000 to 120,000 g/mol, more preferably 85,000 to 120,000 g/mol, even more preferably 90,000 to It may be 110,000 g/mol, and there is an advantage in that impact resistance, fluidity, heat resistance and blackness are excellent within this range.
[64]
In the present description, the weight average molecular weight may be measured as a relative value with respect to a standard PS (standard polystyrene) sample through a gel permeation chromatograph using tetrahydrofuran as an eluent. At this time, as a specific example of measurement, solvent: THF, column temperature: 40°C, flow rate: 0.3ml/min, sample concentration: 20mg/ml, injection amount: 5 μl, column model: 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing: Agilent ChemStation S/W, test method (Mn, Mw and PDI): It can be measured under the conditions of OECD TG 118.
[65]
The (B) first copolymer may have, for example, a refractive index of 1.50 to 1.57, preferably 1.52 to 1.55, and both have excellent heat resistance and blackness within this range.
[66]
In the present description, the refractive index may be measured at 25° C. using an Abbe refractometer in accordance with ASTM D542.
[67]
(B) first copolymer of the present description is a terpolymer comprising all of alkyl-substituted styrene, (meth)acrylate and vinyl cyanide, that is, a polymerized terpolymer, and a binary copolymer including only two of the above components It is a copolymer different from the co-polymer, and the thermoplastic resin composition of the present invention has the advantage of greatly improving blackness while maintaining excellent impact resistance, fluidity and heat resistance, including the first copolymer, which is the ternary copolymer.
[68]
In addition, the thermoplastic resin composition of the present disclosure is, for example, characterized in that it does not include the binary copolymer, and the binary copolymer may be, for example, an alkyl-substituted styrene-acrylonitrile copolymer.
[69]
[70]
(C) second copolymer
[71]
The (C) second copolymer of the present disclosure may include, for example, an alkyl unsubstituted styrene, (meth)acrylate and a vinyl cyan compound, in which case blackness is greatly improved.
[72]
The alkyl unsubstituted styrene means that any hydrogen of styrene is not substituted with alkyl, and in this case, it does not exclude that it includes a substituent other than an alkyl group.
[73]
The alkyl unsubstituted styrene may be, for example, at least one selected from the group consisting of styrene, p-bromo styrene, o-bromo styrene, and p-chloro styrene, and may preferably be styrene.
[74]
The type of (meth)acrylate and vinyl cyan compound included in the (C) second copolymer is the same as the type of (meth)acrylate and vinyl cyan compound included in the (B) first copolymer of the present description may be within.
[75]
The (C) second copolymer may include, for example, 15 to 30% by weight of an alkyl unsubstituted styrene, 60 to 80% by weight of a (meth)acrylate, and 3 to 15% by weight of a vinyl cyanide compound, within this range Impact resistance, fluidity, heat resistance and blackness are all excellent effects.
[76]
In the (C) second copolymer, the alkyl unsubstituted styrene is, for example, 15 to 30% by weight, preferably 17 to 26% by weight, more preferably 20 to 25% by weight based on 100% by weight of the second copolymer. and excellent fluidity and blackness within this range.
[77]
(C) The (meth)acrylate in the second copolymer is, for example, 60 to 80% by weight, preferably 63 to 78% by weight, more preferably 65 to 75% by weight based on 100% by weight of the second copolymer. may be, and within this range, there is an advantage in that the colorability is improved without lowering the impact resistance.
[78]
(C) The vinyl cyanide compound in the second copolymer may be, for example, 3 to 15% by weight, preferably 5 to 15% by weight, more preferably 6 to 11% by weight based on 100% by weight of the second copolymer and excellent chemical resistance and rigidity can be provided within this range.
[79]
The (C) second copolymer may be, for example, 5 to 25% by weight, preferably 5 to 20% by weight, based on 100% by weight of the thermoplastic resin composition, and has excellent fluidity within this range and has excellent impact resistance, heat resistance and There is an advantage that blackness is improved.
[80]
The (C) second copolymer may be a methyl methacrylate-styrene-acrylonitrile copolymer as the most preferred example, and in this case, the desired effect of the present invention is best expressed.
[81]
The (C) second copolymer may have, for example, a glass transition temperature of 80 to 120° C., preferably 90 to 110° C., and has excellent heat resistance within this range, particularly in fields requiring high heat resistance, such as automotive exterior materials. It has the advantage that it can be applied with high quality to
[82]
The (C) second copolymer may have, for example, a weight average molecular weight of 80,000 to 200,000 g/mol, preferably 100,000 to 170,000 g/mol, more preferably 120,000 to 155,000 g/mol, within this range. It has advantages of excellent impact resistance, fluidity, heat resistance and blackness.
