Title of Invention: Thermoplastic resin composition, manufacturing method thereof, and molded article comprising same
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application has the benefit of priority based on the Korean Patent Application No. 10-2019-0132326 dated October 23, 2019 and the Korean Patent Application No. 10-2020-0121468, which was re-applied on September 21, 2020 based thereon. All contents disclosed in the document of the corresponding Korean patent application are incorporated as a part of this specification.
[3]
The present invention relates to a thermoplastic resin composition, a method for manufacturing 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 scratch resistance and colorability, a method for manufacturing the same, and a molded article comprising the same it's about
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 a 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. This ASA resin has excellent weather resistance and aging resistance, so it is used in various fields such as automobiles, ships, leisure products, building materials, and horticulture.
[6]
In particular, the ASA resin for interior and exterior of automobiles can realize light weight, improved design and design freedom, and reduced production costs, so the market is growing. There is an increasing demand for high blackness.
[7]
For this purpose, it is implemented by methods such as painting and plating on ASA resin, but considering the environmental aspect, there is a demand for a product that can be implemented without painting. However, the unpainted product has a problem in that the product value is lowered due to the deterioration of appearance characteristics such as scratch resistance and color compared to the painted product.
[8]
In addition, when kneading ASA resin with α-methylstyrene-based heat-resistant copolymer to impart heat resistance, heat resistance is improved, but satisfactory blackness is not realized due to insufficient coloration due to the high refractive index of α-methylstyrene. there is a problem.
[9]
Therefore, it is necessary to develop a resin excellent in colorability that can realize high blackness while imparting heat resistance and scratch resistance to the ASA resin.
[10]
[Prior art literature]
[11]
[Patent Document] (Patent Document 1) Korea 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 scratch resistance and colorability.
[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 is (A) 65 to 83% by weight of an (meth)acrylic acid alkylester compound, 2 to 12% by weight of an N-substituted maleimide compound, 1 to 6% by weight of a vinyl cyanide compound, and an aromatic vinyl compound 55 to 70% by weight of a non-grafted copolymer comprising 7 to 17% by weight; (B) 20 to 42 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 composition is provided.
[17]
[18]
In addition, the present substrate is (A) 65 to 83% by weight of an (meth)acrylic acid alkyl ester compound, 2 to 12% by weight of an N-substituted maleimide compound, 1 to 6% by weight of a vinyl cyanide compound, and 7 to 17% by weight of an aromatic vinyl compound 55 to 70 wt% of a non-graft copolymer comprising; (B) 20 to 42 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; It provides a method for producing a thermoplastic resin composition comprising; kneading and extruding under rpm conditions.
[19]
In addition, the present substrate provides a molded article, characterized in that produced from the thermoplastic resin composition.
Effects of the Invention
[20]
Advantageous Effects of Invention According to the present invention, there is an effect of providing a thermoplastic resin composition excellent in weather resistance and heat resistance and excellent scratch resistance and colorability, a method for manufacturing the same, and a molded article including the same. In addition, the conversion rate of the N-substituted maleimide compound including the aromatic vinyl compound in the non-grafted copolymer included in the thermoplastic resin composition is improved, and the residual amount of the N-substituted maleimide compound in the recovered solution after polymerization is reduced, so that the volatilization process The problem of precipitation of the N-substituted maleimide compound in the pipe transferred to the residual monomer recovery tank is solved, and thus productivity is increased.
Best mode for carrying out the invention
[21]
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.
[22]
The present inventors prepared a non-graft copolymer comprising a (meth)acrylic acid alkyl ester compound, a vinyl cyan compound, an aromatic vinyl compound, and an N-substituted maleimide compound together with two ASA resins having different rubber particle diameters within a predetermined content range. In the case of mixing, it was confirmed that weather resistance, heat resistance, scratch resistance and colorability were all improved, and based on this, further research was devoted to complete the present invention.
[23]
The thermoplastic resin composition of the present disclosure comprises (A) 65 to 83 wt% of a (meth)acrylic acid alkylester compound, 2 to 12 wt% of an N-substituted maleimide compound, 1 to 6 wt% of a vinyl cyanide compound, and 7 to 17 wt% of an aromatic vinyl compound. 55 to 70 wt% of a non-graft copolymer comprising wt%; (B) 20 to 42 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; In this case, the weather resistance and heat resistance are excellent, and in particular, the scratch resistance and colorability are improved.
[24]
Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each configuration.
