[Cross Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0132327 dated October 23, 2019, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article comprising the same, and more particularly, to a thermoplastic resin composition having excellent weather resistance and heat resistance while having excellent colorability, processability and scratch resistance, a method for producing the same, and a method for manufacturing the same It's about molded products.
background
[4]
ABS resin is an acrylonitrile-butadiene-styrene terpolymer, and has excellent impact resistance, rigidity, chemical resistance, and processability, and is used for various purposes in various fields such as electrical and electronics, architecture, and automobiles. However, since the ABS resin uses butadiene rubber polymer, there is a problem in that it is not suitable as an outdoor material because of its weak weather resistance.
[5]
In order to solve this problem, in order to obtain a thermoplastic resin with excellent physical properties and excellent weather resistance and aging resistance, a crosslinked alkyl acrylate rubber polymer without ethylenically unsaturated polymer that causes aging due to ultraviolet rays in the graft copolymer was used. ASA (acrylonitrile-styrene-acrylate copolymer) resins have been developed. Such ASA resin has excellent weather resistance and aging resistance, and is used in various fields such as automobiles, ships, leisure products, building materials, and horticulture.
[6]
In particular, in the case of ASA resin applied to automobiles, excellent colorability, heat resistance, scratch resistance, etc. are required in addition to weather resistance for a beautiful appearance.
[7]
To this end, in the case of mixing the ASA resin with a copolymer of a vinyl cyan compound and an α-methylstyrene compound, heat resistance is improved, but injection stability is reduced due to a large amount of gas generated, and not only is the gloss lowered, but the color of the resin itself is very yellow, so the colorability is improved. There is a problem with this decreasing.
[8]
In addition, when the ASA resin is compounded with a polymethyl methacrylate resin, colorability and scratch resistance are improved, but heat resistance is lowered, and when toughened PMMA (Toughened PMMA) is used, workability is reduced.
[9]
Therefore, there is a need to develop a resin excellent in heat resistance, weather resistance, colorability, scratch resistance and processability for ASA resin.
[10]
[Prior art literature]
[11]
[Patent Document] Korean Patent No. 1478394 (B1)
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[12]
In order to solve the problems of the prior art as described above, an object of the present invention is to provide a thermoplastic resin composition that is excellent in weather resistance and heat resistance, and has excellent colorability, processability and scratch resistance.
[13]
Another object of the present disclosure is to provide a method for preparing the above-mentioned thermoplastic resin composition.
[14]
Another object of the present invention is to provide a molded article prepared from the above-mentioned thermoplastic resin composition.
[15]
The above and other objects of the present disclosure can all be achieved by the present disclosure described below.
means of solving the problem
[16]
In order to achieve the above object, the present substrate comprises (A) 76 to 92% by weight of an (meth)acrylic acid alkylester compound, 1 to 8% by weight of an N-substituted maleimide compound, and 5 to 16% by weight of an aromatic vinyl compound. 65 to 85% by weight of a heat resistant copolymer; (B) 10 to 30 wt% of an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 200 nm; and (C) 1 to 15 wt% of an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 300 to 600 nm; The copolymer provides a thermoplastic resin composition, characterized in that the weight ratio of the aromatic vinyl compound to the N-substituted maleimide compound is 1.5 to 8.
[17]
In addition, the present substrate is (A) (meth) acrylic acid alkyl ester compound 76 to 92% by weight, N- substituted maleimide compound 1 to 8% by weight and aromatic vinyl compound 5 to 16% by weight of a heat-resistant copolymer comprising 65 to 85% by weight; (B) 10 to 30 wt% of an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 200 nm; and (C) 1 to 15 wt% of an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 300 to 600 nm; kneading and extruding under rpm conditions; including, wherein the (A) heat-resistant copolymer has a weight ratio of an aromatic vinyl compound and an N-substituted maleimide compound of 1.5 to 8. Provides a method for producing a thermoplastic resin composition do.
[18]
In addition, the present substrate provides a molded article, characterized in that produced from the thermoplastic resin composition.
Effects of the Invention
[19]
Advantageous Effects of Invention According to the present invention, there is an effect of providing a thermoplastic resin composition having excellent weather resistance and heat resistance and excellent colorability, processability and scratch resistance, a method for manufacturing the same, and a molded article including the same.
Best mode for carrying out the invention
[20]
Hereinafter, the thermoplastic resin composition of the present disclosure, a method for manufacturing the same, and a molded article including the same will be described in detail.
[21]
The present inventors found that when mixing a heat-resistant copolymer comprising a (meth)acrylic acid alkyl ester compound, an N-substituted maleimide compound, and an aromatic vinyl compound together with two ASA-based resins having different rubber particle diameters within a predetermined content range, heat resistance , weather resistance, colorability, processability and scratch resistance were all improved, and based on this, further research was devoted to complete the present invention.
[22]
The thermoplastic resin composition of the present disclosure is a heat-resistant copolymer comprising (A) 76 to 92 wt% of a (meth)acrylic acid alkylester compound, 1 to 8 wt% of an N-substituted maleimide compound, and 5 to 16 wt% of an aromatic vinyl compound 65 to 85% by weight; (B) 10 to 30 wt% of an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 200 nm; and (C) 1 to 15 wt% of an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 300 to 600 nm; The copolymer is characterized in that the weight ratio of the aromatic vinyl compound to the N-substituted maleimide compound is 1.5 to 8, and in this case, there is an effect of improving colorability, processability and scratch resistance while maintaining weather resistance and heat resistance.
