Title of Invention: Thermoplastic resin composition, manufacturing method thereof, and molded article manufactured therefrom
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application has the benefit of priority based on Korean Patent Application No. 10-2019-0114947 dated September 18, 2019 and Korean Patent Application No. 10-2020-0114753 filed again on September 08, 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 manufactured therefrom, and more particularly, it satisfies economic efficiency and chemical resistance at the same time by including a predetermined additive at a lower cost than conventional additives for chemical resistance, and It relates to a thermoplastic resin composition excellent in heat resistance and impact strength, a method for manufacturing the same, and a molded article manufactured therefrom.
background
[4]
The acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as 'ASA resin') has excellent weather resistance, light resistance, colorability, chemical resistance and impact resistance, and is used in various fields such as automobiles, miscellaneous goods, and construction materials. In particular, in the field of exterior materials, as the emotional quality level demanded by the market increases, research has been conducted to satisfy the needs of consumers by finishing the substrates such as PVC, wood, and iron with ASA resin.
[5]
ASA resin is an eco-friendly material that has superior processing stability and does not contain heavy metals compared to conventional PVC or PP resins, and is attracting attention in the field of exterior materials such as decor sheets.
[6]
However, ASA resin has a problem of occurrence of press marks generated during storage or a problem of deformation of the dimensions of the sheet during processing, and in particular, a problem of dissolving in the solvent component of the adhesive used in the bonding process with the substrate occurs.
[7]
Therefore, there is a need for the development of a thermoplastic resin composition that can sufficiently satisfy the needs of consumers by improving not only the appearance quality but also the chemical resistance.
[8]
[Prior art literature]
[9]
[Patent Literature]
[10]
(Patent Document 1) Korean Patent Publication No. 2006-0065980
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[11]
In order to solve the problems of the prior art as described above, the present invention is a thermoplastic resin composition that simultaneously satisfies economic efficiency and chemical resistance by including a predetermined additive at a lower cost compared to the conventional additive for chemical resistance, and also has excellent heat resistance and impact strength. An object of the present invention is to provide a method for manufacturing the same, and a molded article manufactured therefrom.
[12]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[13]
In order to achieve the above object, the present invention provides A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm as a core, A-2) an average particle diameter 100 weight of a base resin comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber of 0.3 to 0.6 μm as a core, B-1) an aromatic vinyl polymer, and B-2) a heat-resistant aromatic vinyl polymer wealth; and C) 0.5 to 10 parts by weight of a polyolefin elastomer, wherein the heat deflection temperature (HDT) is 89° C. or higher.
[14]
In addition, the present invention provides A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm as a core, and A-2) an acryl having an average particle diameter of 0.3 to 0.6 μm. 100 parts by weight of a base resin composed of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a late rubber as a core, B-1) an aromatic vinyl polymer, and B-2) a heat-resistant aromatic vinyl polymer; and C) 0.5 to 10 parts by weight of a polyolefin elastomer; kneading and extruding at 200 to 330 ° C. and 100 to 500 rpm conditions to prepare a thermoplastic resin composition, wherein the thermoplastic resin composition has a heat deflection temperature (HDT) It provides a method for producing a thermoplastic resin composition, characterized in that 89 ℃ or more.
[15]
In addition, the present invention provides a molded article comprising the thermoplastic resin composition.
[16]
In addition, the present invention is A-1) 1 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm as a core, A-2) an average particle diameter of 0.3 5 to 50 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having a thickness of 0.6 μm as a core, B-1) 40 to 85 wt% of an aromatic vinyl polymer, and B-2) heat resistance 100 parts by weight of a base resin consisting of 5 to 50% by weight of an aromatic vinyl polymer; and C) a thermoplastic resin composition comprising 0.5 to 10 parts by weight of a polyolefin elastomer.
Effects of the Invention
[17]
According to the present invention, a thermoplastic resin composition which satisfies economic efficiency and chemical resistance at the same time by including a predetermined additive at a lower cost compared to conventional additives for chemical resistance, and also has excellent heat resistance and impact strength, a manufacturing method thereof, and a molded article manufactured therefrom has the effect of providing
Best mode for carrying out the invention
[18]
Hereinafter, the thermoplastic resin composition of the present disclosure, a method for producing the same, and a molded article prepared therefrom will be described in detail.
