Title of Invention: Thermoplastic resin composition and molded article thereof
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0091651 dated July 23, 2020, and is disclosed in the document of the Korean patent application
[3]
All contents are incorporated as part of this specification.
[4]
The present invention relates to a thermoplastic resin composition and a molded article thereof, and more particularly, to a variety of colors without deterioration of mechanical properties and processability, and excellent solvent resistance and chemical resistance, so that discoloration and cracks do not occur It relates to a thermoplastic resin composition suitable for industrial use of a bogie, a molded article thereof, and the like.
background
[5]
Industrial carts exposed to various chemicals are changing the trend of manufacturing methods from painting/painting steel pipes during the manufacturing process to no-painting methods of steel/plastic co-extrusion.
[6]
The acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as 'ASA resin') has weather resistance, aging resistance, chemical resistance, rigidity, impact resistance, and processability. It is widely used in the field.
[7]
However, the conventional ASA resin has disadvantages in that cracks or discoloration occur and physical properties are deteriorated when exposed to various solvents or chemicals.
[8]
In order to solve the above difficulties, a method of increasing the molecular weight of the ASA resin, or a method of increasing the content or average particle size of rubber, etc. have been tried, but satisfactory levels of chemical substances such as pesticides or disinfectants used in the field have been attempted. of solvent resistance or chemical resistance could not be obtained.
[9]
Therefore, the thermoplastic ASA for co-extrusion of steel/plastics that does not cause discoloration and cracks due to the fact that various colors can be realized without deterioration of mechanical properties and processability, and excellent solvent resistance to various types of solvents or chemical resistance to chemicals There is a need for the development of resins.
[10]
[Prior art literature]
[11]
[Patent Literature]
[12]
KR 2009-0095764 A
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[13]
In order to solve the problems of the prior art as described above, the present invention is capable of implementing various colors while maintaining the same or higher mechanical properties and processability compared to conventional ASA-based resins, and has excellent solvent and chemical resistance, resulting in discoloration and cracking An object of the present invention is to provide a thermoplastic resin composition and a molded article thereof suitable for co-extrusion of steel/plastic of industrial bogies because this does not occur.
[14]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[15]
In order to achieve the above object, the present invention provides A-1) 10 to 50 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, A- 2) 5 to 40 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 0.05 μm or more to less than 0.3 μm, and B) 20 to 65 wt% of an aromatic vinyl polymer 100 parts by weight of the base resin; and C) 0.5 to 12 parts by weight of polyamide, and solvent resistance measured as the time at which cracks occur in a solvent composed of 98% by weight of water, 1% by weight of citric acid, and 1% by weight of malic acid is 15 days or more It provides a thermoplastic resin composition comprising.
[16]
In addition, the present invention is A-1) 10 to 50% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, A-2) an average particle diameter of 0.05 μm 100 parts by weight of a base resin comprising 5 to 40% by weight of an acrylate-aromatic vinyl compound-vinylcyan compound graft copolymer containing an acrylate rubber having an acrylate rubber of not less than 0.3 μm and B) 20 to 65% by weight of an aromatic vinyl polymer ; and C) 0.5 to 12 parts by weight of polyamide, per 100 ml of permethrin (cis:trans isomer ratio of 25:75) dissolved in 0.25 g of permethrin diluted emulsion solution per 100 ml The time at which cracks occur It is possible to provide a thermoplastic resin composition, characterized in that the measured chemical resistance is 15 days or more.
[17]
The permethrin diluted emulsion solution is not particularly limited when the permethrin is an emulsion solution diluted with water, but specific examples include 0.25% by weight of permethrin, 0.075% by weight of octylphenol polyethylene glycol ether, 0.075% by weight of calcium dodecylbenzenesulfonate, and 0.075% by weight of castor oil polyglycol It may be an emulsion solution comprising 0.1% by weight of ether, 0.75% by weight of cyclohexanone, 1.25% by weight of a xylene mixture, and 97.5% by weight of dilution water.
[18]
In addition, the present invention is A-1) 10 to 50% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, A-2) an average particle diameter of 0.05 μm 100 parts by weight of a base resin comprising 5 to 40% by weight of an acrylate-aromatic vinyl compound-vinylcyan compound graft copolymer containing an acrylate rubber having an acrylate rubber of not less than 0.3 μm and B) 20 to 65% by weight of an aromatic vinyl polymer ; and C) 0.5 to 12 parts by weight of polyamide, and may provide a thermoplastic resin composition, characterized in that the gloss (gloss) measured at 45° with a gloss meter VG7000 is 30 or less.
[19]
In addition, the present invention provides a molded article comprising the thermoplastic resin composition.
[20]
In addition, the present invention is A-1) 10 to 50% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, A-2) an average particle diameter of 0.05 μm 100 parts by weight of a base resin comprising 5 to 40% by weight of an acrylate-aromatic vinyl compound-vinylcyan compound graft copolymer containing an acrylate rubber having an acrylate rubber of not less than 0.3 μm and B) 20 to 65% by weight of an aromatic vinyl polymer ; and C) preparing pellets by introducing 0.5 to 12 parts by weight of polyamide into an extruder; and co-extruding the prepared pellets and steel pipe to prepare a non-painting coated pipe, wherein the unpainted coated pipe is cracked under a solvent consisting of 98 wt% of water, 1 wt% of citric acid, and 1 wt% of malic acid It provides a method of manufacturing a non-painting coated pipe, characterized in that the solvent resistance measured by the time to be 15 days or more.
[21]
In addition, the present invention is A-1) 10 to 50% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, A-2) an average particle diameter of 0.05 μm 100 parts by weight of a base resin comprising 5 to 40% by weight of an acrylate-aromatic vinyl compound-vinylcyan compound graft copolymer containing an acrylate rubber having an acrylate rubber of not less than 0.3 μm and B) 20 to 65% by weight of an aromatic vinyl polymer ; and C) preparing pellets by introducing 0.5 to 12 parts by weight of polyamide into an extruder; and co-extruding the prepared pellets and steel pipe to prepare a unpainted coated pipe, wherein the unpainted coated pipe contains 0.25 g of permethrin (cis:trans isomer ratio 25:75) dissolved per 100 ml per 100 ml of permethrin It is possible to provide a method for manufacturing a coating-free pipe, characterized in that the chemical resistance measured as the time for cracking under the dilute emulsion solution is 15 days or more.