[25]
(A) Non-grafted copolymer
[26]
The (A) non-graft copolymer may be, for example, 55 to 70 wt%, preferably 60 to 70 wt%, more preferably 63 to 67 wt%, based on the total weight of the thermoplastic resin composition, within this range It has excellent weather resistance and heat resistance, and in particular, has an effect of improving scratch resistance and colorability.
[27]
The (A) non-graft copolymer is, for example, 65 to 83% by weight of a (meth)acrylic acid alkylester compound, 2 to 12% by weight of an N-substituted maleimide compound, 1 to 6% by weight of a vinyl cyanide compound, and an aromatic vinyl compound 7 to 17 wt%, excellent scratch resistance and colorability within this range, and improved polymerization rate of the N-substituted maleimide compound during polymerization. The problem of precipitation in the pipe transferred from the devolatilizer to the residual monomer recovery tank is improved, thereby improving productivity.
[28]
(A) The (meth)acrylic acid alkyl ester compound contained in the non-grafted copolymer is, for example, 65 to 83% by weight, preferably 70 to 80% by weight, based on the total weight of the (A) non-grafted copolymer, more Preferably, it may be 73 to 80% by weight, and more preferably 73 to 75% by weight. Within this range, the weather resistance and heat resistance are excellent, and in particular, scratch resistance and colorability are improved.
[29]
The N-substituted maleimide compound contained in the (A) non-graft copolymer may be, for example, 2 to 12 wt%, preferably 4 to 10 wt%, more preferably 6 to 10 wt%, It has excellent weather resistance and heat resistance within the range, and in particular, has an effect of improving scratch resistance and colorability.
[30]
The vinyl cyanide compound included in the (A) non-grafted copolymer is, for example, 1 to 6% by weight, preferably 2 to 5% by weight, more preferably 3 based on the total weight of the (A) non-grafted copolymer. It may be to 5% by weight, and while excellent in weather resistance and heat resistance within this range, there is an effect of particularly improving scratch resistance and colorability.
[31]
The aromatic vinyl compound contained in the (A) non-grafted copolymer is, for example, 7 to 17 wt%, preferably 10 to 15 wt%, more preferably 12 to (A) the total weight of the non-grafted copolymer. to 15% by weight, and while excellent in weather resistance and heat resistance within this range, there is an effect of particularly improving scratch resistance and colorability.
[32]
(A) The (meth)acrylic acid alkyl ester compound contained in the non-grafted copolymer is, for example, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethyl It may be at least one selected from the group consisting of hexyl ester, (meth)acrylic acid decyl ester, and (meth)acrylic acid lauryl ester, and may preferably be methyl methacrylate, in which case fluidity is appropriate and weather resistance and heat resistance are excellent. It works.
[33]
The N-substituted maleimide compound contained in the (A) non-graft 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 imides, preferably N-phenyl maleimide, and in this case, heat resistance and scratch resistance are excellent.
[34]
The vinyl cyanide compound included in the (A) non-graft copolymer may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof, and in this case, impact resistance and processability are excellent.
[35]
The aromatic vinyl compound contained in the (A) non-graft copolymer may be, for example, at least one selected from the group consisting of styrene, vinyltoluene, t-butylstyrene, and chlorostyrene, preferably styrene, In this case, the fluidity is adequate, so that the processability is excellent and the mechanical properties such as impact resistance are excellent.
[36]
The aromatic vinyl compound contained in the (A) non-graft copolymer is, for example, excluding α-methylstyrene.
[37]
The (A) non-graft copolymer may have, for example, a weight average molecular weight of 95,000 to 130,000 g/mol, preferably 96,000 to 120,000 g/mol, more preferably 99,000 to 115,000 g/mol, within this range. It has the effect of imparting fluidity suitable for processing while having excellent mechanical properties such as impact strength.
[38]
The (A) non-graft copolymer may have, for example, a polydispersity index (PDI) of 1.80 to 2.2, preferably 1.83 to 2.1, more preferably 1.90 to 2.10, and an increase in molecular weight within this range This has the effect of solving the problem of lowering fluidity and providing improved properties and processability at the same time.
[39]
In the present description, the polydispersity index (PDI) is calculated as a value obtained by dividing the weight average molecular weight by the number average molecular weight, and a smaller value indicates a more uniform molecular weight distribution.