[19]
In order to increase the chemical resistance of the ASA resin, the present inventors have found that when a low-cost, predetermined polymer elastomer is included within a certain range instead of a conventional additive for chemical resistance such as polymethyl methacrylate, while improving economic efficiency, chemical resistance, heat resistance and impact All of the strength has been improved, so it is confirmed that it can be applied with high quality to fields that require both high chemical resistance, heat resistance, and impact strength, such as exterior materials, especially deco sheets. invention was completed.
[20]
The thermoplastic resin composition of the present invention is A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm as a core, A-2) an average particle diameter of 0.3 to 0.6 μm 100 parts by weight of a base resin comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber of B-1) an aromatic vinyl polymer, and B-2) a heat-resistant aromatic vinyl polymer; and C) 0.5 to 10 parts by weight of a polyolefin elastomer, wherein the heat deflection temperature (HDT) is 89° C. or higher. In this case, the thermoplastic resin composition has excellent economic feasibility and chemical resistance at the same time by including a predetermined additive at a low cost compared to conventional additives for chemical resistance, and has excellent heat resistance and impact strength.
[21]
In addition, the thermoplastic resin composition of the present invention is A-1) 1 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm as a core, A-2 ) 5 to 50 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.3 to 0.6 μm as a core, B-1) 40 to 85 wt% of an aromatic vinyl polymer, and B -2) 100 parts by weight of a base resin comprising 5 to 50% by weight of a heat-resistant aromatic vinyl polymer; and C) a thermoplastic resin composition comprising 0.5 to 10 parts by weight of a polyolefin elastomer, and in this case, economical efficiency, impact strength, chemical resistance and heat resistance are all excellent.
[22]
Hereinafter, each component constituting the thermoplastic resin composition of the present disclosure will be described in detail as follows.
[23]
A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
[24]
A-1) The acrylate rubber of the graft copolymer may have, for example, an average particle diameter of 0.05 to 0.15 μm, preferably 0.1 to 0.15 μm, more preferably 0.12 to 0.15 μm, still more preferably 0.12 to 0.15 μm. It is 0.14 μm, and excellent weather resistance and impact strength can be imparted to the finally manufactured thermoplastic resin composition within this range.
[25]
In the present description, the average particle diameter may be measured using dynamic light scattering, and in detail, may be measured using Nicomp 380 equipment (manufacturer: PSS).
[26]
In addition, in the present description, the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, specifically, an average particle diameter of scattering intensity.
[27]
The A-1) graft copolymer is, for example, 1 to 30% by weight, preferably 1 to 20% by weight, more preferably 5 to 15% by weight, even more preferably 5 to 10% by weight relative to the base resin, Within this range, the weather resistance, fluidity, tensile strength and impact strength are excellent.
[28]
The A-1) graft copolymer may be included, for example, in a smaller amount than the A-2) graft copolymer, preferably the A-1) graft copolymer and the A-2) graft copolymer. A weight ratio of 1:1.1 to 1:5, more preferably 1:1.2 to 1:4, still more preferably 1:1.2 to 1:3, most preferably 1:1.5 to 1:2.5, It has excellent effects in weather resistance, fluidity and impact strength.
[29]
The A-1) graft copolymer may include, for example, 40 to 60% by weight of an acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, and has weather resistance within this range. , excellent fluidity and impact strength.
[30]
As a preferred example, the A-1) graft copolymer may include 45 to 55% by weight of an acrylate rubber, 30 to 50% by weight of an aromatic vinyl compound, and 5 to 20% by weight of a vinyl cyanide compound, within this range It has excellent weather resistance, fluidity and impact strength.
[31]
As a more preferred example, the A-1) graft copolymer may include 45 to 55% by weight of an acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, within this range It has excellent effects in weather resistance, fluidity and impact strength.
[32]
In the present description, a polymer including a certain compound means a polymer polymerized including the compound, and a unit in the polymerized polymer is derived from the compound.
[33]
The A-1) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, chemical resistance, weather resistance, fluidity, tensile strength and impact strength are excellent.
[34]
The emulsion polymerization is not particularly limited if the emulsion graft polymerization method commonly carried out in the art to which the present invention belongs.
[35]
The acrylate may be, for example, at least one selected from the group consisting of alkyl acrylates having 2 to 8 carbon atoms in the alkyl group, preferably an alkyl acrylate having 4 to 8 carbon atoms in the alkyl group, more preferably butyl acryl lactate or ethylhexyl acrylate.
[36]
The aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, and is preferably styrene.
[37]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methnitrolonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, preferably acrylonitrile.