[22]
In addition, the present invention is A-1) 10 to 50% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, A-2) an average particle diameter of 0.05 μm 100 parts by weight of a base resin comprising 5 to 40% by weight of an acrylate-aromatic vinyl compound-vinylcyan compound graft copolymer containing an acrylate rubber having an acrylate rubber of not less than 0.3 μm and B) 20 to 65% by weight of an aromatic vinyl polymer ; and C) preparing pellets by introducing 0.5 to 12 parts by weight of polyamide into an extruder; and co-extruding the produced pellets and steel pipe to produce a non-painting coated pipe, wherein the unpainted coated pipe has a gloss measured at 45° with a gloss meter VG7000 of 30 or less. It is possible to provide a manufacturing method of
Effects of the Invention
[23]
According to the present invention, the effect of providing a thermoplastic resin composition and molded articles thereof, etc. that do not deteriorate mechanical properties and processability, can implement various colors, and do not cause discoloration and cracks due to excellent solvent resistance and chemical resistance, etc. have.
[24]
In addition, according to the present invention, there is an effect of providing a thermoplastic resin composition suitable for steel/plastic co-extrusion, particularly steel/plastic co-extrusion used as a material for an industrial bogie, and a molded article thereof.
Brief description of the drawing
[25]
1 is a photograph of the central portion of the co-extrusion samples prepared in Examples and Comparative Examples for measuring solvent resistance (left photograph) and immersed in the lower portion (right photograph).
[26]
2 is a photograph taken with an optical microscope at 30 magnification after each of the samples prepared in Examples and Comparative Examples were treated for 15 days as in FIG. 1 to measure solvent resistance.
[27]
3 is a photograph taken by the film extruder used in Examples and Comparative Examples.
Modes for carrying out the invention
[28]
Hereinafter, the thermoplastic resin composition of the present disclosure and a molded article thereof will be described in detail.
[29]
In the process of continuously developing an ASA resin having both mechanical properties and chemical resistance suitable for steel/plastic co-extrusion use of industrial bogies, the present inventors added a predetermined aromatic vinyl polymer and polyamide to heterogeneous ASA resins with different rubber particle diameters at a constant composition ratio. In the case of mixing and adjusting the solvent resistance value or chemical resistance value measured by a specific method within a predetermined range, mechanical properties and processability are maintained at the same level or higher compared to conventional ASA-based resins, and various colors can be realized, discoloration and Since cracks do not occur, it was confirmed that it was particularly suitable for industrial use of a bogie, and based on this, further research was completed to complete the present invention.
[30]
[31]
The thermoplastic resin composition of the present invention is A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing acrylate rubber having an average particle diameter of 0.3 to 0.5 μm (hereinafter referred to as 'general diameter ASA resin') 10 to 50% by weight, A-2) An acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 0.05 μm or more to less than 0.3 μm (hereinafter referred to as “small-diameter ASA resin”) ) 100 parts by weight of a base resin comprising 5 to 40% by weight and B) 20 to 65% by weight of an aromatic vinyl polymer; and C) 0.5 to 12 parts by weight of polyamide, and solvent resistance measured as the time at which cracks occur in a solvent composed of 98% by weight of water, 1% by weight of citric acid, and 1% by weight of malic acid is 15 days or more In this case, there is an advantage suitable for the use of industrial bogies because mechanical properties and processability are not deteriorated, various colors can be implemented, and discoloration and cracks do not occur.
[32]
In addition, the thermoplastic resin composition of the present invention comprises A-1) 10 to 50% by weight of a general-diameter ASA resin, A-2) 5 to 40% by weight of a small-diameter ASA resin, and B) 20 to 65% by weight of an aromatic vinyl polymer 100 parts by weight of the base resin; and C) 0.5 to 12 parts by weight of polyamide, per 100 ml of permethrin (cis:trans isomer ratio of 25:75), in which 0.25 g of permethrin diluted emulsion solution is dissolved. It is characterized in that the measured chemical resistance is 15 days or more, and in this case, mechanical properties and processability are not significantly deteriorated, various colors can be realized, and discoloration and cracks do not occur. can do.
[33]
In addition, the thermoplastic resin composition of the present invention comprises A-1) 10 to 50% by weight of a general-diameter ASA resin, A-2) 5 to 40% by weight of a small-diameter ASA resin, and B) 20 to 65% by weight of an aromatic vinyl polymer 100 parts by weight of the base resin; and C) 0.5 to 12 parts by weight of polyamide, characterized in that the injection glossiness measured at 45° with a gloss meter VG7000 is 30 or less, in this case, mechanical properties and processability are not significantly reduced, It is possible to implement various colors, and since discoloration and cracks do not occur, it is possible to provide a thermoplastic resin composition suitable for industrial use of a bogie.
[34]
In the present description, solvent resistance means a property to withstand a solvent, and chemical resistance means a property to withstand not only a solvent but also a chemical substance. Therefore, in the present description, if a chemical substance other than a solvent is included, it is indicated as chemical resistance.
[35]
[36]
Hereinafter, each component constituting the thermoplastic resin composition of the present disclosure will be described in detail as follows.
[37]
[38]
A-1) Normal diameter ASA resin
[39]
The acrylate rubber of i) general diameter ASA resin of the present description may have, for example, an average particle diameter of 0.3 to 0.5 μm, preferably 0.35 to 0.5 μm, more preferably 0.35 to 0.45 μm, more preferably 0.40 to 0.40 μm. It is 0.45 ㎛, and it has good weather resistance within this range and has excellent mechanical strength such as fluidity, tensile strength and impact strength.
[40]
In this description, the average particle diameter can be measured using a dynamic light scattering method, and in detail, the Nicomp 380 equipment (product name, manufacturer: PSS) is used to Gaussian mode using the intensity value. can be measured with
[41]
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. At this time, as a specific example of measurement, the sample is prepared by diluting 0.1 g of Latex (TSC 35-50 wt%) 1,000-5,000 times with distilled water, and the measurement method is auto-dilution and measured with a flow cell, and the measurement mode is dynamic light scattering ( Dynamic light scattering) method/Intensity 300KHz/Intensity-weight Gaussian Analysis can be used, and the setting value can be measured with a temperature of 23℃, a measurement wavelength of 632.8nm, and a channel width of 10μsec.
[42]
[43]
The i) general bore ASA resin is preferably 10 to 50% by weight, more preferably 15 to 40% by weight, still more preferably 20 to 40% by weight, most preferably based on 100% by weight of the total base resin. is 20 to 35% by weight, and within this range, weather resistance, fluidity, tensile strength and impact strength are excellent.