[23]
Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each configuration.
[24]
(A) Heat-resistant copolymer
[25]
The (A) heat-resistant copolymer may be, for example, 65 to 85 wt%, preferably 70 to 80 wt%, more preferably 72 to 77 wt%, based on the total weight of the thermoplastic resin composition, within this range, heat resistance While this is maintained, there is an effect of improving weather resistance, colorability, workability and scratch resistance.
[26]
In the present description, the heat-resistant copolymer refers to a copolymer having a glass transition temperature of 117° C. or higher measured using a differential calorimeter (manufacturer: Ta Instruments, product name: DISCOVERY DSC25).
[27]
The (A) heat-resistant copolymer may include, for example, 76 to 92% by weight of a (meth)acrylic acid alkylester compound, 1 to 8% by weight of an N-substituted maleimide compound, and 5 to 16% by weight of an aromatic vinyl compound, Within this range, heat resistance and weather resistance are excellent, and in particular, colorability, workability and scratch resistance are improved.
[28]
The (meth)acrylic acid alkyl ester compound contained in the (A) heat-resistant copolymer is, for example, 76 to 92 wt%, preferably 78 to 90 wt%, more preferably 84, based on the total weight of the heat-resistant copolymer (A). to 90% by weight, while excellent in heat resistance and weather resistance within this range, particularly has the effect of improving colorability, processability and scratch resistance.
[29]
The N-substituted maleimide compound contained in the (A) heat-resistant copolymer is, for example, 1 to 8 wt%, preferably 2 to 7 wt%, more preferably 3 to 8 wt%, based on the total weight of the heat-resistant copolymer (A) It may be 7% by weight, and while excellent in heat resistance and weather resistance within this range, particularly, there is an effect of improving colorability, workability and scratch resistance.
[30]
The aromatic vinyl compound included in the (A) heat-resistant copolymer is, for example, 5 to 16 wt%, preferably 7 to 15 wt%, more preferably 7 to 10 wt%, based on the total weight of the heat-resistant copolymer (A) In this range, heat resistance and weather resistance are excellent, and in particular, colorability, processability and scratch resistance are improved.
[31]
The weight ratio (SM/MI) of the aromatic vinyl compound (SM) and the N-substituted maleimide compound (MI) contained in the (A) heat-resistant copolymer is, for example, 1.5 to 8, preferably 1.6 to 7.5, more preferably may be 1.6 to 3.5, and more preferably 1.65 to 2.5, and in this range, heat resistance and weather resistance are excellent, and in particular, colorability, processability and scratch resistance are improved.
[32]
(A) The (meth)acrylic acid alkyl ester compound contained in the heat-resistant copolymer is, for example, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester , (meth)acrylic acid decyl ester, and (meth)acrylic acid lauryl ester may be at least one selected from the group consisting of, preferably methyl methacrylate, in which case fluidity is appropriate and the effect of excellent weather resistance and heat resistance is obtained. have.
[33]
The N-substituted maleimide compound contained in the (A) heat-resistant copolymer is, for example, N-phenyl maleimide, N-methyl maleimide, N-ethyl maleimide, N-butyl maleimide and N-cyclohexyl maleimide. It may be at least one selected from the group consisting of, preferably N-phenyl maleimide, and in this case, heat resistance and scratch resistance are excellent.
[34]
The aromatic vinyl compound contained in the (A) heat-resistant copolymer is, for example, styrene, α-methyl styrene, o-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, selected from the group consisting of ο-brobo styrene, ρ-bromo styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyltoluene, vinylxylene, fluorostyrene and vinylnaphthalene. It may be one or more types, and may preferably be styrene, and in this case, the fluidity is appropriate and processability is excellent, and mechanical properties such as impact resistance are excellent.
[35]
The (A) heat-resistant copolymer may be, for example, a low-refractive-index heat-resistant copolymer having a refractive index of 1.515 or less, preferably 1.499 to 1.515, more preferably 1.499 to 1.512, and there is an excellent effect of colorability within this range.
[36]
The refractive index in the present description is measured at 25° C. using an Abbe refractometer in accordance with ASTM D542.
[37]
The (A) heat-resistant copolymer may have, for example, a glass transition temperature of 117 ° C. or higher, preferably 117 to 130 ° C., more preferably 117 to 125 ° C., and has excellent weather resistance and heat resistance within this range and processability, It has excellent scratch resistance and colorability.
[38]
In this description, the glass transition temperature is measured using a differential calorimeter (manufacturer: Ta Instruments, product name: DISCOVERY DSC25).
[39]
The (A) heat-resistant copolymer may have, for example, a weight average molecular weight of 80,000 to 130,000 g/mol, preferably 83,000 to 125,000 g/mol, and has excellent mechanical strength such as impact strength and scratch resistance within this range. And there is an effect excellent in colorability.