[38]
A-2) Acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
[39]
A-2) The acrylate rubber of the graft copolymer may have, for example, an average particle diameter of 0.3 to 0.6 μm, preferably 0.35 to 0.5 μm, more preferably 0.4 to 0.5 μm, further preferably 0.45 to 0.45 μm. It is 0.50 ㎛, and within this range, the weather resistance is good and the mechanical strength such as fluidity and impact strength is excellent.
[40]
The A-2) graft copolymer is, for example, 5 to 50% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight, more preferably 11 to 25% by weight relative to the base resin, Within this range, the weather resistance, fluidity and impact strength are excellent.
[41]
The A-2) graft copolymer may include, for example, 40 to 60% by weight of an acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, and has weather resistance within this range. , excellent fluidity and impact strength.
[42]
As a preferred example, the A-2) graft copolymer may include 45 to 55% by weight of an acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, within this range It has excellent weather resistance, fluidity and impact strength.
[43]
The A-2) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, it has excellent effects in weather resistance, fluidity, tensile strength and impact strength.
[44]
The emulsion polymerization is not particularly limited if the emulsion graft polymerization method commonly carried out in the art to which the present invention belongs.
[45]
B-1) Aromatic vinyl polymer
[46]
The B-1) aromatic vinyl polymer may be, for example, 40 to 85% by weight, preferably 50 to 80% by weight, more preferably 60 to 85% by weight or 55 to 75% by weight, further Preferably, it is 60 to 70% by weight, and within this range, there is an advantage of excellent flow and weather resistance, little yellowing, and easy coloring.
[47]
The B-1) aromatic vinyl polymer may be, for example, an aromatic vinyl compound-vinyl cyan compound copolymer, and in this case, chemical resistance and fluidity are excellent.
[48]
B-1) The aromatic vinyl polymer preferably contains 65 to 80 wt% of an aromatic vinyl compound and 20 to 35 wt% of a vinyl cyanide compound, and within this range, chemical resistance, processability and impact strength are excellent. .
[49]
The B-1) aromatic vinyl polymer has, for example, a weight average molecular weight of 100,000 to 210,000 g/mol, preferably 120,000 to 200,000 g/mol, and more preferably 150,000 to 200,000 g/mol, within this range. It has excellent effects such as fluidity and chemical resistance.
[50]
In the present description, unless otherwise defined, the weight average molecular weight may be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as the eluent. ) can be measured as a relative value for a standard PS (standard polystyrene) sample.
[51]
The aromatic vinyl compound-vinyl cyan compound copolymer may be a styrene-acrylonitrile copolymer (SAN resin) as a preferred example, and in this case, it has excellent fluidity and the like.
[52]
The B-1) aromatic vinyl polymer may be prepared by, for example, solution polymerization or bulk polymerization, and in this case, heat resistance and fluidity are excellent.
[53]
The solution polymerization and bulk polymerization are not particularly limited in the case of solution polymerization and bulk polymerization methods commonly carried out in the art to which the present invention pertains, respectively.
[54]
B-2) Heat-resistant aromatic vinyl polymer
[55]
The B-2) heat-resistant aromatic vinyl polymer may be, for example, 5 to 50% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight, more preferably 10 to 20% by weight, there is an effect excellent in heat resistance and chemical resistance within this range.
[56]
In the present disclosure, the heat-resistant aromatic vinyl polymer is not particularly limited if it is a polymer commonly referred to as a heat-resistant aromatic vinyl polymer in the art to which the present invention belongs, but specifically, a monomer having a high glass transition temperature (based on polymer) compared to the styrene monomer, that is, heat resistance It may mean an aromatic vinyl polymer comprising a monomer.
[57]
The heat-resistant monomer may be, for example, at least one selected from the group consisting of alpha-methylstyrene and maleimide-based compounds, and the maleimide-based compounds include, for example, maleimide, N-methyl maleimide, N-ethyl maleimide, N -Propyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-isobutyl maleimide, Nt-butyl maleimide, N-lauryl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide , N- (4-chlorophenyl) maleimide, 2-methyl-N-phenyl maleimide, N- (4-bromophenyl) maleimide, N- (4-nitrophenyl) maleimide, N- (4- It may be at least one member selected from the group consisting of hydroxyphenyl) maleimide, N-(4-methoxyphenyl) maleimide, N-(4-carboxyphenyl) maleimide, and N-benzyl maleimide, preferably alpha-methylstyrene.