[44]
The i) general diameter ASA resin may include, for example, 40 to 60% by weight of an acrylate rubber, 20 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, and preferably, an acrylate rubber 45 to 55% by weight, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, more preferably 50 to 55% by weight of an acrylate rubber, 30 to 35% by weight of an aromatic vinyl compound, and vinyl It may include 10 to 20% by weight of the cyanide compound, and within this range, weather resistance, fluidity, tensile strength and impact strength are excellent.
[45]
The polymer comprising any of the above compounds means a polymer polymerized including the compound, and the unit in the polymerized polymer is derived from the compound.
[46]
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.
[47]
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.
[48]
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.
[49]
[50]
The i) general-diameter ASA resin 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.
[51]
The emulsion polymerization is not particularly limited in the case of emulsion graft polymerization generally carried out in the art to which the present invention pertains.
[52]
[53]
A-2) Small diameter ASA resin
[54]
A-2) The acrylate rubber of the small-diameter ASA resin of the present description may have, for example, an average particle diameter of 0.1 to 0.2 μm, preferably 0.1 to 0.18 μm, more preferably 0.11 to 0.15 μm, still more preferably It is 0.11 to 0.13 μm, and excellent weather resistance, colorability, impact strength, chemical resistance and gloss can be imparted to the finally manufactured thermoplastic resin composition within this range.
[55]
A-2) The small-diameter ASA resin is preferably 5 to 40% by weight, more preferably 5 to 30% by weight, even more preferably 10 to 30% by weight, most preferably based on 100% by weight of the base resin in total. Preferably, it is 10 to 25 wt%, and within this range, weather resistance, fluidity, tensile strength and impact strength are excellent.
[56]
[57]
The sum of the weights of the A-1) general-diameter ASA resin and A-2) small-diameter ASA resin is preferably 30 to 60% by weight, more preferably 35 to 55% by weight, based on 100% by weight of the total base resin. %, more preferably 35 to 50% by weight, and there is an effect excellent in gloss, solvent resistance and chemical resistance within this range.
[58]
The weight ratio (A-1:A-2) of the A-1) general-diameter ASA resin and A-2) small-diameter ASA resin is preferably in an excess of A-1) general-diameter ASA resin, more Preferably it may be 1:0.1 to 1:0.9, more preferably 1:0.3 to 1:0.8, and most preferably 1:0.4 to 1:0.8, within which gloss, solvent resistance and chemical resistance are It has an excellent effect.
[59]
[60]
The A-2) small-diameter ASA resin may include, for example, 40 to 60% by weight of an acrylate rubber, 20 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, preferably an acrylate rubber 45 to 55% by weight, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, more preferably 50 to 55% by weight of an acrylate rubber, 30 to 35% by weight of an aromatic vinyl compound and 10 to 20 wt% of a vinyl cyanide compound, and has excellent effects in weather resistance, fluidity, tensile strength and impact strength within this range.
[61]
[62]
The A-2) small-diameter ASA resin may be prepared by, for example, emulsion polymerization, and in this case, chemical resistance, weather resistance, fluidity, tensile strength and impact strength are excellent.
[63]
The emulsion polymerization is not particularly limited in the case of emulsion graft polymerization generally carried out in the art to which the present invention pertains.
[64]
[65]
B) aromatic vinyl polymer
[66]
B) aromatic vinyl polymer of the present substrate is preferably 20 to 65% by weight, more preferably 30 to 65% by weight, still more preferably 30 to 60% by weight, even more preferably 40% by weight based on the total weight of the base resin. to 60% by weight, most preferably 45 to 55% by weight, and excellent weather resistance and excellent gloss within this range.
[67]
[68]
The B) aromatic vinyl polymer is preferably selected from the group consisting of i) an aromatic vinyl compound-vinyl cyan compound copolymer, ii) a heat-resistant styrenic resin, and iii) a methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer. At least one, more preferably an aromatic vinyl compound-vinyl cyan compound copolymer, methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer, or a mixture thereof, more preferably an aromatic vinyl compound-vinyl cyan compound copolymer It is a composite, and has excellent weather resistance and matt properties within this range, and excellent solvent resistance and chemical resistance.
[69]
[70]
i) Aromatic vinyl compound-vinyl cyan compound copolymer
[71]
The i) aromatic vinyl compound-vinyl cyan compound copolymer is preferably 20 to 60% by weight, more preferably 30 to 60% by weight, still more preferably 40 to 50% by weight, most preferably based on the total weight of the base resin. It is preferably 45 to 50% by weight, and there is an excellent effect in solvent resistance and chemical resistance within this range.
[72]
[73]
The i) aromatic vinyl compound-vinyl cyan compound copolymer may be preferably an aromatic vinyl compound-vinyl cyan compound copolymer comprising 65 to 80 wt% of an aromatic vinyl compound and 20 to 35 wt% of a vinyl cyan compound, More preferably, i) the aromatic vinyl compound-vinyl cyan compound copolymer is an aromatic vinyl compound-vinyl cyan compound copolymer comprising 65 to 75 wt% of an aromatic vinyl compound and 25 to 35 wt% of a vinyl cyan compound, More preferably, i) the aromatic vinyl compound-vinyl cyan compound copolymer is an aromatic vinyl compound-vinyl cyan compound copolymer comprising 70 to 75 wt% of an aromatic vinyl compound and 25 to 30 wt% of a vinyl cyan compound, Most preferably, i) the aromatic vinyl compound-vinyl cyan compound copolymer is an aromatic vinyl compound-vinyl cyan compound copolymer comprising 72 to 75 wt% of an aromatic vinyl compound and 25 to 28 wt% of a vinyl cyan compound, Within this range, there is an effect excellent in solvent resistance and chemical resistance.
[74]
[75]
The i) aromatic vinyl compound-vinyl cyan compound copolymer preferably has a weight average molecular weight of 100,000 to 200,000 g/mol, more preferably 110,000 to 180,000 g/mol, preferably 120,000 to 170,000 g/mol, and , there is an effect excellent in solvent resistance and chemical resistance within this range.
[76]
In another preferred example, i) the aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of 100,000 to 150,000 g/mol, more preferably 110,000 to 140,000 g/mol, and even more preferably 120,000 to 130,000 g/mol And within this range, all of the matte properties, solvent resistance and chemical resistance have excellent effects.