[40]
In this description, the weight average molecular weight is relative to a standard PS (Standard polystyrene) sample using tetrahydrofuran (THF) as a solvent at a temperature of 40 ° C. through gel chromatography (GPC) filled with porous silica as a column packing material. measure
[41]
(B) An acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 200 nm
[42]
The (B) acrylate-based rubber containing an acrylate-based rubber having an average particle diameter of 50 to 200 nm-aromatic vinyl compound-vinyl cyan compound graft copolymer (hereinafter referred to as 'small-diameter graft copolymer') is an example It may be 10 to 30% by weight, preferably 15 to 25% by weight, more preferably 20 to 25% by weight based on the total weight of the thermoplastic resin composition, and mechanical properties such as impact strength and tensile strength within this range It has excellent heat resistance, weather resistance, scratch resistance and colorability while excellent, and when it is less than the above range, a problem of lowering impact resistance may occur. .
[43]
The (B) small-diameter graft copolymer may be, for example, an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 200 nm, in this case It has excellent mechanical properties such as impact strength and tensile strength, but also has excellent heat resistance, colorability and weather resistance.
[44]
The acrylate-based rubber contained in the (B) small-diameter graft copolymer may have, for example, an average particle diameter of 50 to 200 nm, preferably 70 to 150 nm, more preferably 100 to 130 nm, , within this range, mechanical properties, heat resistance and weather resistance are all excellent, and if it is less than the above range, there may be a problem that mechanical properties such as impact strength and tensile strength are lowered. can occur
[45]
The acrylate-based rubber contained in the (B) small-diameter graft copolymer is, for example, 20 to 60% by weight, preferably 30 to 55% by weight, more preferably based on the total weight of the (B) small-diameter graft copolymer. It may be 40 to 50% by weight, and there is an excellent effect in weather resistance, impact strength and scratch resistance within this range.
[46]
In the present description, the average particle diameter is measured using an intensity gaussian distribution (Nicomp 380) by a dynamic laser light scattering method.
[47]
The acrylate-based rubber may be prepared by emulsion polymerization of an acrylate-based monomer, for example, and as a specific example, it may be prepared by emulsion polymerization by mixing an acrylate-based monomer, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte, and water. , in this case, the grafting efficiency is excellent and there is an effect of excellent physical properties such as impact resistance.
[48]
The acrylate-based monomer may be, for example, at least one selected from the group consisting of an alkyl acrylate having 2 to 8 carbon atoms, preferably an alkyl acrylate having 4 to 8 carbon atoms in the alkyl group, more preferably butyl acryl lactate or ethylhexyl acrylate.
[49]
The emulsifier may be, for example, a fatty acid metal salt having 12 to 20 carbon atoms, a metal rosin acid salt having 12 to 20 carbon atoms, or a mixture thereof, and the fatty acid metal salt having 12 to 20 carbon atoms is, for example, sodium fatty acid, sodium laurate, oleic acid It may be at least one selected from sodium and potassium oleate, and the metal rosin acid salt having 12 to 20 carbon atoms may be, for example, sodium rosinate, potassium rosinate, or a mixture thereof, in which case impact resistance and weather resistance are improved. there is
[50]
The emulsifier may be, for example, 1 to 4 parts by weight, preferably 1.5 to 3 parts by weight, based on 100 parts by weight of the acrylate-based monomer. It has the effect of improving weather resistance.
[51]
The initiator may be, for example, an inorganic peroxide, an organic peroxide, or a mixture thereof, and specific examples include: a water-soluble initiator such as potassium persulfate, sodium persulfate, or ammonium persulfate; and a fat-soluble initiator such as cumene hydroperoxide or benzoyl peroxide; and may be at least one selected from the group consisting of, in this case, the impact resistance and weather resistance are improved by facilitating the polymerization reaction.
[52]
The initiator may be, for example, 0.05 to 1 part by weight, preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the acrylate-based monomer, and the effect of improving the impact resistance and weather resistance by facilitating the polymerization reaction within this range is have.
[53]
The crosslinking agent is, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neo It may be at least one selected from the group consisting of pentyl glycol dimethacrylate, trimethylolpropane trimethacrylate and trimethylolmethane triacrylate, and in this case, the elasticity of the acrylate-based rubber is further increased, impact strength, tensile strength, etc. has the effect of improving the mechanical properties of
[54]
The crosslinking agent may be, for example, 0.02 to 0.3 parts by weight, preferably 0.05 to 0.2 parts by weight, based on 100 parts by weight of the acrylate-based monomer, and within this range, the elasticity of the acrylate-based rubber is further increased, impact strength, and tensile strength There is an effect of improving mechanical properties such as strength.
[55]
The electrolyte may be, for example, at least one selected from the group consisting of sodium hydrogen carbonate (NaHCO 3 ), disodium disulfide (Na 2 S 2 O 7 ) and potassium carbonate (K 2 CO 3 ).
[56]
The electrolyte may be, for example, 0.01 to 0.5 parts by weight based on 100 parts by weight of the acrylate-based monomer.
[57]
The acrylate-based rubber may further include, for example, a molecular weight regulator, and the molecular weight regulator may be, for example, t-dodecyl mercaptan, n-octyl mercaptan, or a mixture thereof. In this case, the acrylate-based rubber There is an effect of improving the impact resistance and weather resistance of the composition by controlling the weight average molecular weight of the composition.
[58]
The molecular weight modifier may be, for example, 0.01 to 1 part by weight, preferably 0.01 to 0.3 part by weight, based on 100 parts by weight of the acrylate-based monomer, and has an effect of improving impact resistance and weather resistance within this range.