[58]
B-2) The heat-resistant aromatic vinyl polymer is preferably at least one selected from the group consisting of an alpha-methylstyrene-vinyl cyan compound copolymer and a maleimide-based compound-aromatic vinyl compound copolymer, more preferably alpha-methyl It is a styrene-vinyl cyan compound copolymer, more preferably an alpha-methylstyrene-acrylonitrile copolymer, and in this case, heat resistance and impact strength are excellent.
[59]
The alpha-methylstyrene-vinyl cyan compound copolymer preferably contains 50 to 80 wt% of alpha-methylstyrene and 20 to 50 wt% of the vinyl cyan compound, and more preferably 55 to 50 wt% of alpha-methylstyrene. 75% by weight and 25 to 45% by weight of the vinyl cyan compound, more preferably 60 to 75% by weight of alpha-methylstyrene and 25 to 40% by weight of the vinyl cyan compound, a preferred embodiment The furnace may include 60 to 70% by weight of alpha-methylstyrene, 5 to 10% by weight of styrene, and 20 to 30% by weight of acrylonitrile, and in another preferred embodiment, 65 to 70% by weight of alpha-methylstyrene %, may include 5 to 10% by weight of styrene and 25 to 30% by weight of acrylonitrile, and within this range, there is an excellent effect of heat resistance and the like.
[60]
The alpha-methylstyrene-vinyl cyan compound copolymer preferably has a weight average molecular weight of 80,000 to 150,000 g/mol, more preferably 80,000 to 120,000 g/mol, and has excellent heat resistance within this range. have.
[61]
The alpha-methylstyrene-vinyl cyan compound copolymer preferably has a glass transition temperature of 110 to 150 °C, more preferably 110 to 140 °C, and has excellent heat resistance within this range.
[62]
In the present disclosure, the glass transition temperature (Tg) may be measured using a differential scanning calorimetry (DSC), and as a specific example, it may be measured using a differential scanning calorimeter manufactured by TA Instruments.
[63]
The maleimide-based compound-aromatic vinyl compound copolymer may be at least one selected from the group consisting of a maleimide-based compound-styrene copolymer and a maleimide-based compound-styrene-vinyl cyan compound copolymer, more preferably A maleimide-based compound-styrene copolymer, more preferably an N-substituted maleimide compound-styrene-maleic anhydride copolymer, has excellent heat resistance and impact strength within this range.
[64]
The maleimide-based compound may be included, for example, in an amount of 30 to 70% by weight in the heat-resistant aromatic vinyl polymer, preferably 45 to 55% by weight, and within this range, heat resistance and impact strength are excellent.
[65]
The aromatic vinyl compound may be included, for example, in an amount of 25 to 65% by weight in the heat-resistant aromatic vinyl polymer, preferably in an amount of 40 to 50% by weight, and has excellent heat resistance and impact strength within this range.
[66]
Each of the vinyl cyanide compound and the maleic anhydride may be included in an amount of 1 to 30 wt %, preferably 1 to 10 wt %, in the heat-resistant aromatic vinyl polymer, and heat resistance and impact strength within this range are It has an excellent effect.
[67]
The B-2) heat-resistant aromatic vinyl polymer may be prepared by, for example, solution polymerization or bulk polymerization, and in this case, heat resistance and fluidity are excellent.
[68]
The solution polymerization and bulk polymerization are not particularly limited in the case of solution polymerization and bulk polymerization methods commonly carried out in the art to which the present invention pertains, respectively.
[69]
C) polyolefin elastomer
[70]
The polyolefin elastomer C) may preferably be at least one selected from the group consisting of ethylene-alpha-olefin copolymer (elastomer) and linear low-density polyethylene (LLDPE), more preferably linear low-density polyethylene (LLDPE), ethylene-1 -butene elastomer (EBR), ethylene-1-pentene elastomer (EPR), ethylene-1-heptene elastomer (HER), and at least one selected from the group consisting of ethylene-1-octene elastomer (EOR), more preferably It is at least one selected from the group consisting of ethylene-1-octene elastomer (EOR) and ethylene-1-butene elastomer (EBR), and has an effect of improving chemical resistance, impact strength and heat resistance within this range.
[71]
C) The polyolefin elastomer has a melt index (190° C., 2.16 kg) of preferably 0.3 to 20 g/10 min, more preferably 0.5 to 10 g/10 min, still more preferably 1 to 6 g/10 min. , and more preferably 1 to 5 g/10 min, and has the effect of improving chemical resistance, impact strength and heat resistance within this range.