[83]
The (C) second copolymer may have, for example, a refractive index of 1.45 to 1.55, preferably 1.50 to 1.53, and has excellent blackness within this range.
[84]
[85]
(D) (meth)acrylate polymer
[86]
The (D) (meth)acrylate polymer of the present disclosure may be, for example, polymerized including 70% by weight or more of a methacrylate compound, and preferably a polymethylmethacrylate resin containing 100% by weight of the methacrylate compound. may be, and in this case, there is an advantage of excellent impact resistance, fluidity, heat resistance and blackness.
[87]
The (D) (meth)acrylate polymer may be, for example, 25 to 45 wt%, preferably 30 to 40 wt%, based on 100 wt% of the thermoplastic resin composition, and within this range, colorability, scratch resistance and weather resistance There is an advantage that blackness is improved while being excellent.
[88]
The (D) (meth)acrylate polymer may have, for example, a glass transition temperature of 80 to 130° C., preferably 95 to 120° C., and has excellent heat resistance within this range.
[89]
The (D) (meth) acrylate polymer may have, for example, a weight average molecular weight of 60,000 to 120,000 g/mol, preferably 85,000 to 120,000 g/mol, more preferably 80,000 to 100,000 g/mol, within this range There is an advantage of excellent blackness in the interior.
[90]
The (D) (meth)acrylate polymer may have, for example, a refractive index of 1.40 to 1.55, preferably 1.45 to 1.52, and has excellent blackness within this range.
[91]
[92]
Thermoplastic resin composition
[93]
The thermoplastic resin composition may include, for example, (meth)acrylate in an amount of 40 to 59% by weight, preferably 45 to 59% by weight, more preferably 48 to 53% by weight based on 100% by weight of the thermoplastic resin composition, , there is an advantage in that both impact resistance and high blackness are improved while maintaining excellent heat resistance and fluidity within this range.
[94]
In addition, in the present invention, when the (meth)acrylate is less than the above range, there is a problem in realizing high blackness, and when it exceeds the above range, there is a problem in that impact resistance, fluidity and heat resistance are lowered, so it is preferable to adjust it within the above range Do.
[95]
The thermoplastic resin composition may further include, for example, a silicone compound, in which case fluidity and impact resistance are improved.
[96]
The silicone compound may be, for example, polyester modified siloxane, and in this case, there is an advantage in that fluidity and impact resistance are improved and high blackness can be realized.
[97]
The polyester-modified siloxane may mean polyester-modified siloxane.
[98]
The silicone compound may be included, for example, in an amount of 0.5 to 3 parts by weight, preferably 0.7 to 2 parts by weight, and more preferably 0.8 to 1.2 parts by weight, based on 100 parts by weight of the thermoplastic resin composition.
[99]
The thermoplastic resin composition is, for example, a colorant, a lubricant, an antioxidant, a UV stabilizer, an optical brightener, a chain extender, a release agent, a pigment, a dye, an antibacterial agent, a processing aid, a metal deactivator, a smoke inhibitor, an inorganic filler, glass fiber, It may further include one or more additives selected from the group consisting of a friction agent, a wear resistance agent, a heat stabilizer and a UV stabilizer. There is this.
[100]
The additive may be included, for example, in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 7 parts by weight, more preferably 1 to 5 parts by weight, within this range, based on 100 parts by weight of the total thermoplastic resin composition. There is an advantage in that the desired effect of the present invention is well expressed without reducing the original physical properties of the thermoplastic resin composition.
[101]
The colorant may be, for example, an anthraquinone-based dye, and in a preferred embodiment, may be a black organic dye containing 50 wt% or more of 1,4-bis(p-tolylamino)anthraquinone, and the black organic dye is green ( As a black organic dye of green tone, it has the advantage of easy expression of high blackness due to excellent compatibility with the composition of the present invention.
[102]
The colorant may be included, for example, in an amount of 0.1 to 1.5 parts by weight, preferably 0.3 to 1.0 parts by weight, based on 100 parts by weight of the thermoplastic resin composition, and has excellent blackness within this range.