[59]
The aromatic vinyl compound contained in the (B) small-diameter graft copolymer is, for example, 10 to 50% by weight, preferably 20 to 45% by weight, more preferably based on the total weight of the (B) small-diameter graft copolymer. may be 30 to 40% by weight, and within this range, mechanical properties such as tensile strength and impact strength and workability are excellent.
[60]
The aromatic vinyl compound included in the (B) small-diameter graft copolymer is, for example, styrene, α-methyl styrene, o-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t- butyl styrene, ο-brobo styrene, ρ-bromo styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyltoluene, vinylxylene, fluorostyrene and vinylnaphthalene It may be one or more types selected from the group, and in this case, the fluidity is appropriate and the workability is excellent, and mechanical properties such as tensile strength and impact strength are also excellent.
[61]
The vinyl cyan compound contained in the (B) small-diameter graft copolymer is, for example, 5 to 30% by weight, preferably 5 to 25% by weight, more preferably based on the total weight of the (B) small-diameter graft copolymer. may be 10 to 20% by weight, and within this range, there is an excellent effect of impact resistance, processability, and the like.
[62]
The vinyl cyan compound included in the (B) small-diameter graft copolymer may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof, and in this case, impact resistance and processability are excellent.
[63]
(C) An acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 300 to 600 nm
[64]
The (C) acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer (hereinafter referred to as 'large-diameter graft copolymer') comprising an acrylate-based rubber having an average particle diameter of 300 to 600 nm is an example 1 to 15 wt%, preferably 1 to 10 wt%, more preferably 3 to 7 wt%, based on the total weight of the thermoplastic resin composition, excellent mechanical properties such as impact strength and tensile strength within this range It has excellent effects in heat resistance, weather resistance, scratch resistance and colorability. If it is less than the above range, a problem of lowering impact resistance may occur, and if it exceeds the above range, a graft rate may be lowered, thereby causing a problem in that hardness and scratch resistance are lowered.
[65]
The (C) large-diameter graft copolymer may be, for example, an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 300 to 600 nm, in which case the impact It has excellent mechanical properties such as strength and tensile strength, and has excellent heat resistance, colorability and weather resistance.
[66]
The (C) large-diameter graft copolymer comprises, for example, 20 to 60% by weight of an acrylate-based rubber having an average particle diameter of 300 to 600 nm, 10 to 50% by weight of an aromatic vinyl compound, and 5 to 30% by weight of a vinyl cyanide compound. may be, and there is an effect of improving mechanical properties, heat resistance and weather resistance within this range.
[67]
The acrylate-based rubber contained in the (C) large-diameter graft copolymer may have, for example, an average particle diameter of 300 to 600 nm, preferably 300 to 500 nm, more preferably 350 to 450 nm, within this range. It has excellent mechanical properties such as impact strength and tensile strength. If it is less than the above range, impact resistance may be reduced, and if it exceeds the above range, problems may occur in which fluidity, processability and glossiness are lowered.
[68]
The acrylate-based rubber contained in the (C) large-diameter graft copolymer is, for example, 20 to 60% by weight, preferably 30 to 55% by weight, more preferably based on the total weight of the (C) large-diameter graft copolymer. It may be 40 to 50% by weight, there is an effect of improving the impact resistance and scratch resistance within this range.
[69]
The acrylate-based rubber may be prepared by emulsion polymerization of an acrylate-based monomer, for example, and as a specific example, it may be prepared by emulsion polymerization by mixing an acrylate-based monomer, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte, and water. , in this case, the grafting efficiency is excellent and there is an effect of excellent physical properties such as impact resistance.
[70]
The acrylate-based monomer, emulsifier, initiator, grafting agent, cross-linking agent, electrolyte and solvent used for preparing the acrylate-based rubber contained in the (C) large-diameter graft copolymer is the (B) small-diameter graft copolymer of the present invention. It may be selected within the same type and content range as those used in manufacturing the acrylate-based rubber included in the .
[71]
The aromatic vinyl compound contained in the (C) large-diameter graft copolymer is, for example, 10 to 50% by weight, preferably 20 to 45% by weight, more preferably 30 to 50% by weight based on the total weight of the (C) large-diameter graft copolymer. It may be 40% by weight, and there is an excellent effect in impact resistance, weather resistance and chemical resistance within this range.
[72]
The vinyl cyan compound included in the (C) large-diameter graft copolymer is, for example, 5 to 30% by weight, preferably 5 to 25% by weight, more preferably 10% by weight based on the total weight of the (C) large-diameter graft copolymer. to 20% by weight, there is an excellent effect in mechanical strength, discoloration resistance, etc. within this range.
[73]
In the present description, the term "total weight of the copolymer" may mean the actual total weight of the obtained copolymer or the total weight of the total monomers added instead of it.
[74]
The types of the vinyl cyan compound and the aromatic vinyl compound included in the (C) large-diameter graft copolymer may be the same as the types of the vinyl cyan compound and the aromatic vinyl compound included in the (B) small-diameter graft copolymer of the present disclosure. .
[75]
Thermoplastic resin composition
[76]
The thermoplastic resin composition may be, for example, at least one selected from the group consisting of lubricants, antioxidants, UV stabilizers, release agents, pigments, dyes and UV stabilizers, and in this case, weather resistance, heat resistance, processability and resistance without lowering mechanical properties It has the effect of maintaining excellent scratch properties.