[72]
The C) polyolefin elastomer may have, for example, a weight average molecular weight of 60,000 to 120,000 g/mol, preferably 80,000 to 110,000 g/mol, more preferably 90,000 to 110,000 g/mol, and chemical resistance and impact strength within this range. And there is an effect that the heat resistance is improved.
[73]
Said C) polyolefin elastomer preferably comprises 50 to 90% by weight of ethylene; and 10 to 50% by weight of butene, pentene, heptene or octene, more preferably 60 to 90% by weight of ethylene; and 10 to 40 wt% of butene, pentene, heptene or octene, more preferably 60 to 70 wt% of ethylene; And butene, pentene, heptene, or 30 to 40% by weight of octene; may be made, within this range, there is an effect that chemical resistance, impact strength and heat resistance are further improved.
[74]
The polyolefin elastomer C) preferably has a density of 0.85 to 0.89, more preferably a density of 0.856 to 0.887, still more preferably a density of 0.860 to 0.867, even more preferably 0.860. to 0.864, and has the effect of improving chemical resistance, impact strength and heat resistance within this range.
[75]
The polyolefin elastomer C) may be an ethylene-butene elastomer having a butene content of 10 to 40% by weight, a weight average molecular weight of 60,000 to 120,000 g/mol, and a density of 0.860 to 0.887 as a more preferred example, and a more preferred example of the polyolefin elastomer is a butene content. It is an ethylene-butene elastomer having a 30 to 40 wt%, a weight average molecular weight of 90,000 to 110,000 g/mol, and a density of 0.860 to 0.864, and within this range, the chemical resistance, impact strength and heat resistance are significantly improved. have.
[76]
In the present description, the density may be measured based on a measurement method commonly used in the technical field to which the present invention belongs, and as a specific example, it may be measured according to ASTM D-792.
[77]
The C) polyolefin elastomer may be, for example, 0.5 to 10 parts by weight, preferably 0.5 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, and still more preferably 2 to 4 parts by weight based on 100 parts by weight of the base resin. negative, and has the effect of improving chemical resistance, impact strength and heat resistance within this range.
[78]
The C) polyolefin elastomer may be prepared by, for example, a bulk polymerization method or a solution polymerization method, and is preferably prepared by a solution polymerization method. It can be carried out using a strong catalyst.
[79]
E) other additives
[80]
The thermoplastic resin composition of the present disclosure is, for example, an antioxidant, a UV stabilizer, a UV stabilizer, an optical brightener, a lubricant, a chain extender, a release agent, a pigment, a dye, an antibacterial agent, a processing aid, a metal deactivator, a smoke suppressant, an inorganic filler, glass It may further include one or more additives selected from the group consisting of fibers, anti-friction agents and anti-wear agents, and the additives are, for example, 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the base resin; More preferably, it may be 0.1 to 1 part by weight, and in this case, the improvement of physical properties is excellent and the manufacturing cost is low, and thus economic efficiency is excellent.
[81]
The thermoplastic resin composition of the present disclosure preferably has an Izod impact strength (1/4", 23° C.) measured according to ASTM D256 of 6 kgf·cm/cm 2 or more, 6 to 15 kgf·cm/cm 2 , or 9 to 12 kgf·cm/cm 2 , and a balance of chemical resistance, impact strength and heat resistance within this range has an excellent effect.
[82]
The thermoplastic resin composition of the present disclosure may preferably have a melt index (220 ° C., 10 kg) measured according to ASTM D1238 of 9 g/10 min or more, 9 to 16 g/10 min, or 9 to 15 g/10 min, Within this range, the balance of chemical resistance, impact strength and heat resistance has an excellent effect.
[83]
The thermoplastic resin composition of the present disclosure may preferably have a hardness (ASTM D785, R-Scale) of less than 116, or 112 or more to less than 116, and the balance of chemical resistance, impact strength and heat resistance within this range has an excellent effect. .
[84]
The thermoplastic resin composition of the present disclosure preferably has a heat deflection temperature (HDT) measured in accordance with ASTM D648 of 89.6 ° C. or higher, more preferably 89.8 ° C. or higher, more preferably 90 ° C. or higher, even more preferably 90.1 ° C. or higher. , there is an excellent effect in the balance of chemical resistance, impact strength and heat resistance within this range.
[85]
Hereinafter, a method for producing the thermoplastic resin composition of the present invention and a molded article including the composition will be described. In describing the method for producing the thermoplastic resin composition of the present invention and a molded article including the composition, all of the above-described thermoplastic resin composition is included.