[40]
In this description, unless otherwise defined, the weight average molecular weight and horizontal group molecular weight are prepared by dissolving 1 g of the copolymer in tetrahydrofuran (THF) at a temperature of 40° C., followed by gel chromatography (GPC) filled with porous silica. can be measured using At this time, the molecular weight is measured after calibration using polystyrene (PS) as a standard material.
[41]
The (A) non-graft copolymer may have, for example, a glass transition temperature of 107° C. or higher, preferably 107 to 130° C., more preferably 110 to 125° C., and has excellent heat resistance and scratch resistance within this range. It has excellent properties and colorability.
[42]
In the present disclosure, the glass transition temperature is measured using DSC equipment.
[43]
The (A) non-graft copolymer may have, for example, a refractive index of 1.520 or less, preferably 1.510 to 1.520, more preferably 1.513 to 1.519, and has an excellent effect of colorability within this range.
[44]
In the present description, the refractive index is measured at 25° C. using an Abbe refractometer in accordance with ASTM D542.
[45]
(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
[46]
The (B) acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymer (hereinafter referred to as 'small-diameter graft copolymer') comprising an acrylate-based rubber having an average particle diameter of 50 to 200 nm is a thermoplastic 20 to 42 wt%, preferably 25 to 37 wt%, and more preferably 28 to 33 wt%, based on the total weight of the resin composition, while excellent in 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, and when it is less than the above range, a problem of lowering impact resistance may occur.
[47]
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, and has excellent heat resistance, colorability and weather resistance.
[48]
The acrylate-based rubber included 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 within the above range, and if it is less than the above range, a problem may occur in which mechanical properties such as impact strength and tensile strength are lowered. .
[49]
The acrylate-based rubber contained in the (B) small-diameter graft copolymer is, for example, 20 to 60% by weight, 30 to 55% by weight, preferably 40 to 60% by weight, based on the total weight of the (B) small-diameter graft copolymer. It may be 50% by weight, and there is an excellent effect in weather resistance, impact strength and scratch resistance within this range.
[50]
In the present description, the average particle diameter is measured using an intensity gaussian distribution (Nicomp 380) by a dynamic laser light scattering method.
[51]
The acrylate-based rubber may be prepared by emulsion polymerization of, for example, an acrylate-based monomer, 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.
[52]
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.
[53]
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
[54]
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.
[55]
The initiator may be, for example, an inorganic peroxide, an organic peroxide, or a mixture thereof, and specific examples thereof 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; may be at least one selected from the group consisting of, in this case, the effect of improving the impact resistance and weather resistance by facilitating the polymerization reaction.
[56]
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.
[57]
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
[58]
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 and impact strength and tensile strength There is an effect of improving mechanical properties such as.
[59]
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 ).
[60]
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.
[61]
The acrylate-based rubber may further include, for example, a molecular weight control agent, and the molecular weight control agent may be, for example, t-dodecyl mercaptan, n-octyl mercaptan, or a mixture thereof, in which case the acrylate-based rubber It has the effect of improving the impact resistance and weather resistance of the composition by controlling the weight average molecular weight of the composition.
[62]
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.
[63]
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.
[64]
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.
[65]
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.
[66]
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.
[67]
(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
[68]
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% by weight, preferably 1 to 10% by weight, more preferably 2 to 7% by weight based on the total weight of the thermoplastic resin composition, and 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.
[69]
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 excellent heat resistance, colorability and weather resistance.
[70]
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.
[71]
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.
[72]
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.
[73]
The acrylate-based rubber may be prepared by emulsion polymerization of, for example, an acrylate-based monomer, and specific examples include emulsion polymerization by mixing an acrylate-based monomer, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte, and a solvent. , in this case, the grafting efficiency is excellent and there is an effect of excellent physical properties such as impact resistance.
[74]
The acrylate-based monomer, emulsifier, initiator, grafting agent, cross-linking agent, electrolyte and water used in the production of 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 .
[75]
The (C) aromatic vinyl compound contained in the large-diameter graft copolymer is, for example, 10 to 50% by weight, preferably 20 to 45% by weight, more preferably 30% by weight based on the total weight of (C) the large-diameter graft copolymer. to 40% by weight, there is an excellent effect of impact resistance, weather resistance and chemical resistance within this range.
[76]
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.
[77]
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. .
[78]
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.
[79]
Thermoplastic resin composition
[80]
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 and scratch resistance without deterioration of mechanical properties This has the effect of keeping it excellent.
[81]
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.