[77]
The lubricant may be, for example, at least one selected from the group consisting of ethylene bis stearamide, oxidized polyethylene wax and magnesium stearate, and may preferably be ethylene bis stearamide, in which case the wettability of the composition of the present substrate is improved. At the same time, there is an effect of excellent mechanical properties.
[78]
The lubricant is, for example, 0.1 to 3 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of (A) heat-resistant copolymer, (B) small-diameter graft copolymer, and (C) large-diameter graft copolymer. , more preferably 0.05 to 1.5 parts by weight, and there is an effect of improving the wettability of the composition of the present base material within this range and at the same time having excellent mechanical properties.
[79]
The antioxidant may include, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, or a mixture thereof, and in this case, it prevents oxidation due to heat during the extrusion process and has excellent mechanical properties of the present invention.
[80]
The antioxidant is, for example, 0.01 to 3 parts by weight, preferably 0.01 to 1 parts by weight, based on 100 parts by weight of (A) heat-resistant copolymer, (B) small-diameter graft copolymer, and (C) large-diameter graft copolymer. parts, more preferably 0.1 to 1 part by weight, and within this range, oxidation due to heat is prevented during the extrusion process and the mechanical properties of the present invention are excellent.
[81]
The dye is, for example, 0.1 to 1.5 parts by weight, preferably 0.5 to 1 part by weight, based on 100 parts by weight of (A) heat-resistant copolymer, (B) small-diameter graft copolymer, and (C) large-diameter graft copolymer. In this range, there is an excellent effect of color expression without reducing the original physical properties of the thermoplastic resin composition of the present base material.
[82]
The thermoplastic resin composition may have, for example, weather resistance (ΔE) of 1.75 or less, preferably 1.0 to 1.75, and more preferably 1.5 to 1.7, and has an excellent effect of property balance within this range.
[83]
Weather resistance (ΔE) in this substrate can be measured with a weather resistance measuring device (QUV), and the measurement conditions are UV lamp illuminance 0.77 W/m 2 , humidity 50%, BLACK PANEL temperature 60 ℃, and to stay for 20 hours, ΔE is the arithmetic mean value of Hunter Lab values ​​before and after residence, and the closer the value is to 0, the better the weather resistance is.
[84]
△E = √{(L-L') 2 + (a-a') 2 + (b-b') 2 } (√ : radical sign)
[85]
The thermoplastic resin composition may have an L value (colorability) of 24.7 or less, preferably 20 to 24.7, more preferably 23 to 24.6, measured using Hunter Lab, for example, within this range. There is an excellent effect of balance.
[86]
The thermoplastic resin composition may have a fluidity of 11 to 15.5 g/10min, preferably 12 to 15 g/10min, measured at 220°C under a load of 10 kg according to ASTM D1238, and excellent processability within this range. there is
[87]
The thermoplastic resin composition may have a pencil hardness of 2H or more, preferably 2H to 4H, measured at a 45° angle with a load of 0.5 kg based on ASTM D3363 using a pencil hardness tester (Cometech), for example, within this range There is an excellent effect in the physical property balance and scratch resistance.
[88]
The thermoplastic resin composition may have, for example, a heat deflection temperature of 89° C. or higher, preferably 89 to 100° C., more preferably 89 to 93° C., measured according to ASTM D648, and has excellent physical property balance within this range. It works.
[89]
The thermoplastic resin composition has, for example, an Izod impact strength (1/4", 23° C.) measured according to ASTM D256 of 5 kgfcm/cm or more, preferably 5 to 10 kgfcm/cm, more preferably 5 to 8 It may be kgfcm/cm, and within this range, all physical property balances have an excellent effect.
[90]
Method for producing a thermoplastic resin composition
[91]
The method for preparing the thermoplastic resin composition of the present disclosure includes, for example, (A) (meth)acrylic acid alkylester compound 76 to 92% by weight, N-substituted maleimide compound 1 to 8% by weight, and aromatic vinyl compound 5 to 16% by weight 65 to 85% by weight of the heat-resistant copolymer; (B) 10 to 30 wt% of an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 200 nm; and (C) 1 to 15 wt% of an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 300 to 600 nm; kneading and extruding under rpm conditions; but, the (A) heat-resistant copolymer is characterized in that the weight ratio of the aromatic vinyl compound to the N-substituted maleimide compound is 1.5 to 8, and in this case, the weather resistance and heat resistance are It has excellent effects in colorability, processability and scratch resistance while being excellent.
[92]
The method for preparing the thermoplastic resin composition is, for example, a heat-resistant copolymer comprising 76 to 92% by weight of a (meth)acrylic acid alkylester compound, 1 to 8% by weight of an N-substituted maleimide compound, and 5 to 16% by weight of an aromatic vinyl compound. (A) preparing a heat-resistant copolymer by polymerizing a polymerization solution in which 25 to 40 parts by weight of a reaction solvent and 0.01 to 1 parts by weight of an initiator are mixed with 100 parts by weight of a monomer mixture containing 65 to 85% by weight. .