[86]
Method for producing a thermoplastic resin composition
[87]
The method for producing the thermoplastic resin composition of the present invention is preferably A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm as a core, A-2) average Base resin 100 comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having a particle diameter of 0.3 to 0.6 μm as a core, B-1) an aromatic vinyl polymer, and B-2) a heat-resistant aromatic vinyl polymer parts by weight; and C) 0.5 to 10 parts by weight of a polyolefin elastomer; kneading and extruding at 200 to 330 ° C. and 100 to 500 rpm conditions to prepare a thermoplastic resin composition, wherein the thermoplastic resin composition has a heat deflection temperature (HDT) It may be 89 ° C. or higher, and in this case, the thermoplastic resin composition produced has excellent economic feasibility and chemical resistance at the same time by including a predetermined additive at a low cost compared to conventional additives for chemical resistance, and has excellent heat resistance and impact strength.
[88]
The kneading may be, for example, kneading the base resin first, then kneading the polymer by adding the plasticizer, and in another example, kneading the base resin and the polymer plasticizer at once.
[89]
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.
[90]
The kneading and extrusion may be performed, for example, at a barrel temperature of 150 to 330 °C, 180 to 300 °C, 180 to 280 °C, or 200 to 250 °C, in which case the throughput per unit time is adequate and sufficient melt kneading. This may be possible, and there is an effect that does not cause problems such as thermal decomposition of the resin component.
[91]
The kneading and extrusion may be performed under the condition that, for example, the number of screw rotations is 50 to 400 rpm, 100 to 350 rpm, 100 to 300 rpm, 120 to 300 rpm, or 150 to 250 rpm, in which case the throughput per unit time is appropriate Thus, while excellent in process efficiency, there is an effect of suppressing excessive cutting.
[92]
molded product
[93]
The molded article of the present substrate may be made of, for example, the thermoplastic resin composition of the present substrate, and in this case, it has excellent mechanical properties such as impact strength, and excellent chemical resistance, processability and heat resistance expressed in melt index.
[94]
The molded article may include, for example, housings of home appliances such as air conditioners, vacuum cleaners, washing machines, refrigerators and TV back covers; housings of OA equipment such as computers, notebook computers, monitors, facsimiles, telephones, copiers and scanners; automotive parts such as interior and exterior materials for automobiles; building interior and exterior materials; member for toys; leisure goods; And it may be an interior decoration, more preferably a building exterior material, and more preferably a decorative sheet, in this case, the thermoplastic resin composition of the present base material has a higher quality than the chemical resistance, impact strength and heat resistance required in the market. There are advantages that can be provided by
[95]
Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such variations and modifications fall within the scope of the appended claims.
[96]
[Example]
[97]
A-1) First graft copolymer of emulsion polymerization (Core: 50 wt% of butyl acrylate polymer having an average particle diameter of 130 nm, Shell: 35 wt% of styrene, 15 wt% of acrylnitrile)
[98]
A-2) Second graft copolymer of emulsion polymerization (Core: 50 wt% of butyl acrylate polymer having an average particle diameter of 500 nm, Shell: 35 wt% of styrene, 15 wt% of acrylnitrile)
[99]
B-1) Bulk polymerization type SAN resin (97HC, manufactured by LG Chem)
[100]
B-2) Bulk polymerization type heat-resistant SAN resin (98UHM, manufactured by LG Chem)
[101]
C-1) Polyolefin elastomer: EBR (LG168) having a melt index (190°C, 2.16kg) of 1.2 g/10min, a butylene content of 30-40% by weight, a density of 0.860-0.864, and a weight average molecular weight of 90,000-110,000 , manufactured by LG Chem) was used.
[102]
C-2) Polyolefin elastomer: EBR (LC565) having a melt index (190° C., 2.16 kg) of 5.0 g/10 min, a butylene content of 30 to 40 wt %, a density of 0.863 to 0.867, and a weight average molecular weight of 60,000 to 80,000 , manufactured by LG Chem) was used.
[103]
C-3) Polyolefin elastomer: EOR (LC150, having a melt index (190°C, 2.16kg) of 1.0 g/10min, an octene content of 30-40% by weight, a density of 0.856-0.860, and a weight average molecular weight of 120,000-140,000 LG Chem) was used.
[104]
C-4) Polyolefin elastomer: EBR (LC185) having a melt index (190° C., 2.16 kg) of 1.2 g/10 min, a butylene content of 10 to 20 wt %, a density of 0.883 to 0.887, and a weight average molecular weight of 800,000 to 1.2 million , manufactured by LG Chem) was used.