[103]
The lubricant may be, for example, at least one selected from the group consisting of an ester lubricant, a metal salt lubricant, a carboxylic acid lubricant, a hydrocarbon lubricant, and an amide lubricant, preferably an amide lubricant, and more preferably a stera lubricant. It is a mid-type lubricant, and more preferably an alkylene bis (steramide) having 1 to 10 carbon atoms in the alkylene, in which case the original effect of the lubricant is well expressed without degrading the mechanical properties and thermal stability of the resin. There is an advantage.
[104]
The steramide-based lubricant may include a steramide substituent in which at least one of steramide and its hydrogen is substituted with another substituent.
[105]
The ester-based lubricant, metal salt-based lubricant, carboxylic acid-based lubricant, hydrocarbon-based lubricant, and amide-based lubricant are not particularly limited as long as they are materials commonly used as a corresponding type of lubricant in the technical field to which the present invention belongs.
[106]
The lubricant may be included, for example, in an amount of 0.1 to 3 parts by weight, preferably 0.5 to 1.5 parts by weight, based on 100 parts by weight of the total thermoplastic resin composition, while improving the wettability of the composition of the present substrate within this range and at the same time having impact resistance etc. have excellent effects.
[107]
[108]
The thermoplastic resin composition may have a Charpy impact strength (thickness 4.0mm, notch width 8mm, 23°C) measured according to ISO 179-1, for example, of 5 kJ/m 2 or more, preferably 6 to 12 kJ /m 2 And within this range, the impact resistance of the thermoplastic resin composition of the present substrate is excellent.
[109]
The thermoplastic resin composition has, for example, a flow index of 4 to 20 g/10min, preferably 5 to 15 g/10min, more preferably 5 to 10 g, measured under conditions of 220°C and 10kgf according to ISO 1133-1. It may be /10 min, and within this range, it has excellent fluidity and has the advantage of easy injection molding into various shapes.
[110]
The thermoplastic resin composition may have, for example, a heat deflection temperature of 70 to 100 ° C, preferably 75 to 85 ° C, measured in accordance with ISO 75, and has an effect of improving heat resistance while having excellent balance of properties within this range .
[111]
The thermoplastic resin composition may have, for example, a softening point temperature (VST) measured in accordance with ISO 306 of 90 to 120° C., preferably 94 to 110° C., and has excellent balance of properties within this range and the effect of improving heat resistance there is
[112]
The thermoplastic resin composition may have a blackness (L) of 4 or less, preferably 1 to 3.5, more preferably 1 to 2.5, measured in the SCE mode as an example, and realize high blackness within this range to provide a luxurious look. It has the advantage of providing a product with a feel.
[113]
[114]
Hereinafter, a method for producing the thermoplastic resin composition of the present invention and a molded article including the above-described thermoplastic resin composition will be described. In describing the method for manufacturing the thermoplastic resin composition and the molded article of the present invention, all of the above-described thermoplastic resin composition of the present invention is included.
[115]
[116]
Method for producing a thermoplastic resin composition
[117]
The method for producing the thermoplastic resin composition of the present invention is, for example, (A) two or more types of acrylic graft resins having different average particle diameters; (B) a first copolymer comprising an alkyl-substituted styrene, (meth)acrylate and a vinyl cyan compound; (C) a second copolymer comprising an alkyl unsubstituted styrene, (meth)acrylate and a vinyl cyan compound; and (D) a (meth)acrylate polymer, but comprising 40 to 59% by weight of (meth)acrylate based on the total weight of the thermoplastic resin composition, and in this case, it has excellent impact resistance, fluidity and heat resistance, , there is an advantage that high black color can be realized while providing economic advantages by not increasing the processing cost.
[118]
Unless otherwise defined in the present description, "consisting of" includes the meaning of "including and polymerized".
[119]
The kneading and extrusion may be performed by, for example, a single-screw extruder, a twin-screw extruder, or a Banbury mixer, in which case the composition is uniformly dispersed to have excellent compatibility.
[120]
In the kneading and extrusion, the processing temperature may be, for example, 200 to 300° C., preferably 220 to 270° C., in this case, sufficient melt-kneading may be possible while adequate throughput per unit time, and problems such as thermal decomposition of the resin component It has no effect.
[121]
The kneading and extrusion may be performed under the condition that, for example, the number of screw rotations is 100 to 500 rpm, 150 to 400 rpm, 100 to 350 rpm, 200 to 310 rpm, preferably 250 to 350 rpm, in which case the throughput per unit time It is appropriate and has an effect of suppressing excessive cutting while being excellent in process efficiency.