[93]
The reaction solvent in the step (A) for preparing the heat-resistant copolymer may be, for example, at least one selected from the group consisting of ethylbenzene, toluene, methylethyl ketone and xylene, in this case, viscosity control is easy and polymerization conversion rate is high It has the effect of inhibiting the decrease.
[94]
The reaction solvent may be, for example, 25 to 40 parts by weight, preferably 30 to 40 parts by weight, based on 100 parts by weight of the monomer mixture, within this range, the effect of reducing the excessive increase in viscosity or reduction in conversion and molecular weight have.
[95]
The initiator in the step (A) for preparing the heat-resistant copolymer is, for example, t-butylperoxy-2-ethylhexanoate (tert-Butylperoxy-2-ethylhexanoate), benzoyl peroxide (benzoyl peroxide), t-butyl Peroxyisobutyrate (t-butylperoxyisobutyrate), 1,1-bis (t-butylperoxy) cyclohexane (1,1-bis (tbutylperoxy) cyclohexane), 2,2-bis (4,4-di-t- Butylperoxycyclohexane)propane (2,2-bis(4,4-di-t-butylperoxy cyclohexane)propane, t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxy t-butylperoxylaurate, t-butyl peroxy isopropylmonocarbonate, t-butyl peroxy 2-ethylhexylmonocarbonate, t-hexyl per thexylperoxybenzoate, t-butyl peroxyacetate, 2,2-bis(t-butyl peroxy)butane, t- Butyl peroxybenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane (2,5-dimethyl-2,5-bis ( t-butyl peroxy)hexane), t-butyl cumyl peroxide,It may be at least one selected from the group consisting of di-t-butyl peroxide and di-t-amyl peroxide, preferably t-butyl peroxide It may be -2-ethylhexanoate (tert-Butylperoxy-2-ethylhexanoate), and in this case, it has the effect of facilitating the polymerization reaction to maintain excellent mechanical properties, weather resistance, heat resistance and scratch resistance.
[96]
The initiator may be, for example, 0.01 to 1 part by weight, preferably 0.01 to 0.5 part by weight, and more preferably 0.01 to 0.2 part by weight, based on 100 parts by weight of the monomer mixture, and within this range, the polymerization reaction is facilitated and the mechanical It has the effect of maintaining excellent physical properties, weather resistance, heat resistance and scratch resistance.
[97]
The polymerization in the step (A) for preparing the heat-resistant copolymer is, for example, continuously inputting the polymerization solution into a continuous reactor at a rate of 7 to 20 kg/hr, preferably 10 to 15 kg/hr, and a temperature of 130 to 160 ℃, preferably 140 to 150 ℃ can be carried out, and in this case, the particle stability of the copolymer is improved compared to the case of batch injection to make the internal structure of the particles uniform, so that mechanical properties, weather resistance, heat resistance, scratch resistance and colorability are improved. It has an excellent effect.
[98]
In the present description, "continuous polymerization" refers to a process in which a material participating in polymerization is continuously supplied into a reactor, a product produced by polymerization is continuously discharged, and unreacted monomer is recovered and reused using a volatilization process. .
[99]
The kneading and extrusion may be performed by, for example, a single screw extruder, a twin screw extruder, or a Banbury mixer, and in this case, the composition is uniformly dispersed to have excellent compatibility.
[100]
The kneading and extrusion may be performed, for example, at a barrel temperature of 200 to 300 ° C., preferably within a range of 200 to 250 ° C. In this case, the throughput per unit time may be adequate and sufficient melt kneading may be possible, and There is an effect that does not cause problems such as thermal decomposition.
[101]
The kneading and extrusion may be performed under the condition that the screw rotation speed is 200 to 300 rpm, preferably 250 to 300 rpm, for example. there is
[102]
The molded article of the present substrate may be prepared from the thermoplastic resin composition of the present substrate, for example, and in this case, there is an effect of improving weather resistance, colorability, workability and scratch resistance while maintaining heat resistance.
[103]
The molded article may be, for example, at least one selected from the group consisting of automobile parts, electric/electronic parts, or building materials, and preferably may be interior/exterior materials for automobiles.
[104]
In describing the thermoplastic resin composition of the present invention, its manufacturing method and molded article, other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation. do.
[105]
Hereinafter, preferred examples are presented to help the understanding of the present disclosure, but the following examples are merely illustrative of the present disclosure, 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 disclosure, It goes without saying that such variations and modifications fall within the scope of the appended claims.
[106]
[Example]
[107]
Materials used in the following Examples and Comparative Examples are as follows.
[108]
* (B) Small-diameter graft copolymer: a graft copolymer with an average rubber particle diameter of 120 nm (SA130 from LG Chem)
[109]
* (C) Large-diameter graft copolymer: a graft copolymer with an average rubber particle diameter of 400 nm (SA927 from LG Chem)
[110]
* Lubricant: Ethylene Bis Stearamide (EBA)
[111]
* Antioxidant: Songnox 11B from Songwon Industries
[112]
* Dye: LG Chem's BK-39
[113]
Example 1
[114]
< (A) Preparation of heat-resistant copolymer >
[115]
33.3 parts by weight of toluene, 90% by weight of methyl methacrylate (hereinafter referred to as 'MMA'), 3% by weight of N-phenylmaleimide (hereinafter referred to as 'PMI') and 7% by weight of styrene (hereinafter referred to as 'SM') A polymerization solution in which 0.04 parts by weight of dicumyl peroxide was added as an initiator was continuously introduced into a continuous reactor at a rate of 12 kg/hr for 24 hours, and after polymerization at a temperature of 145 ° C. (A) heat-resistant copolymer in the form of pellets was removed and prepared, and the prepared copolymer had a refractive index of 1.4996, a glass transition temperature of 120.5° C., and a weight average molecular weight of 84,000 g/mol.