[105]
D) Polymethyl methacrylate (BA611, manufactured by LG MMA)
[106]
Examples 1 to 13 and Comparative Examples 1 to 2
[107]
In each of the components and contents shown in Table 1 below, 0.5 parts by weight of EBS resin (manufactured by Sunjoo Chemical) as a lubricant, 0.3 parts by weight of Irganox 1076 (manufactured by BASF) and 0.3 parts by weight of Irgafos 168 (manufactured by BASF) as an antioxidant, as a UV stabilizer 0.2 parts by weight of Tinuvin 770 (manufactured by BASF) was kneaded and extruded at 230° C. to prepare pellets. Melt index was measured with the prepared pellets. In addition, the prepared pellets were injected at a molding temperature of 220° C. to prepare a specimen for measuring physical properties.
[108]
[Test Example]
[109]
The properties of the pellets and specimens prepared in Examples 1 to 13 and Comparative Examples 1 to 2 were measured by the following method, and the results are shown in Table 2 below.
[110]
* Melt index (MI): The prepared pellets were measured by the ASTM D1238 method under the conditions of 220 ℃ / 10 kg.
[111]
* Izod impact strength (kg·cm/cm; IMP): The thickness of the specimen was 1/4 inch and was measured by ASTM 256 method.
[112]
* Hardness (R-Scale): measured according to ASTM D785.
[113]
* Heat deflection temperature (HDT): It was measured under the condition of 18.6 kg in accordance with ASTM D648.
[114]
* Chemical resistance: Compare the degree of melting by dropping MEK (methyl ethyl ketone) as a solvent on the specimen and maintain the original state for a long time. ○ (good), if it is easily broken and cracked before the appropriate time, it was evaluated as X (bad).
[115]
[Table 1]
Classification (parts by weight) A-1) graft copolymer A-2) graft copolymer B-1) SAN resin B-2) Heat-resistant SAN resin C-1) Polyolefin elastomer C-2) Polyolefin elastomer D)PMMA
Example 1 7 14 64 15 0.5 - -
Example 2 7 14 64 15 One - -
Example 3 7 14 64 15 3 - -
Example 4 7 14 64 15 5 - -
Example 5 7 14 64 15 10 - -
Example 6 7 14 64 15 - 0.5 -
Example 7 7 14 64 15 - One -
Example 8 7 14 55 24 3 - -
Example 9 7 14 69 10 3 - -
Comparative Example 1 7 14 64 15 - - -
Comparative Example 2 7 14 64 15 - - 0.5
[116]
[Table 2]
division MI IMP Hardness HDT chemical resistance
Example 1 9.4 9.8 115.4 90.3 ○
Example 2 9.8 9.3 114.9 90.8 ◎
Example 3 10.4 8.9 114.2 91.1 ◎
Example 4 11.1 7.6 113.6 91.0 ◎
Example 5 12.3 6.7 112.8 90.8 ◎
Example 6 10.3 9.3 115.7 89.8 ○
Example 7 11.1 8.7 114.6 90.4 ◎
Example 8 10.5 8.8 114.4 92.4 ◎
Example 9 10.1 9.1 115.5 90.4 ◎
Comparative Example 1 9.0 8.8 116.0 89.5 X
Comparative Example 2 9.8 8.5 116.5 88.8 X
[117]
As shown in Tables 1 and 2, the thermoplastic resin compositions (Examples 1 to 9) according to the present invention had a hardness compared to Comparative Example 1 which did not include both the polyolefin elastomer according to the present invention and the conventional additive for chemical resistance. It was confirmed that the heat resistance expressed by the melt index and the heat deflection temperature was excellent while maintaining the same or higher level, and in particular, the chemical resistance was significantly improved. In addition, the thermoplastic resin composition (Examples 1 to 9 ) compared to Comparative Example 2 including the conventional chemical resistance additive, the melt index, impact strength, and hardness were confirmed to be significantly superior to heat resistance and chemical resistance while maintaining the same or higher levels.