[77]
[78]
In another example, the i) aromatic vinyl compound-vinyl cyan compound copolymer is a) 10 to 60 wt % of the aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 100,000 to 150,000 g/mol, based on the total weight of the base resin , and b) an aromatic vinyl compound having a weight average molecular weight of more than 150,000 g/mol to 150,000 g/mol or less, and 0 to 40% by weight of a vinyl cyan compound copolymer, within this range, tensile strength and impact strength, etc. It has an excellent effect.
[79]
In another preferred embodiment, i) the aromatic vinyl compound-vinyl cyan compound copolymer comprises a) 20 to 50 weights of the aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 100,000 to 150,000 g/mol, based on the total weight of the base resin %, and b) 20 to 40 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of greater than 150,000 g/mol to 150,000 g/mol or less, within this range, tensile strength and impact strength, etc. This has an excellent effect.
[80]
As a more preferred example, the i) aromatic vinyl compound-vinyl cyan compound copolymer comprises a) 20 to 50 wt % of the aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 100,000 to 150,000 g/mol, based on the total weight of the base resin. , and b) 30 to 40% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of greater than 150,000 g/mol to 150,000 g/mol or less, and within this range, tensile strength and impact strength, etc. It has an excellent effect.
[81]
In a more specific example, i) the aromatic vinyl compound-vinyl cyan compound copolymer comprises a) 10 to 30 wt %, preferably 15 to 25 wt %, of the aromatic vinyl compound-vinyl cyan compound copolymer, based on the total weight of the base resin, and b) 25 to 45 wt%, more preferably 30 to 40 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer, and within this range, there is an excellent effect in tensile strength and impact strength.
[82]
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, in this case mechanical It has the advantage of being excellent in strength.
[83]
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, in which case mechanical strength is There are excellent advantages.
[84]
The aromatic vinyl compound-vinyl cyan compound copolymer may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, and in this case, heat resistance and fluidity are excellent.
[85]
The suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are not particularly limited in the case of solution polymerization and block polymerization methods commonly performed in the art to which the present invention pertains, respectively.
[86]
[87]
ii) heat-resistant styrenic resin
[88]
The ii) heat-resistant styrene-based resin is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less, based on the total weight of the base resin, and in a preferred embodiment, it is added to the base resin. It is not included, and in this case, there is an advantage of excellent solvent resistance and chemical resistance.
[89]
As another example, the ii) heat-resistant styrene-based resin may be included in an amount of 1 to 20% by weight, preferably 5 to 17% by weight, more preferably 5 to 15% by weight, and within this range, mechanical properties and heat resistance, etc. This has excellent advantages.
[90]
[91]
The ii) heat-resistant styrene-based resin preferably contains 60 to 80% by weight of α-methylstyrene, 20 to 40% by weight of a vinyl cyanide compound, and 0 to 10% by weight of an aromatic vinyl compound (except α-methylstyrene) and more preferably 60 to 75% by weight of α-methylstyrene, 20 to 30% by weight of a vinyl cyan compound, and 0 to 10% by weight of an aromatic vinyl compound, and mechanical properties and heat resistance within this range There are excellent advantages.
[92]
The ii) heat-resistant styrene-based resin may preferably be an α-methylstyrene-vinyl cyan compound copolymer, and in this case, mechanical properties and heat resistance are excellent.
[93]
[94]
The ii) heat-resistant styrenic resin preferably has a weight average molecular weight of 80,000 to 150,000 g/mol, more preferably 80,000 to 120,000 g/mol, still more preferably 80,000 to 100,000 g/mol, and heat resistance within this range Also, there is an excellent effect.
[95]
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 with respect to a standard PS (standard polystyrene) sample. At this time, as a specific example of measurement, solvent: THF, column temperature: 40°C, flow rate: 0.3ml/min, sample concentration: 20mg/ml, injection amount: 5 μl, column model: 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing: Agilent ChemStation S/W, test method (Mn, Mw and PDI): It can be measured under the conditions of OECD TG 118.
[96]
[97]
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, in this case mechanical It has the advantage of being excellent in strength.
[98]
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, in which case mechanical strength is There are excellent advantages.
[99]
[100]
The ii) heat-resistant styrenic resin may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, and in this case, heat resistance and fluidity are excellent.
[101]
The suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are not particularly limited in the case of solution polymerization and block polymerization methods commonly performed in the art to which the present invention pertains, respectively.
[102]
[103]
iii ) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer
[104]
The iii) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer is preferably 40% by weight or less, more preferably 30% by weight or less, based on the total weight of the base resin, and specific examples include 1 to 40% by weight, A preferred example is 10 to 40% by weight, more preferably 10 to 30% by weight, and more preferably 20 to 30% by weight. Within this range, weather resistance is greatly improved, and mechanical properties such as tensile strength and hardness are excellent. It works.
[105]
The iii) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer preferably comprises 60 to 85 wt% of a methacrylate compound, 5 to 30 wt% of an aromatic vinyl compound, and 5 to 30 wt% of a vinyl cyan compound may be made, more preferably 60 to 80% by weight of a methacrylate compound, 5 to 20% by weight of an aromatic vinyl compound, and 15 to 30% by weight of a vinyl cyan compound, more preferably a methacrylate compound 70 to 80% by weight, 5 to 15% by weight of an aromatic vinyl compound, and 15 to 25% by weight of a vinyl cyanide compound, the weather resistance is greatly improved within this range, and excellent mechanical properties such as tensile strength and hardness It works.
[106]
The methacrylate compound may be included in an amount of preferably 60 to 80% by weight, more preferably 65 to 80% by weight, based on the total weight of the iii) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer, Within this range, weather resistance is greatly improved, and mechanical properties such as tensile strength and hardness are excellent.
[107]
[108]
The methacrylate compound may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples thereof include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2 - May be at least one selected from the group consisting of ethylhexyl methacrylate and lauryl methacrylate, preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, more preferably methyl methacrylate It may be a acrylate.
[109]
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, in this case mechanical It has the advantage of being excellent in strength.
[110]
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, in which case mechanical strength is There are excellent advantages.
[111]
[112]
The iii) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer may preferably have a weight average molecular weight of 80,000 to 200,000 g/mol, more preferably 100,000 to 150,000 g/mol, still more preferably Preferably, it is 120,000 to 140,000 g/mol, and within this range, weather resistance is greatly improved, and mechanical properties such as tensile strength and hardness are excellent.