[116]

[117]
(A) 75 parts by weight of the heat-resistant copolymer prepared above, (B) 20 parts by weight of the small-diameter graft copolymer, and (C) 5 parts by weight of the large-diameter graft copolymer 1 part by weight of a lubricant, 0.5 parts by weight of an antioxidant and 0.5 parts by weight of the dye was added and put into an extruder (28Ψ) at 230°C to prepare a resin in a pellet state, and then injected to prepare a specimen.
[118]
Examples 2 to 7
[119]
The same procedure as in Example 1 was carried out, except that the components and contents of Table 1 below were used to prepare the (A) heat-resistant copolymer.
[120]
Comparative Examples 1 to 7
[121]
The same procedure as in Example 1 was carried out, except that the components and contents of Table 2 below were used to prepare the (A) heat-resistant copolymer.
[122]
[Test Example]
[123]
The properties of the specimens prepared in Examples 1 to 7 and Comparative Examples 1 to 7 were measured in the following manner, and the results are shown in Tables 1 and 2 below.
[124]
How to measure
[125]
* Refractive index: measured at 25 ℃ using an Abbe refractometer in accordance with ASTM D542.
[126]
* Weight average molecular weight (g/mol): Standard PS (Standard polystyrene) sample using tetrahydrofuran (THF) as a solvent at a temperature of 40 ° C through gel chromatography (GPC) filled with porous silica as a column packing material. Relative values ​​were measured.
[127]
* Glass transition temperature (℃): was measured using a differential calorimeter (manufacturer: Ta Instruments, product name: DISCOVERY DSC25).
[128]
* Izod impact strength (kgf·cm/cm): It was measured according to ASTM D256 using a specimen thickness of 1/4″.
[129]
* Fluidity (g/10min): According to ASTM D1238, it was measured at 220 °C under a load of 10 kg for 10 minutes.
[130]
* Thermal deformation temperature (℃): According to ASTM D648, it was measured under a load of 18.6 kgf/cm 2 using a specimen having a thickness of 6.4 mm .
[131]
* Pencil hardness: Using a pencil hardness tester (Cometech), according to ASTM D3363, fix the pencil at a load of 0.5 kg and an angle of 45°, and then scrape the surface of the specimen by hardness (in order of 2B, B, HB, F, H). It was measured whether or not it was scratched with the naked eye.
[132]
* Colorability (blackness; Color L): Based on the CIE1976 L*a*b* color system, the color L value was measured using a color meter (model name: Color Eye 7000A). At this time, L=100 means pure white, and L=0 means pure black, and the lower the L value, the better the black feeling.
[133]
* Weather resistance (ΔE): Measured with a weather resistance measuring device (QUV), measurement conditions are UV lamp illumination 0.77 W/m 2 , humidity 50 %, BLACK PANEL temperature 60 ° C., and staying for 20 hours, ΔE is retention It is an arithmetic mean value of the Hunter Lab values ​​before and after. The closer the value is to 0, the better the weather resistance is.
[134]
△E = √v{(L-L') 2 + (a-a') 2 + (b-b') 2 } (√radical sign)
[135]
[Table 1]
division Example
1 Example
2 Example
3 Example
4 Example
5 Example
6 Example
7
(A) Heat-resistant
copolymer
composition MMA 90 86 81 78 84 83 80
PMI 3 4 4 7 6 2 5
SM 7 10 15 15 10 15 15
(A) Heat-resistant
copolymer
properties refractive index 1.4996 1.5038 1.5088 1.5125 1.5118 1.5117 1.5150
Mw 84,000 113,000 122,000 103,000 98,000 96,000 85,000
Tg 120.5 120.8 117.9 121.7 123.1 117.4 120.3
Thermoplastic
resin
composition
composition (A) 75 75 75 75 75 75 75
(B) 20 20 20 20 20 20 20
(C) 5 5 5 5 5 5 5
Thermoplastic
resin
composition
physical properties impact strength 5 6 7 6 6 6 5
liquidity 15 13 12 14 14 14 15
heat deflection
temperature 91 91 89 92 93 89 91
pencil hardness 2H 2H 2H 2H 2H 2H 2H
colorability 23.8 24.1 24.3 24.5 24.4 24.4 24.6
weather resistance 1.5 1.6 1.6 1.7 1.6 1.6 1.6
[136]
[Table 2]
division Comparative Example
1 Comparative Example
2 Comparative Example
3 Comparative Example
4 Comparative Example
5 Comparative Example
6 Comparative Example
7
(A) Heat-resistant
copolymer
composition MMA 95 79 76 60 84 92 70
PMI 5 3 4 10 10 4 3
SM 0 18 20 30 6 4 27
(A) Heat-resistant
copolymer
properties refractive index 1.4981 1.5168 1.5178 1.5311 - - 1.5246
Mw 70,000 96,000 140,000 142,000 - - 149,000
Tg 121.8 117.7 114.5 114.2 - - 110.7
Thermoplastic
resin
composition
composition (A) 75 75 75 75 - - 75
(B) 20 20 20 20 - - 20
(C) 5 5 5 5 - - 5
Thermoplastic
resin
composition
physical properties impact strength 3 6 9 10 - 10
liquidity 16 14 10 10 - - 9
heat deflection
temperature 92 89 86 86 - - 82
pencil hardness H H H F - - F
colorability 23.8 24.7 25.0 25.5 - - 25.3
weather resistance 1.5 1.7 1.8 1.9 - - 1.9
[137]
As shown in Tables 1 and 2, Examples 1 to 7 prepared according to the present invention, compared to Comparative Examples 1 to 7 out of the scope of the present invention, excellent impact strength, heat resistance and weather resistance, fluidity, thermal deformation temperature , excellent effects of pencil hardness (scratch resistance) and colorability were confirmed.