[82]
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) non-grafted copolymer, (B) small-diameter graft copolymer, and (C) large-diameter graft copolymer. It may be a weight part, more preferably, 0.05 to 1.5 weight part, 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.
[83]
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.
[84]
The antioxidant is, for example, 0.01 to 3 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of (A) non-grafted copolymer, (B) small-diameter graft copolymer, and (C) large-diameter graft copolymer. It may be 1 part by weight, more preferably 0.1 to 1 part by weight, and within this range, oxidation due to heat during the extrusion process is prevented and mechanical properties are excellent.
[85]
The dye is, for example, 0.1 to 1.5 parts by weight, preferably 0.5 to 1 parts by weight, based on 100 parts by weight of (A) non-grafted copolymer, (B) small-diameter graft copolymer, and (C) large-diameter graft copolymer. It may be a part by weight, and within this range, there is an excellent effect of color expression without reducing the original physical properties of the thermoplastic resin composition of the present invention.
[86]
The thermoplastic resin composition may have an L value (colorability) of 25.5 or less, preferably 20 to 25.5, more preferably 24 to 25, measured using Hunter Lab, for example, within this range. There is an excellent effect of balance.
[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 according to ASTM D3363 using a pencil hardness tester (Cometech), for example, within this range There is an excellent effect of the physical property balance in
[88]
The thermoplastic resin composition may have, for example, a heat deflection temperature of 90° C. or higher, preferably 90 to 105° C., and more preferably 90 to 100° 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 5.5 kgf·cm/cm or more, preferably 5.5 to 10 kgf·cm/cm, more preferably may be 5.8 to 6.5 kgf·cm/cm, and within this range, all physical property balances have an excellent effect.
[90]
The thermoplastic resin composition has, for example, a tensile strength of 500 kg/cm 2 or more, preferably 500 to 550 kg/cm 2 , more preferably 503 to 530 kg/cm 2 , measured according to ASTM D638. There is an effect excellent in the physical property balance within this range.
[91]
The thermoplastic resin composition may have, for example, a falling ball impact strength of 29 N or more, 29 to 35 N, more preferably 29.3 to 31 N, measured with a 3.2 mm thick specimen according to ASTM D3763, and the physical property balance within this range has an excellent effect.
[92]
Method for producing a thermoplastic resin composition
[93]
The method for preparing the thermoplastic resin composition of the present disclosure is, for example, (A) 65 to 85% by weight of an (meth)acrylic acid alkylester compound, 1 to 10% by weight of a vinyl cyanide compound, 7 to 17% by weight of an aromatic vinyl compound, and an N-substituted maleic compound 55 to 70% by weight of a non-graft copolymer comprising 2 to 12% by weight of the mid compound; (B) 20 to 42 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; and, in this case, has excellent scratch resistance and colorability while excellent weather resistance and heat resistance.
[94]
The method for preparing the thermoplastic resin composition includes, for example, 65 to 85% by weight of a (meth)acrylic acid alkylester compound, 1 to 10% by weight of a vinyl cyanide compound, 7 to 17% by weight of an aromatic vinyl compound, and 2 to 12% by weight of an N-substituted maleimide compound. (A) preparing a non-graft 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 the monomer mixture including weight %.
[95]
The reaction solvent in the step (A) for preparing the non-graft copolymer may be, for example, at least one selected from the group consisting of ethylbenzene, toluene, methyl ethyl ketone and xylene, and in this case, viscosity control is easy and polymerization It has the effect of suppressing the reduction in conversion rate.
[96]
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.
[97]
The initiator in the step of preparing the (A) non-graft copolymer is, for example, t-butylperoxy-2-ethylhexanoate (tert-Butylperoxy-2-ethylhexanoate), 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 t-butylperoxylaurate, t-butyl peroxy isopropylmonocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t- hexylperoxybenzoate, t-butyl peroxyacetate, 2,2-bis(t-butylperoxy)butane, t-butyl peroxybenzoate, dicumylperoxide, 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, the polymerization reaction is facilitated and impact resistance and weather resistance are improved.
[98]
The initiator may be, for example, 0.01 to 1 parts by weight, 0.01 to 0.5 parts by weight, preferably 0.01 to 0.4 parts by weight, based on 100 parts by weight of the monomer mixture, and facilitates the polymerization reaction within this range to improve mechanical properties, weather resistance, It has the effect of maintaining excellent heat resistance and scratch resistance.