[113]
As another example, the iii) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer is a methyl methacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 80,000 to 110,000 g/mol (hereinafter, 'low molecular weight SAMMA resin) and a methyl methacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 120,000 to 200,000 g/mol (hereinafter referred to as 'high molecular weight SAMMA resin') may be mixed.
[114]
The low molecular weight SAMMA resin and the high molecular weight SAMMA resin may have, for example, a weight ratio of 1: 0.1 to 0.45, preferably 1: 0.2 to 0.45, more preferably 1: 0.3 to 0.45, and still more preferably 1: It may be 0.35 to 0.45, and there is an advantage of excellent weather resistance within this range.
[115]
[116]
The iii) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer may be prepared by, for example, solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and the solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization are each In the case of emulsion polymerization and suspension polymerization methods commonly practiced in the art to which the present invention pertains, it is not particularly limited.
[117]
[118]
C) polyamide
[119]
C) polyamide of the present substrate greatly contributes to solvent resistance and chemical resistance, preferably 0.5 to 12 parts by weight, more preferably 1 to 10 parts by weight, still more preferably 3 parts by weight based on 100 parts by weight of the base resin. to 10 parts by weight, more preferably 4 to 10 parts by weight, and most preferably 6 to 10 parts by weight, there is an advantage of excellent solvent resistance and chemical resistance within this range and excellent balance of physical properties.
[120]
[121]
C) Polyamide refers to a thermoplastic polymer including an amide bond, and specific examples include polyamide 6, polyamide 66 (PA 6.6), polyamide 46, polyamide ll, polyamide 12, polyamide 610, polyamide 612 , polyamide 6/66, polyamide 6/612, polyamide MXD6, polyamide 6/MXD6, polyamide 66/MXD6, polyamide 6T, polyamide 6I, polyamide 6/6T, polyamide 6/6I, poly Amide 66/6T, Polyamide 66/6I, Polyamide 6/6T/6I, Polyamide 66/6T/6I, Polyamide 9T, Polyamide 9I, Polyamide 6/9T, Polyamide 6/9I, Polyamide 66 /9T, polyamide 6/12/9T, polyamide 66/12/9T, polyamide 6/12/9I, and polyamide 66/12/6I may be at least one selected from the group consisting of, preferably polyamide It is at least one selected from the group consisting of 6 (PA 6) and polyamide 66 (PA 6.6), and has excellent solvent resistance and chemical resistance within this range, and an excellent balance of physical properties.
[122]
The polyamide C) more preferably includes nylon 6 and nylon 66, and in this case, there is an advantage in that it has excellent solvent resistance and chemical resistance as well as excellent gloss properties.
[123]
The weight ratio of nylon 6 to nylon 66 (nylon 6: nylon 66) is preferably 1: 1.1 to 10, more preferably 1: 1.5 to 5, still more preferably 1: 2 to 5, most preferably 1 : 2 to 4, and in this case, it has excellent solvent resistance and chemical resistance as well as excellent low gloss properties.
[124]
[125]
C) The polyamide is, for example, a low-melting polyamide having a melting point of 260° C. or less, preferably 240° C. or less, more preferably 230° C. or less, and still more preferably 210 to 220° C. for the purpose of balancing chemical resistance and physical properties. It is preferable to use at least one type of polyamide, and for low gloss properties, it is preferable to use at least one polyamide having a high melting point of 230 °C or higher, preferably 240 °C or higher, more preferably 260 °C or higher, preferably A mixture of the low melting point polyamide and the high melting point polyamide is used.
[126]
In the present description, the melting point may be measured using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 2920) manufactured by TA. As a specific measurement example, the melting point is measured by bringing the DSC to equilibrium at a temperature of 0 ℃, increasing it by 20 ℃ per minute, raising it to 180 ℃, decreasing it by 20 ℃ per minute to -60 ℃, and increasing it by 10 ℃ per minute It can be measured by increasing the temperature up to 180 °C. Here, the melting point is obtained by taking the area of ​​the apex of the endothermic curve during the second temperature rise.
[127]
C) As an example, it is preferable to use a polyamide having a relative viscosity (96% sulfuric acid solution) of 2.0 to 4.0, preferably 2.0 to 3.5, more preferably 2.0 to 3.0, and still more preferably 2.4 to 2.7.
[128]
In the present description, % means % by weight unless otherwise defined.
[129]
In the present description, the relative viscosity can be measured with an Ubbelohde viscometer by the ISO 307 sulfuric acid method.
[130]
[131]
C) The method for preparing polyamide is not particularly limited as long as it is a polymerization method commonly practiced in the art to which the present invention belongs, and may be commercially purchased and used if it meets the definition of polyamide according to the present invention.
[132]
[133]
Thermoplastic resin composition
[134]
The thermoplastic resin composition of the present invention preferably has a solvent resistance of 15 days or more, measured as the time at which cracks occur in a solvent consisting of 98% by weight of water, 1% by weight of citric acid, and 1% by weight of malic acid, and in this case, the conventional Compared to the ASA-based resin of ASA resin, mechanical properties and processability are maintained at the same or higher level, and in particular, various colors can be realized and discoloration and cracks do not occur, so it is suitable for industrial use of bogies.
[135]
The thermoplastic resin composition preferably has chemical resistance measured as the time for cracking under a permethrin diluted emulsion solution in which 0.25 g of permethrin (cis:trans isomer ratio 25:75), an insecticidal active ingredient, per 100 ml is dissolved 15 days or longer, and in this case, mechanical properties and processability are maintained at the same level or higher compared to conventional ASA-based resins, and in particular, various colors are possible and discoloration and cracks do not occur, so there is an advantage suitable for industrial use of bogies.
[136]
The thermoplastic resin composition preferably has an injection gloss (gloss) of 30 or less measured at 45° with a gloss meter VG7000, and in this case, mechanical properties and processability compared to conventional ASA-based resins are maintained at the same level or higher, and in particular, various Color can be implemented and discoloration and cracks do not occur, so it has the advantage of being suitable for industrial use.
[137]
[138]
The thermoplastic resin composition more preferably has an injection gloss (gloss) of 29 or less measured at 45° with a gloss meter VG7000, 15 to 30 in a preferred embodiment, 16 to 29 in a more preferred embodiment, Within this range, it has excellent matt properties and excellent solvent resistance and chemical resistance.