[122]
[123]
molded product
[124]
The molded article of the present substrate may include, for example, the thermoplastic resin composition of the present substrate, and the molded article has excellent heat resistance and impact resistance, so there is little change due to external environment, and a high level of blackness is realized to give a luxurious feeling. has the effect of providing.
[125]
The molded article may be, for example, an automobile exterior material, and in this case, it is possible to provide a high-quality molded article by satisfying all of the heat resistance, impact resistance, fluidity, high blackness and economy required in the market by the thermoplastic resin composition of the present invention.
[126]
The automobile exterior material may be, for example, a side mirror housing, a radiator grille, a filler, or a garnish, which provides economic advantages by increasing cost competitiveness compared to the prior art, and satisfies the needs of consumers by satisfying all of heat resistance, impact resistance and high blackness There are benefits to being satisfied.
[127]
[128]
In describing the thermoplastic resin composition of the present disclosure and a molded article including the same, other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation. .
[129]
[130]
Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such variations and modifications fall within the scope of the appended claims.
[131]
[132]
[Example]
[133]
Materials used in the following Examples and Comparative Examples are as follows.
[134]
(A1) First acrylic graft resin: ASA resin having an average particle diameter of 450 to 500 nm (prepared by graft polymerization of styrene and acrylonitrile to butyl acrylate rubber)
[135]
(A2) Second acrylic graft resin: ASA resin having an average particle diameter of 300 to 350 nm (prepared by graft polymerization of styrene and acrylonitrile to butyl acrylate rubber)
[136]
(A3) Third acrylic graft resin: ASA resin having an average particle diameter of 80 to 130 nm (prepared by graft polymerization of styrene and acrylonitrile to butyl acrylate rubber)
[137]
(B1) containing α-methylstyrene (AMS) 30 to 40% by weight, methyl methacrylate (MMA) 40 to 50 and acrylonitrile (AN) 15 to 30, a glass transition temperature of about 120° C., a weight average molecular weight AMS-MMA-AN terpolymer with 85,000 to 120,000 g/mol, refractive index 1.5336
[138]
(B2) AMS-AN copolymer comprising 65 to 75% by weight of α-methylstyrene and 25 to 35% by weight of acrylonitrile, having a glass transition temperature of about 123° C., a weight average molecular weight of 85,000 to 120,000 g/mol, and a refractive index of 1.5695
[139]
(C1) 65 to 75 methyl methacrylate, 20 to 25 % by weight of styrene (SM), and 5 to 15% by weight of acrylonitrile, a glass transition temperature of about 102° C., a weight average molecular weight of 100,000 to 170,000 g/mol, MMA-SM-AN copolymer with refractive index 1.515
[140]
(D1) polymethyl methacrylate having a glass transition temperature of about 113° C., a weight average molecular weight of 85,000 to 120,000 g/mol, and a refractive index of 1.49
[141]
(E1) polyester-modified silicone compound (EVONIK TEGOMER 6441P) (melting point (Tm): about 54° C.)
[142]
(F1) Coloring agent whose main component is 1,4-bis(p-tolylamino)anthraquinone
[143]
[144]
Examples 1 to 6, Comparative Examples 1 to 9, and Reference Examples 1 to 2
[145]
A thermoplastic resin composition was prepared by mixing and stirring the above-described components in the amounts shown in Table 1 below.
[146]
[147]
[Table 1]
division Example comparative example Reference example
One 2 3 4 5 6 One 2 3 4 5 6 7 8 9 One 2
(A1) ASA resin 3 - - 2 4 - - - 10 10 2 - 2 3 2 20 30
(A2) ASA resin - 10 7 - - 4 10 - - - - 10 - - - - -
(A3) ASA resin 30 23 26 35 29 32 23 33 23 23 35 23 35 30 35 13 3
(B1) AMS-MMA-AN copolymer 18 20 18 21 18 21 - 18 - - - 7 30 - 28 18 18
(B2) AMS-AN copolymer - - - - - - - - - - - - - 18 - - -
(C1) MMA-SM-AN copolymer 15 15 15 7 15 7 - 15 - 30 28 10 23 15 - 15 15
(D1) PMMA 34 32 34 35 34 36 67 34 67 33 35 55 5 34 35 34 34
(E1) silicone compound 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
(F1) colorant 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6
MMA total weight [wt%] 51-54 50-53 51-54 48-51 51-54 49-52 67 51-54 67 53-56 53-56 64~66 32-37 44-45 46-49 51-54 51-54
[148]
In Table 1, each content of (A1), (A2), (A3), (B1), (B2), (C1) and (D1) is a weight percent based on their total weight, (E1) and Each content of (F1) is a part by weight based on 100 parts by weight of the total weight of (A1), (A2), (A3), (B1), (B2), (C1) and (D1). In addition, in Table 1, the total weight of MMA is the total weight of MMA contained in components (B1), (B2), (C1) and (D1), (A1), (A2), (A3), (B1) ), (B2), (C1) and (D1) total 100% by weight.