[99]
The polymerization in the step (A) for preparing the non-graft copolymer is, for example, continuously introduced into a continuous reactor at a rate of 7 to 20 kg/hr, preferably 10 to 15 kg/hr, of the polymerization solution to a temperature of 130 to 160 ° C., preferably 140 to 150 ° C., and in this case, the particle stability of the copolymer is improved compared to the case of batch input to make the particle internal structure uniform, so that mechanical properties, weather resistance, heat resistance, scratch resistance and It has the effect of making it excellent in colorability.
[100]
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. .
[101]
The polymerization in the step (A) for preparing the non-graft copolymer is, for example, the residual N-substituted maleamide compound content in the recovered solution after polymerization is 0.12% by weight or less, preferably 0.05 to 0.12% by weight, more preferably may be 0.07 to 0.10 wt %, and the conversion rate of the N-substituted maleimide compound is improved within this range, so that the N-substituted maleimide compound does not precipitate in the pipe that is transferred from the volatilization process to the residual monomer recovery tank even during long-term operation. Therefore, the effect of improving productivity is excellent.
[102]
In the present description, the content of the residual N-substituted maleamide compound may be measured by gas chromatography.
[103]
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.
[104]
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, and in this case, the throughput per unit time may be adequate and sufficient melt-kneading may be possible, There is an effect that does not cause problems such as thermal decomposition.
[105]
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
[106]
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 scratch resistance and colorability while having excellent weather resistance and heat resistance.
[107]
The molded article may be, for example, an automobile part, an electric/electronic part, a ship part, or a building material, and preferably may be an automobile interior/exterior material.
[108]
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.
[109]
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 technical spirit of the present disclosure, It goes without saying that such variations and modifications fall within the scope of the appended claims.
[110]
[Example]
[111]
Materials used in the following Examples and Comparative Examples are as follows.
[112]
* (B) Small-diameter graft copolymer: a graft copolymer with an average rubber particle diameter of 120 nm (SA130 of LG Chem)
[113]
* (C) Large-diameter graft copolymer: a graft copolymer with an average rubber particle diameter of 400 nm (SA927 from LG Chem)
[114]
* Lubricant: Ethylene Bis Stearamide (EBA)
[115]
* Antioxidant: SONGNOX 1076 from Songwon Industries
[116]
* Dye: Yedam Chemicals Papilion Back S-KL2
[117]
Example 1
[118]
< (A) non-graft copolymer preparation >
[119]
25 parts by weight of toluene, 75 parts by weight of methyl methacrylate (hereinafter referred to as 'MMA'), 7 parts by weight of N-phenylmaleimide (hereinafter referred to as 'PMI'), 3 parts by weight of acrylonitrile (hereinafter referred to as 'AN') 3 A polymerization solution in which 0.03 parts by weight of dicumyl peroxide was added as an initiator to 15 parts by weight and 15 parts by weight of styrene (hereinafter referred to as 'SM') was continuously introduced into a continuous reactor at a rate of 12 kg/hr for 14 hours, followed by polymerization at a temperature of 145° C. After that, the unreacted monomer and the reaction solvent were removed through a 250°C volatilization tank to prepare (A) non-grafted copolymer in the form of pellets. The prepared copolymer had a refractive index of 1.5183, a glass transition temperature of 115.5°C, and a weight average molecular weight of 103,315 g. /mol and PDI 2.09, and the residual PMI in the recovered solution was 0.09 wt%.
[120]

[121]
(A) 65 parts by weight of the non-grafted copolymer, (B) 30 parts by weight of the small-diameter graft copolymer, and (C) 5 parts by weight of the large-diameter graft copolymer prepared above, 1 part by weight of lubricant, 0.5 parts by weight of antioxidant Part and 0.6 parts by weight of the dye were 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.
[122]
Examples 2 to 5
[123]
Example 1 was carried out in the same manner as in Example 1, except that the components and contents of Table 1 below were used to prepare the (A) non-graft copolymer.
[124]
Comparative Examples 1 to 10
[125]
Example 1 was carried out in the same manner as in Example 1, except that the components and contents of Tables 2 to 3 were used in the preparation of the (A) non-graft copolymer in Example 1.
[126]
[Test Example]
[127]
The properties of the specimens prepared in Examples 1 to 5 and Comparative Examples 1 to 10 were measured in the following manner, and the results are shown in Tables 1 to 3 below.