[118]
In addition, Examples 1 to 5 containing an ethylene-butene elastomer having a butene content of 30 to 40% by weight, a weight average molecular weight of 90,000 to 110,000 g/mol, and a density of 0.860 to 0.864 as the polyolefin elastomer according to the present invention The butene content is 30 to 40% by weight, the weight average molecular weight is 60,000 to 80,000 g/mol, and the ethylene-butene elastomer having a density of 0.863 to 0.867 is superior in impact strength and heat resistance compared to Examples 6 and 7 was able to confirm
[119]
[Table 3]
Classification (parts by weight) A-1) graft copolymer A-2) graft copolymer B-1) SAN resin B-2) Heat-resistant SAN resin C-3) Polyolefin elastomer C-4) Polyolefin elastomer D)PMMA
Example 10 7 14 64 15 One - -
Example 11 7 14 64 15 3 - -
Example 12 7 14 64 15 - One -
Example 13 7 14 64 15 - 3 -
[120]
[Table 4]
division MI IMP Hardness HDT chemical resistance
Example 10 9.7 9.5 114 89.5 ◎
Example 11 10.2 9.4 113.5 89.1 ◎
Example 12 9.7 9.0 115.2 89.6 ◎
Example 13 10.3 8.7 115 89.4 ◎
[121]
As shown in Tables 3 and 4, the thermoplastic resin composition (Examples 10 to 13) according to the present invention compared with Comparative Example 1 as in Examples 1 to 9 above, hardness and heat resistance are equivalent or higher level It can be seen that the melt index is excellent while maintaining there was.
Claims
[Claim 1]
A-1) An acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm as a core, A-2) an acrylate rubber having an average particle diameter of 0.3 to 0.6 μm as a core 100 parts by weight of a base resin comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, B-1) an aromatic vinyl polymer, and B-2) a heat-resistant aromatic vinyl polymer; and C) 0.5 to 10 parts by weight of a polyolefin elastomer, wherein the thermoplastic resin composition has a heat deflection temperature (HDT) of 89° C. or higher.
[Claim 2]
The method according to claim 1, wherein A-1) the graft copolymer is 1 to 30% by weight, A-2) the graft copolymer is 5 to 50% by weight, and B-1) the aromatic vinyl polymer is 40 to 85% by weight. % by weight, and B-2) the heat-resistant aromatic vinyl polymer is 5 to 50% by weight.
[Claim 3]
The method according to claim 1, wherein the A-1) graft copolymer and the A-2) graft copolymer are independently 40 to 60% by weight of an acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10% by weight of a vinyl cyanide compound to 20% by weight of the thermoplastic resin composition.
[Claim 4]
The thermoplastic resin composition according to claim 1, wherein the weight ratio of the A-1) graft copolymer to the A-2) graft copolymer is 1:1.1 to 1:5.
[Claim 5]
The thermoplastic resin composition according to claim 1, wherein the aromatic vinyl polymer B-1) is an aromatic vinyl compound-vinyl cyan compound copolymer.
[Claim 6]
The thermoplastic resin composition according to claim 1, wherein B-2) the heat-resistant aromatic vinyl polymer comprises at least one selected from the group consisting of alpha-methylstyrene and maleimide as a heat-resistant monomer.
[Claim 7]
The thermoplastic resin composition of claim 1, wherein C) the polyolefin elastomer is at least one selected from the group consisting of ethylene-alpha-olefin copolymers and linear low-density polyethylene (LLDPE).
[Claim 8]
The thermoplastic resin composition according to claim 1, wherein C) the polyolefin elastomer has a melt index (190° C., 2.16 kg) of 0.3 to 20 g/10 min.
[Claim 9]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an Izod impact strength (1/4 inch, ASTM D1238) of 6 kg.cm/cm or more.
[Claim 10]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a melt index (220° C., 10 kg) of 9 g/10 min or more.
[Claim 11]
A-1) An acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm as a core, A-2) an acrylate rubber having an average particle diameter of 0.3 to 0.6 μm as a core 100 parts by weight of a base resin comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, B-1) an aromatic vinyl polymer, and B-2) a heat-resistant aromatic vinyl polymer; and C) 0.5 to 10 parts by weight of a polyolefin elastomer; kneading and extruding at 200 to 330 ° C. and 100 to 500 rpm conditions to prepare a thermoplastic resin composition, wherein the thermoplastic resin composition has a heat deflection temperature (HDT) Method for producing a thermoplastic resin composition, characterized in that 89 ℃ or higher.
[Claim 12]
A molded article comprising the thermoplastic resin composition of any one of claims 1 to 10.
[Claim 13]
A-1) 1 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm as a core, A-2) Acryl having an average particle diameter of 0.3 to 0.6 μm 5 to 50% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a late rubber as a core, B-1) 40 to 85% by weight of an aromatic vinyl polymer, and B-2) 5 to 5 to a heat-resistant aromatic vinyl polymer 100 parts by weight of a base resin consisting of 50% by weight; and C) 0.5 to 10 parts by weight of a polyolefin elastomer.