[149]
[Test Example]
[150]
The thermoplastic resin compositions prepared in Examples 1 to 6, Comparative Examples 1 to 9, and Reference Examples 1 to 2 were put into an extrusion kneader (processing temperature: 240° C.) and extruded to prepare pellets. The prepared pellets were prepared as specimens using a 120 MT injection machine (processing temperature: 240° C.) based on ISO standards, which were measured by the following method, and the results are shown in Table 2 below. For reference, the blackness specimen was manufactured as a square high-gloss specimen having a thickness of 3 mm X 10 cm X 10 cm, and the high-gloss specimen had a glossiness of 85 to 95 measured at 60° using a GLOSS meter.
[151]
(1) Charpy impact strength (kJ/m 2 , Notched, thickness 4.0mm, notch width 8mm): It was measured at 23° C. using IMPACT TESTER manufactured by Tinius Olsen in accordance with ISO 179-1. Here, the higher the measured value, the better the impact resistance.
[152]
(2) Flow index (g/10min): According to ISO 1133-1, using GOTTFERT's MI-4, the weight was measured for 10 minutes at a temperature of 220° C. and a load of 10 kg. Here, the higher the measured value, the better the fluidity.
[153]
(3) Heat deflection temperature (℃): The heat deflection temperature was measured with TOYOSEIKI's Auto HDT Tester 6A-2 device in accordance with ISO 75. Here, the higher the measured value, the better the heat resistance.
[154]
(4) Softening point temperature (℃): The softening point temperature was measured with a TOYOSEIKI instrument in accordance with ISO 306. Here, the higher the measured value, the better the heat resistance.
[155]
(5) Blackness (L): L value was measured in SCE mode using a Ci7800 device manufactured by X-rite. Here, the L value is a numerical value for determining the White to Black values ​​in the L*a*b color system, and the lower the L value, the better the black feeling.
[156]
[157]
[Table 2]
division Example comparative example Reference example
One 2 3 4 5 6 One 2 3 4 5 6 7 8 9 One 2
Charpy impact strength
[kJ/m 2 ] 8 9 8 9.1 8.3 8.4 8 5.9 8.6 8 8.2 6 8.6 8 9.2 9.8 11.8
Flow index (MI) [g/10min] 6.7 6 6.5 5.2 6.3 5.7 4.4 6.8 3.8 5.5 4.8 4.5 5.8 5.8 5.8 5.8 5.3
Heat Deflection Temperature (HDT)[℃] 78 80 78 80 80 80 78 77 78 76 77 78 79 79 81 78 78
Softening Point Temperature (VST)[℃] 96 97 96 97 97 97 96 95 96 94 94 95 97 96 98 96 96
Blackness (L) 2.1 3.2 3.0 2.0 2.0 2.4 4.7 2.2 5.7 4.8 4.9 3.1 4.2 6 5.3 4.4 4.7
[158]
As shown in Table 2, it was confirmed that the thermoplastic resin compositions (Examples 1 to 6) of the present invention were superior to those of Comparative Examples 1 to 9 in heat resistance and fluidity, while improving both impact resistance and blackness. , the thermoplastic resin composition of the present invention includes two types of acrylic graft resins having different average particle diameters in a specific weight ratio, thereby providing a luxurious feeling by realizing a high level of blackness while having excellent impact resistance, fluidity and heat resistance. could
[159]
On the other hand, it was confirmed that the thermoplastic resin composition of the present invention significantly improved fluidity and blackness compared to Comparative Examples 1 and 3 not including (B1) and (C1), and furthermore, the comparison without (B1) It was confirmed that the blackness was also significantly improved compared to Example 4 and Comparative Example 5.