[139]
As another example, the thermoplastic resin composition has a film gloss of 10 or less, preferably 8 or less, more preferably 7 or less, measured at 60° using a gloss meter VG7000 with a sheet of 0.15T, and is a preferred embodiment An example is 1 to 10, a more preferred embodiment is 2 to 8, and a more preferred embodiment is 3 to 7, and within this range, the matt property is excellent, and there is an effect excellent in solvent resistance and chemical resistance.
[140]
[141]
The thermoplastic resin composition preferably has an Izod impact strength of 4 kg·cm/cm or more, preferably 6 kg·cm/cm or more, as measured by the ASTM 256 method, and a specific example is 6 to 13 kg·cm/cm can
[142]
The thermoplastic resin composition preferably has a hardness (R-Scale) of 80 or more, preferably 85 or more, as measured by the ASTM D785 method, and a specific example is 80 to 105, and a preferable example is 86 to 104, within this range. It has excellent hardness and excellent balance of physical properties.
[143]
The thermoplastic resin composition preferably has a tensile strength (1/8 inch) according to ASTM 638 of 350 kg/cm 2 or more, more preferably 380 kg/cm 2 or more, still more preferably 400 kg/cm 2 or more, and specific examples include 350 to 480 kg/cm2, preferably 380 to 480 kg/cm2, and more preferably 400 to 450 kg/cm2, within this range, has excellent mechanical properties as well as excellent solvent resistance and chemical resistance. have.
[144]
[145]
The thermoplastic resin composition may have a weather resistance (ΔE) of 6 or less, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, measured for 2000 hours by the SAE J1960 method, for example. Within this range, there is an effect that the weather resistance is excellent and the physical property balance is excellent.
[146]
[147]
The thermoplastic resin composition preferably has a flow index (MI) (220° C., load 10 kg) according to ASTM D1238 of 3 g/10 min or more, preferably 4 g/10 min or more, and more preferably 4 to 12 g It may be /10 min, more preferably 5 to 8 g/10 min, and there is an advantage of excellent coextrusion properties within this range.
[148]
[149]
The thermoplastic resin composition is optionally used as a heat stabilizer, light stabilizer, dye, pigment, colorant, mold release agent, antistatic agent, antibacterial agent, processing aid, metal deactivator, flame retardant, flame retardant, dripping inhibitor, anti-friction agent and abrasion-resistant agent, if necessary. It may further include 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.5 to 1 parts by weight of at least one selected from the group consisting of, within this range, the properties of the thermoplastic resin composition of the present invention There is an effect that the necessary physical properties are well realized without lowering the
[150]
[151]
The method for preparing the thermoplastic resin composition of the present invention is preferably A-1) 10 to 50 wt% of a general-diameter ASA resin, A-2) 5-40 wt% of a small-diameter ASA resin, and B) 20 to 65 wt% of an aromatic vinyl polymer % of the base resin including 100 parts by weight; and C) mixing 0.5 to 12 parts by weight of polyamide, and then using an extrusion kneader under 220 to 280 ° C. conditions to prepare pellets, and in this case, if mechanical properties and processability are not reduced In particular, it is possible to implement various colors and has excellent chemical resistance, so discoloration and cracks do not occur, which has the advantage of being provided for steel/plastic co-extrusion of industrial bogies.
[152]
[153]
The method for producing the thermoplastic resin composition shares all the technical characteristics of the aforementioned thermoplastic resin composition. Therefore, a description of the overlapping portion will be omitted.
[154]
[155]
The step of preparing the pellets using the extrusion kneader may be preferably carried out under 220 to 280 ℃, more preferably under 220 to 250 ℃, wherein the temperature means the temperature set in the cylinder.
[156]
The extrusion kneader is not particularly limited if it is an extrusion kneader commonly used in the art to which the present invention belongs, and may preferably be a twin-screw extrusion kneader.
[157]
[158]
molded article
[159]
The molded article of the present substrate is characterized by including the thermoplastic resin composition of the present substrate, and in this case, it is possible to implement various colors while having excellent mechanical properties and processability, and has excellent solvent and chemical resistance, so that discoloration and cracks do not occur There is an advantage.
[160]
The molded article may be preferably a non-painting coated pipe obtained by co-extrusion of the thermoplastic resin composition and a steel pipe, and in this case, it is possible to implement various colors while having excellent mechanical properties and processability, and excellent solvent resistance and chemical resistance to cause discoloration and cracks There is an advantage that this does not occur.
[161]
[162]
The manufacturing method of the unpainted coating pipe is preferably A-1) 10 to 50% by weight of a general diameter ASA resin, A-2) 5 to 40% by weight of a small diameter ASA resin, and B) 20 to 65% by weight of an aromatic vinyl polymer 100 parts by weight of the base resin including; And C) preparing pellets using an extrusion kneader under 220 to 280 ℃ conditions after mixing including 0.5 to 12 parts by weight of polyamide; and co-extruding the prepared pellets and steel pipe to prepare a non-painting coated pipe, wherein the unpainted coated pipe is cracked under a solvent consisting of 98 wt% of water, 1 wt% of citric acid, and 1 wt% of malic acid It is characterized in that the chemical resistance measured by the time taken is 15 days or more, and in this case, various colors can be realized while excellent mechanical properties and processability, and there is an advantage that discoloration and cracks do not occur due to excellent solvent resistance and chemical resistance .
[163]
As another example, the manufacturing method of the unpainted coating pipe comprises: A-1) 10 to 50 wt% of a general diameter ASA resin, A-2) 5 to 40 wt% of a small diameter ASA resin, and B) 20 to 65 wt% of an aromatic vinyl polymer 100 parts by weight of a base resin comprising; And C) preparing pellets using an extrusion kneader under 220 to 280 ℃ conditions after mixing including 0.5 to 12 parts by weight of polyamide; and co-extruding the prepared pellets and steel pipe to prepare a unpainted coated pipe, wherein the unpainted coated pipe contains 0.25 g of permethrin (cis:trans isomer ratio 25:75) dissolved per 100 ml per 100 ml of permethrin It is characterized in that the chemical resistance, measured as the time for cracking under the dilute emulsion solution, is 15 days or more. There is an advantage that discoloration and cracks do not occur.