[128]
How to measure
[129]
* Refractive index: measured at 25°C using an Abbe refractometer in accordance with ASTM D542.
[130]
* Glass transition temperature (℃): measured using a differential calorimeter (manufacturer: Ta Instruments, product name: DSC Q20).
[131]
* Weight average molecular weight (g/mol), number average molecular weight (g/mol): 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 to measure the relative value with respect to the standard PS (Standard polystyrene) sample.
[132]
* PDI: PDI was calculated by dividing the weight average molecular weight by the number average molecular weight.
[133]
* Residual PMI content in the recovered solution (% by weight): measured by gas chromatography.
[134]
* 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. The lower the L value, the better the black feeling.
[135]
* 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 .
[136]
* 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.
[137]
* Izod impact strength (kgf·cm/cm): It was measured in accordance with ASTM D256 using a specimen thickness of 1/4”.
[138]
* Tensile strength (kg/cm 2 ): Measured according to ASTM D638.
[139]
* Falling ball impact strength (N): measured according to ASTM D3763 using a specimen thickness of 3.2 mm.
[140]
[Table 1]
division Example 1 Example 2 Example 3 Example 4 Example 5
(A)
Alesund rapeuteu
copolymer
composition MMA 75 76 75 73 80
PMI 7 4 10 7 4
AN 3 5 5 5 3
SM 15 15 10 15 13
(A)
Alesund rapeuteu
copolymer
properties refractive index 1.5183 1.5153 1.5176 1.5185 1.5131
Tg 115.5 110.8 120.4 116.7 112.2
Mw 103,315 113,991 99,875 104,247 96,279
PDI 2.09 1.96 2.00 2.06 1.83

Residual PMI content in recovered liquid 0.09 0.07 0.10 0.09 0.08
Thermoplastic resin
composition
composition (A) Non-grafted
copolymer 65 65 65 65 65
(B) small diameter
graft copolymer 30 30 30 30 30
(C) large diameter
graft copolymer 5 5 5 5 5
Thermoplastic
resin
composition
physical properties colorability 25.0 24.8 24.9 25.0 24.7
heat deflection temperature 93 90 97 94.2 90.9
pencil hardness 2H 2H 2H 2H 2H
impact strength 6.0 6.4 5.9 6.1 5.8
tensile strength 519 528 503 520 507
falling ball impact 30.1 30.5 29.3 30.2 29.3
[141]
[Table 2]
division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5
(A) Non-
grafted copolymer
composition MMA 50.7 60 60 86 86
PMI 0 0 10 4 4
AN 15.5 7 30 5 0
SM 0 33 0 5 10
α-methylstyrene 33.8 0 0 0 0
(A)
Alesund rapeuteu
copolymer
properties refractive index 1.5293 1.5295 1.5060 1.5053 1.5103
Tg 120.0 102.3 105.6 113.2 119.6
Mw 88,410 79,768 90,628 84,657 75,580
PDI 2.01 1.98 2.22 2.09 1.92
Residual PMI content in recovered liquid (wt%) 0 0 1.67 0.42 0.25
Thermoplastic
resin
composition
composition (A) Non-grafted copolymer 65 65 65 65 65
(B) small diameter
graft copolymer 30 30 30 30 30
(C) large diameter
graft copolymer 5 5 5 5 5
Thermoplastic
resin
composition
physical properties colorability 26.0 26.0 23.7 23.6 24.5
heat deflection temperature 96 84 85 88 95
pencil hardness H 2H 2H 2H 2H
impact strength 5.7 5.2 5.8 5.3 4.9
tensile strength 509 461 480 478 455
falling ball impact 28.9 26.4 29.1 28.3 26.1
[142]
[Table 3]
division Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10
(A) Non-
grafted copolymer
composition MMA 73 74 73 76 71
PMI 4 4 14 4 -
AN 3 7 3 5 7
SM 20 15 10 15 22
α-methylstyrene 0 0 0 0 0
(A) Non-
grafted copolymer
physical properties refractive index 1.5217 1.5159 1.5204 1.5159 1.5144
Tg 110.5 106.4 121.2 108.6 105.6
Mw 120,746 101,874 83,247 64,770 96,929
PDI 2.04 1.95 1.99 1.96 1.77
Residual PMI
content in recovered liquid (wt%) 0.27 0.17 2.13 0.09 0
Thermoplastic
resin
composition
composition (A) Non-grafted copolymer 65 65 65 75 75
(B) small diameter
graft copolymer 30 30 30 20 20
(C) large diameter
graft copolymer 5 5 5 5 5
Thermoplastic
resin
composition
physical properties colorability 25.3 24.8 25.2 24.61 24.58
heat deflection temperature 89 86 96 92.8 86
pencil hardness 2H 2H H 2H 2H
impact strength 6.4 5.8 5.3 3 6.2
tensile strength 476 467 472 528 552
falling ball impact 31.0 29.5 27.3 26.9 28.5
[143]
As shown in Tables 1 to 3, Examples 1 to 5 prepared according to the present invention, while maintaining the impact strength, tensile strength and falling impact strength compared to Comparative Examples 1 to 10 out of the scope of the present invention, colorability, heat It was confirmed that the deformation temperature and the pencil hardness (scratch resistance) were excellent effects.