[138]
In addition, the heat-resistant copolymer of Examples 1 to 7 (A) prepared according to the present invention had a lower refractive index and a higher glass transition temperature, and thus the colorability and heat deformation temperature of the resin composition were improved.
[139]
In addition, (A) Comparative Examples 5 and 6, in which the weight ratio of SM/PMI in the heat-resistant copolymer, was less than 1.5, PMI was precipitated in the volatilization process during polymerization and polymerization was impossible, and Comparative Example 7 in which the weight ratio of SM/PMI exceeded 8 (A) The low glass transition temperature and high refractive index of the heat-resistant copolymer made the resin composition poor in heat deformation temperature, pencil hardness (scratch resistance), colorability and weather resistance.
Claims
[Claim 1]
(A) 65 to 85% by weight of a heat-resistant copolymer comprising 76 to 92% by weight of a (meth)acrylic acid alkylester compound, 1 to 8% by weight of an N-substituted maleimide compound, and 5 to 16% by weight of an aromatic vinyl compound; (B) 10 to 30 wt% of an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 200 nm; and (C) 1 to 15 wt% of an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 300 to 600 nm; The copolymer is a thermoplastic resin composition, characterized in that the weight ratio of the aromatic vinyl compound to the N-substituted maleimide compound is 1.5 to 8.
[Claim 2]
The thermoplastic resin composition according to claim 1, wherein the (A) heat-resistant copolymer has a refractive index of 1.515 or less.
[Claim 3]
The thermoplastic resin composition according to claim 1, wherein the heat-resistant copolymer (A) has a glass transition temperature of 117°C or higher.
[Claim 4]
The thermoplastic resin composition according to claim 1, wherein the heat-resistant copolymer (A) has a weight average molecular weight of 80,000 to 130,000 g/mol.
[Claim 5]
According to claim 1, wherein the (B) graft copolymer has an average particle diameter of 50 to 200 nm acrylate-based rubber 20 to 60% by weight, 10 to 50% by weight of an aromatic vinyl compound, and 5 to 30% by weight of a vinyl cyanide compound A thermoplastic resin composition comprising a.
[Claim 6]
According to claim 1, wherein the (C) graft copolymer has an average particle diameter of 300 to 600 nm acrylate-based rubber 20 to 60% by weight, aromatic vinyl compound 10 to 50% by weight, and vinyl cyanide compound 5 to 30% by weight A thermoplastic resin composition comprising a.
[Claim 7]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a weather resistance (ΔE) of 1.75 or less.
[Claim 8]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an L value (colorability) of 24.7 or less, measured using a Hunter Lab.
[Claim 9]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a fluidity of 11 to 15.5 g/10min, measured at 220°C under a load of 10 kg, according to ASTM D1238.
[Claim 10]
(A) 65 to 85% by weight of a heat-resistant copolymer comprising 76 to 92% by weight of a (meth)acrylic acid alkylester compound, 1 to 8% by weight of an N-substituted maleimide compound, and 5 to 16% by weight of an aromatic vinyl compound; (B) 10 to 30 wt% of an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 200 nm; and (C) 1 to 15 wt% of an acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 300 to 600 nm; A method of producing a thermoplastic resin composition, comprising the steps of kneading and extruding under rpm conditions, wherein (A) the heat-resistant copolymer has an aromatic vinyl compound and an N-substituted maleimide compound in a weight ratio of 1.5 to 8.
[Claim 11]
The method of claim 10, wherein the method for preparing the thermoplastic resin composition comprises 76 to 92 wt% of a (meth)acrylic acid alkylester compound, 1 to 8 wt% of an N-substituted maleimide compound, and 5 to 16 wt% of an aromatic vinyl compound. Polymerizing a polymerization solution in which 25 to 40 parts by weight of a reaction solvent and 0.01 to 1 parts by weight of an initiator are mixed with 100 parts by weight of the monomer mixture (A) to prepare a heat-resistant copolymer .
[Claim 12]
12. The method of claim 11, wherein (A) the polymerization in the step of preparing the heat-resistant copolymer, the polymerization solution is continuously introduced into a continuous reactor at a rate of 7 to 20 kg / hr, characterized in that it is carried out at a temperature of 130 to 160 ℃. A method for producing a thermoplastic resin composition comprising a.
[Claim 13]
10. A molded article, characterized in that made of the thermoplastic resin composition according to any one of claims 1 to 9.