[160]
In addition, it was confirmed that the thermoplastic resin composition of the present invention was significantly excellent in impact resistance while maintaining fluidity, heat resistance, and blackness equal to or more compared to Comparative Example 2, which was tested using one type of ASA resin. Comparative Example 2 was difficult to apply to fields requiring high impact resistance, such as automotive exterior materials.
[161]
Further, (A), (B), (C) and (D) are all included, but Examples 1 to 6 in which the weight of (meth)acrylate falls within the range of the present invention and Comparative Example 6 exceeding the range of the present invention In comparison, it was confirmed that Examples 1 to 6 were superior in impact resistance, fluidity and heat resistance compared to Comparative Example 6.
[162]
As above, comparing Examples 1 to 6 that fall within the scope of the present invention and Comparative Example 7 that is less than the scope of the present invention, it was confirmed that Examples 1 to 6 had significantly superior blackness compared to Comparative Example 7.
[163]
In addition, Comparative Example 8 including a binary copolymer (B2) consisting of an alkyl-substituted styrene and a vinyl cyan compound instead of a terpolymer (B1) containing all of the alkyl-substituted styrene, (meth)acrylate and a vinyl cyan compound is carried out Compared to Examples 1 to 6, the blackness was significantly lowered, and it was confirmed that the high blackness, which is the desired effect of the present invention, could not be realized.
[164]
In addition, compared to Examples 1 to 6, in the case of Comparative Example 9 not including only (C1), it was confirmed that the blackness was greatly deteriorated.
Claims
[Claim 1]
(A) two or more types of acrylic graft resins having different average particle diameters; (B) a first copolymer comprising an alkyl-substituted styrene, (meth)acrylate and a vinyl cyan compound; (C) a second copolymer comprising an alkyl unsubstituted styrene, (meth)acrylate and a vinyl cyan compound; and (D) a (meth)acrylate polymer; however, the thermoplastic resin composition comprising 40 to 59% by weight of (meth)acrylate based on the total weight of the thermoplastic resin composition.
[Claim 2]
According to claim 1, wherein the thermoplastic resin composition is (A) 20 to 45% by weight of an acrylic graft resin; (B) 10 to 30% by weight of the first copolymer; (C) 5 to 25% by weight of a second copolymer; and (D) 25 to 45 wt% of a (meth)acrylate polymer.
[Claim 3]
[Claim 2] The thermoplasticity of claim 1, wherein the (A) acrylic graft resin comprises a first acrylic graft resin having an average particle diameter of 400 to 650 nm and a second acrylic graft resin having an average particle diameter of 50 to 160 nm. resin composition.
[Claim 4]
The thermoplastic resin composition according to claim 3, wherein the (A) acrylic graft resin comprises the first acrylic graft resin and the second acrylic graft resin in a weight ratio of 1:1 to 1:30. .
[Claim 5]
The method according to claim 1, wherein the (B) first copolymer comprises 25 to 50 wt% of alkyl-substituted styrene, 40 to 60 wt% of (meth)acrylate, and 10 to 30 wt% of a vinyl cyanide compound. A thermoplastic resin composition.
[Claim 6]
The method according to claim 1, wherein the (C) second copolymer comprises 15 to 30% by weight of alkyl unsubstituted styrene, 60 to 80% by weight of (meth)acrylate, and 3 to 15% by weight of a vinyl cyanide compound. A thermoplastic resin composition comprising
[Claim 7]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a blackness (L) of 4 or less as measured in SCE mode.
[Claim 8]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a flow index of 4 to 20 g/10 min measured at 220°C and 10 kgf in accordance with ISO 1133-1.
[Claim 9]
The thermoplastic resin composition of claim 1, wherein the Charpy impact strength (thickness 4.0mm, notch width 8mm, 23°C) measured in accordance with ISO 179-1 of the thermoplastic resin composition is 5 kJ/m 2 or more.
[Claim 10]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises a silicone compound.
[Claim 11]
According to claim 1, wherein the thermoplastic resin composition is a colorant, lubricant, antioxidant, UV stabilizer, optical brightener, chain extender, release agent, pigment, dye, antibacterial agent, processing aid, metal deactivator, smoke suppressant, inorganic filler, A thermoplastic resin composition comprising at least one additive selected from the group consisting of glass fiber, anti-friction agent, anti-wear agent, heat stabilizer and UV stabilizer.
[Claim 12]
A molded article comprising the thermoplastic resin composition of any one of claims 1 to 11.
[Claim 13]
The molded article according to claim 12, wherein the molded article is an automobile exterior material.