[164]
As another example, the manufacturing method of the unpainted coating pipe comprises: A-1) 10 to 50 wt% of a general diameter ASA resin, A-2) 5 to 40 wt% of a small diameter ASA resin, and B) 20 to 65 wt% of an aromatic vinyl polymer 100 parts by weight of a base resin comprising; And C) preparing pellets using an extrusion kneader under 220 to 280 ℃ conditions after mixing including 0.5 to 12 parts by weight of polyamide; and co-extruding the produced pellets and steel pipe to prepare a coating-free pipe, wherein the coating-free pipe has a gloss measured at 45° with a gloss meter VG7000 of 30 or less, and in this case It has excellent mechanical properties and processability, while various colors can be implemented, and has excellent solvent and chemical resistance, so discoloration and cracks do not occur.
[165]
The method for manufacturing the unpainted pipe shares all the technical characteristics of the above-described thermoplastic resin composition. Therefore, a description of the overlapping portion will be omitted.
[166]
[167]
The molded article may preferably be manufactured including the step of extruding or injecting the thermoplastic resin composition of the present invention at a molding temperature of 190 to 250 °C, and has the advantage of exhibiting an excellent matting effect within this range.
[168]
In describing the thermoplastic resin composition of the present invention, its manufacturing method and molded article, other conditions or equipment not explicitly described can be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation do.
[169]
[170]
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.
[171]
[172]
[Example]
[173]
Materials used in Examples 1 to 7 and Comparative Examples 1 to 7 below are as follows.
[174]
A-1) General diameter ASA resin (Rubber: 50 wt% of butyl acrylate polymer-derived units having an average particle diameter of 400 nm, 35 wt% of styrene-derived units, 15 wt% of acrylonitrile-derived units)
[175]
A-2) Small-diameter ASA resin (Rubber: 50 wt% of butyl acrylate polymer-derived units having an average particle diameter of 120 nm, 35 wt% of styrene-derived units, and 15 wt% of acrylonitrile-derived units)
[176]
B-1) Bulk polymerization method SAN resin (70% by weight of styrene-derived units, 30% by weight of acrylonitrile-derived units, weight average molecular weight 170,000 g/mol)
[177]
B-2) Bulk polymerization type SAN resin (73 wt% of styrene-derived units, 27 wt% of acrylonitrile-derived units, weight average molecular weight 120,000 g/mol)
[178]
B-3) Heat-resistant SAN resin (73 wt% of units derived from α-methylstyrene, 27 wt% of units derived from acrylonitrile, and a weight average molecular weight of 100,000 g/mol)
[179]
B-4) SAMMA resin (70 wt% of methyl methacrylate-derived units, 22 wt% of styrene-derived units, 8 wt% of acrylonitrile-derived units, and a weight average molecular weight of 80,000 g/mol)
[180]
B-5) MABS resin (MA210 grade, manufactured by LG Chem, particle size 10 ㎛)
[181]
C-1) PA 6.6 (relative viscosity 2.7)
[182]
C-2) PA 6 (relative viscosity 2.3)
[183]
[184]
Examples 1 to 7 and Comparative Examples 1 to 7
[185]
Each of the components and contents listed in Table 1 below were prepared into pellets using an extrusion kneader in a 36 pie standard under 230 ° C in a twin-screw extruder, and this was uniformly made into a film with a thickness of 0.15T through a film extruder, and then this sample ( sample) and the film glossiness was measured by the following measurement method. At this time, the film extruder uses a single screw extruder for sheet molding (manufactured by Collin, E20T product, 15 pie, L/D: 20), and the temperature conditions are 50, 200, 210, 210° C. And the die part temperature was set to 220, 220, 230 ℃. The pellets were sufficiently dried in an oven at 80° C. for 3 hours or longer before input into the film extruder to remove the moisture influence, and then put into the inlet of the film extruder to uniformly produce a film with a thickness of 0.15T. The temperature of the used rear roller was set to 85° C. using water as a medium, and as shown in FIG. 3 below, a type in which only one side of the resin extruded through the T-die was in contact with the roller was used. Here, the RPM of the film extruder screw was fixed at 100 and the linear speed of the roll was adjusted so that the thickness of the film was 0.15T. Among the extruded film surfaces, the film glossiness and the like were measured for the surface in contact with the first roll.
[186]
Meanwhile, the melt index was measured with the prepared pellets.
[187]
In addition, the prepared pellets were injected at a molding temperature of 230° C. to prepare a specimen for measuring physical properties, and impact strength, tensile strength, hardness, and injection glossiness were measured using this .
[188]
[189]
[Test Example]
[190]
The properties of the pellets, sheets and specimens prepared in Examples 1 to 7 and Comparative Examples 1 to 7 were measured by the following method, and the results are shown in Table 1 below.
[191]
* Melt index (MI): The prepared pellets were measured by the ASTM D1238 method under the conditions of 220 ℃ / 10 kg.
[192]
* Tensile strength (kg/cm 2 ): Measured by ASTM D638 method.
[193]
* Hardness (R-Scale): measured by ASTM D785 method.
[194]
* Izod impact strength (kg.cm/cm): Measured by ASTM 256 method.
[195]
* Ejection gloss (gloss): was measured at 45 ° with a gloss meter (gloss meter) VG7000.
[196]
* Film gloss: Measured at 60° with a gloss meter VG7000 with a 0.15T sheet.
[197]
* Solvent resistance (disinfectant): A solvent (manufacturer: Cleanpeace, product name: Alpetzero) consisting of 98% by weight of water, 1% by weight of citric acid and 1% by weight of malic acid is added to the center of the sample as shown in the left photo of FIG. 1 below for 15 days. After contacting for a while, it was confirmed whether cracks occurred by photographing under an optical microscope at 30 magnification. In addition, as shown in the photo on the right of FIG. 1, the lower end of the sample was immersed in the solvent for 15 days and then photographed with an optical microscope at 30 magnification to check whether cracks occurred. Here, the sample was manufactured by a pipe extrusion coating method in which a plastic raw material was extruded onto a pipe and the outer surface of the pipe was coated with plastic.
[198]
* Chemical resistance (insecticide): Permethrin diluted emulsion solution (manufacturer: Green World Pharm, product name: Cleanjet) in which 0.25 g of permethrin (cis:trans isomer ratio 25:75), an insecticidal active ingredient, is dissolved per 100 ml As shown in the picture on the left, after contacting the central part of the sample for 15 days, it was photographed with an optical microscope at 30 magnification to check whether cracks occurred. In addition, as shown in the right photo of FIG. 1, the lower end of the sample was immersed in the solution for 15 days, and then photographed with an optical microscope at 30 magnification to check whether cracks occurred.