[144]
In addition, the (A) non-grafted copolymers of Examples 1 to 5 prepared according to the present invention had a lower refractive index, so that the colorability improvement effect was excellent. Since the conversion rate was improved, N-phenyl maleimide did not precipitate from the pipe transferred to the residual monomer recovery tank in the volatilization process during long-term operation, thereby increasing productivity.
[145]
In addition, (A) Comparative Example 9 including the non-grafted copolymer exceeding the scope of the present invention had lower impact strength and falling impact strength, and (A) the non-grafted copolymer polymerized without including PMI. In Comparative Example 10, including exceeding the scope of the invention, the heat deflection temperature was significantly lowered.
Claims
[Claim 1]
(A) a ratio comprising 65 to 83 wt% of a (meth)acrylic acid alkylester compound, 2 to 12 wt% of an N-substituted maleimide compound, 1 to 6 wt% of a vinyl cyanide compound, and 7 to 17 wt% of an aromatic vinyl compound 55 to 70% by weight of the graft copolymer; (B) 20 to 42 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; composition.
[Claim 2]
The thermoplastic resin composition according to claim 1, wherein the (A) non-grafted copolymer has a weight average molecular weight of 95,000 to 130,000 g/mol.
[Claim 3]
The thermoplastic resin composition according to claim 1, wherein the (A) non-graft copolymer has a glass transition temperature of 107°C or higher.
[Claim 4]
The thermoplastic resin composition according to claim 1, wherein the (A) non-graft copolymer has a refractive index of 1.520 or less.
[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, aromatic vinyl compound 10 to 50% by weight, and vinyl cyanide compound 5 to 30% by weight A thermoplastic resin composition comprising a.
[Claim 6]
The method of 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 an L value (colorability) of 25.5 or less, measured using a Hunter Lab.
[Claim 8]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a pencil hardness of 2H or more measured at a 45° angle under a load of 0.5 kg based on ASTM D3363 using a pencil hardness tester (Cometech).
[Claim 9]
(A) a ratio comprising 65 to 83 wt% of a (meth)acrylic acid alkylester compound, 2 to 12 wt% of an N-substituted maleimide compound, 1 to 6 wt% of a vinyl cyanide compound, and 7 to 17 wt% of an aromatic vinyl compound 55 to 70% by weight of the graft copolymer; (B) 20 to 42 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; Method for producing a thermoplastic resin composition comprising; kneading and extruding under rpm conditions.
[Claim 10]
The method according to claim 9, wherein the method for preparing the thermoplastic resin composition comprises 65 to 83 wt% of a (meth)acrylic acid alkylester compound, 2 to 12 wt% of an N-substituted maleimide compound, 1 to 6 wt% of a vinyl cyanide compound, and an aromatic vinyl compound. (A) preparing a non-graft copolymer by polymerizing a polymerization solution in which 15 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 7 to 17% by weight of the compound Method for producing a thermoplastic resin composition, characterized in that.
[Claim 11]
11. The method of claim 10, wherein the (A) polymerization in the step of preparing the non-grafted copolymer is carried out under a temperature of 130 to 160 ℃ by continuously introducing the polymerization solution into a continuous reactor at a rate of 7 to 20 kg / hr. Method for producing a thermoplastic resin composition, characterized in that.
[Claim 12]
11. The method according to claim 10, wherein the residual N-substituted amide compound content in the recovered solution after polymerization in the step (A) of preparing the non-grafted copolymer is 0.12 wt% or less.
[Claim 13]
A molded article, characterized in that it is made of the thermoplastic resin composition according to any one of claims 1 to 8.