[199]
* Weather resistance: After 2000 hours of measurement by the SAE J1960 method, it was evaluated as ΔE calculated by Equation 1 below. When the ΔE value is low, the weather resistance is excellent.
[200]
[Equation 1]
[201]

[202]
[Table 1]
[203]
As shown in Table 1, the thermoplastic resin composition (see Examples 1 to 7) according to the present invention has mechanical properties such as impact strength, tensile strength, hardness, etc., compared to Comparative Examples 1 to 7, which are out of the scope of the present invention. While maintaining more than that, it was confirmed that the injection gloss and film gloss were more excellent, and the solvent resistance and chemical resistance were remarkably excellent.
[204]
As noteworthy, Examples 1 to 3 and Examples 5 containing 6 parts by weight or more of polyamide and B-2) Examples 1 to 5 and Example 7 containing a bulk polymerization type SAN resin have solvent resistance. And it was confirmed that the chemical resistance was more excellent.
[205]
In addition, in the case of Comparative Examples 6 and 7 containing B-5) MABS resin instead of A-2) small-diameter ASA resin, it was confirmed that solvent resistance and chemical resistance were significantly deteriorated.
[206]
In addition, Comparative Example 1 containing only 4 parts by weight of PA 6 having a relative viscosity of 2.3 and Comparative Example 7 not including a general-diameter ASA resin had good solvent resistance and chemical resistance, but in Comparative Example 1, the injection gloss was 73.7, the film The gloss was 61.9, which did not remarkably fall short of the effects of the present invention, and in the case of Comparative Example 7, the impact strength fell significantly to 2.3, confirming that it was significantly far from the effects of the present invention.
[207]
[208]
In addition, Comparative Example 4 has poor film gloss, Comparative Example 7 has poor impact strength,
[209]
In addition, referring to the optical micrograph of FIG. 2 below, the thermoplastic resin composition (see Examples 1 to 7) according to the present invention maintained a good surface despite exposure to solvents and chemicals for a long time, but the scope of the present invention In Comparative Examples 1 to 7, which deviate, micro-cracks, intermediate cracks, or cracks occurred on the surface in contact with solvents and chemicals, so that it was possible to directly confirm with the naked eye that solvent resistance and chemical resistance were poor.
Claims
[Claim 1]
A-1) 10 to 50 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, A-2) An average particle diameter of 0.05 μm or more to less than 0.3 μm 100 parts by weight of a base resin comprising 5 to 40 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber of B) 20 to 65 wt% of an aromatic vinyl polymer; and C) 0.5 to 12 parts by weight of polyamide, and solvent resistance measured as the time at which cracks occur in a solvent composed of 98% by weight of water, 1% by weight of citric acid, and 1% by weight of malic acid is 15 days or more A thermoplastic resin composition comprising
[Claim 2]
The method according to claim 1, wherein the A-1) and A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises 40 to 60% by weight of acrylate rubber, 20 to 40% by weight of aromatic vinyl compound, and vinyl A thermoplastic resin composition comprising 10 to 20 wt% of a cyanide compound.
[Claim 3]
The method according to claim 1, wherein B) the aromatic vinyl polymer is one selected from the group consisting of an aromatic vinyl compound-vinyl cyan compound copolymer, a heat-resistant styrene-based resin, and a methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer. Thermoplastic resin composition, characterized in that the above.
[Claim 4]
The thermoplastic resin composition according to claim 3, wherein the aromatic vinyl compound-vinyl cyan compound copolymer comprises 65 to 80 wt% of the aromatic vinyl compound and 20 to 35 wt% of the vinyl cyanide compound.
[Claim 5]
4. The method according to claim 3, wherein the aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of 100,000 to 150,000 g/mol, and an aromatic vinyl compound-vinyl cyan compound copolymer, and a weight average molecular weight of greater than 150,000 g/mol to 200,000. A thermoplastic resin composition comprising at least one selected from the group consisting of g/mol or less of an aromatic vinyl compound-vinyl cyan compound copolymer.
[Claim 6]
The thermoplastic resin composition according to claim 3, wherein the heat-resistant styrene-based resin is an α-methylstyrene-vinyl cyan compound copolymer.
[Claim 7]
The thermoplastic resin composition according to claim 6, wherein the heat-resistant styrene-based resin has a weight average molecular weight of 150,000 to 250,000 g/mol.
[Claim 8]
According to claim 3, wherein the methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer comprises 60 to 85% by weight of methacrylate, 5 to 30% by weight of an aromatic vinyl compound, and 5 to 30% by weight of a vinylcyan compound A thermoplastic resin composition comprising:
[Claim 9]
The thermoplastic resin composition according to claim 8, wherein the methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of 80,000 to 200,000 g/mol.
[Claim 10]
The thermoplastic resin composition according to claim 1, wherein C) the polyamide comprises nylon 6 and nylon 66.
[Claim 11]
The thermoplastic resin composition according to claim 10, wherein the weight ratio of nylon 6 to nylon 66 (nylon 6: nylon 66) is 1:1.1 to 10.
[Claim 12]
According to claim 1, wherein the thermoplastic resin composition is per 100 ml permethrin (cis: trans isomer ratio 25:75) permethrin per 100 ml of permethrin diluted emulsion solution in which 0.25 g is dissolved It is measured as the time that cracks occur A thermoplastic resin composition, characterized in that the chemical resistance is 15 days or more.
[Claim 13]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an injection gloss measured at 45° using a gloss meter VG7000 of 30 or less.
[Claim 14]
A molded article comprising the thermoplastic resin composition of any one of claims 1 to 13.
[Claim 15]
15. The molded article according to claim 14, wherein the molded article is a non-painting coated pipe obtained by co-extruding the thermoplastic resin composition and a steel pipe.
[Claim 16]
A-1) 10 to 50 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, A-2) An average particle diameter of 0.05 μm or more to less than 0.3 μm 100 parts by weight of a base resin comprising 5 to 40 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber of B) 20 to 65 wt% of an aromatic vinyl polymer; and C) preparing pellets by introducing 0.5 to 12 parts by weight of polyamide into an extruder; and co-extruding the prepared pellets and steel pipe to prepare a non-painting coated pipe, wherein the unpainted coated pipe is cracked under a solvent consisting of 98 wt% of water, 1 wt% of citric acid, and 1 wt% of malic acid A method of manufacturing a non-coated pipe, characterized in that the solvent resistance measured by the time to be 15 days or more.