Title of Invention: Thermoplastic resin composition, manufacturing method thereof, and molded article manufactured therefrom
technical field
[One]
The present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article manufactured therefrom, and more particularly, to a thermoplastic resin composition having excellent blow moldability and an extended molding temperature range, a method for manufacturing the same, and a molded article manufactured therefrom will be.
background
[2]
[Cross Citation with Application(s)]
[3]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0124006 dated September 24, 2020 and Korean Patent Application No. 10-2021-0086462, filed again on July 1, 2021 based thereon. All content disclosed in the literature of the application is incorporated as a part of this specification.
[4]
A conventional blow-molded acrylonitrile-butadiene-styrene (hereinafter referred to as 'ABS') resin composition for automobiles has a weight average molecular weight of 20,000 g/mol or more in order to secure blow processability and heat resistance, and a styrenic copolymer and phenylmaleimide based copolymers.
[5]
The high molecular weight, complex chain structure, and high polarity of the ABS resin composition for automobiles has a problem of low productivity because it is difficult to control the heat of reaction during polymerization. It is easy to cause melt fracture, and there is a problem in that an excessive amount of lubricant and release agent must be added.
[6]
On the other hand, the lower the molecular weight of the resin, the more likely parison sagging occurs during blow molding. Due to its large size, it is difficult to set the molding temperature for each product weight. In addition, there is a trade-off relationship between the plasticization of the heat-resistant resin and the fluidity of the low molecular weight resin, so the setting of the molding temperature is limited. Since the temperature holding capacity and product weight specifications are different for each blow equipment, the resin composition for blow molding should have a wide molding temperature range.
[7]
Therefore, there is a need to develop a resin composition for blow molding having excellent blow moldability and a wide molding temperature range.
[8]
[Prior art literature]
[9]
[Patent Literature]
[10]
Korean Registered Patent No. 10-0491031
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[11]
In order to solve the problems of the prior art as described above, an object of the present invention is to provide a thermoplastic resin composition having excellent blow moldability and a wide molding temperature range, 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) 10 to 50% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; And (E) a weight average molecular weight of 300,000 to 800,000 g / mol of branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer 1 to 20% by weight; (F) density is 0.9 in 100 parts by weight of a base resin containing to 1.5 g/cm 3 and provides a thermoplastic resin composition comprising 0.1 to 2.5 parts by weight of a high-density polyethylene resin having a weight average molecular weight of 1,000 to 6,500 g/mol.
[14]
[15]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 50% by weight; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; (E) 1 to 20% by weight of a branched vinyl cyanide-aromatic vinyl compound copolymer having a weight average molecular weight of 300,000 to 800,000 g/mol; And (G) aromatic vinyl compound-maleimide compound copolymer 5 to 25 parts by weight; to 100 parts by weight of a base resin comprising; (F) a density of 0.9 to 1.5 g / cm 3 and a weight average molecular weight of 1,000 to 6,500 g / It is possible to provide a thermoplastic resin composition comprising 0.1 to 2.5 parts by weight of the high-density polyethylene resin, which is mol.
[16]
[17]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 50% by weight; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; (E) 1 to 20% by weight of a branched vinyl cyanide-aromatic vinyl compound copolymer having a weight average molecular weight of 300,000 to 800,000 g/mol; And (H) α-methyl styrene-based compound-vinyl cyan compound copolymer 5 to 30% by weight; to 100 parts by weight of a base resin comprising, (F) a density of 0.9 to 1.5 g / cm 3 and a weight average molecular weight of 1,000 to It is possible to provide a thermoplastic resin composition comprising 0.1 to 2.5 parts by weight of a high-density polyethylene resin of 6,500 g/mol.
[18]
[19]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 50% by weight; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; (E) 1 to 20% by weight of a branched vinyl cyanide-aromatic vinyl compound copolymer having a weight average molecular weight of 300,000 to 800,000 g/mol; (G) 5 to 25% by weight of an aromatic vinyl compound-maleimide compound copolymer; And (H) α-methyl styrene-based compound-vinyl cyan compound copolymer 5 to 30% by weight; to 100 parts by weight of a base resin comprising, (F) a density of 0.9 to 1.5 g / cm 3 and a weight average molecular weight of 1,000 to It is possible to provide a thermoplastic resin composition comprising 0.1 to 2.5 parts by weight of a high-density polyethylene resin of 6,500 g/mol.
[20]
[21]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 50% by weight; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; And (E) a weight average molecular weight of 300,000 to 800,000 g / mol of branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer 1 to 20% by weight; (F) density is 0.9 in 100 parts by weight of a base resin containing to 1.5 g/cm 3 and containing 0.1 to 2.5 parts by weight of a high-density polyethylene resin having a weight average molecular weight of 1,000 to 6,500 g/mol, a plate having a length of 500 mm, a thickness of 0.5 mm, and a weight of 500 g at a barrel temperature of 220° C. of a blow molding machine It is possible to provide a thermoplastic resin composition, characterized in that the parison sag measured by discharging the listen and the time it takes to stretch 1% or more of the total length is 40 seconds or more.
[22]
[23]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 50% by weight; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; And (E) a weight average molecular weight of 300,000 to 800,000 g / mol of branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer 1 to 20% by weight; (F) density is 0.9 in 100 parts by weight of a base resin containing to 1.5 g/cm 3 and 2 including 0.1 to 2.5 parts by weight of a high-density polyethylene resin having a weight average molecular weight of 1,000 to 6,500 g/mol It provides a method for producing a thermoplastic resin composition comprising the steps of kneading and extruding under the conditions of 00 to 300 ℃ and 200 to 300 rpm to prepare pellets.
[24]
[25]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 50% by weight; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; (E) 1 to 20% by weight of a branched vinyl cyanide-aromatic vinyl compound copolymer having a weight average molecular weight of 300,000 to 800,000 g/mol; and (G) aromatic vinyl compound-maleimide compound copolymer in 100 parts by weight of a base resin comprising 5 to 25 wt%, (F) having a density of 0.9 to 1.5 g/cm 3 and a weight average molecular weight of 1,000 to 6,500 g/mol It is possible to provide a method for producing a thermoplastic resin composition comprising 0.1 to 2.5 parts by weight of a phosphorus high-density polyethylene resin, and kneading and extruding under the conditions of 200 to 300° C. and 200 to 300 rpm to prepare pellets.
[26]
[27]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 50% by weight; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; (E) 1 to 20% by weight of a branched vinyl cyanide-aromatic vinyl compound copolymer having a weight average molecular weight of 300,000 to 800,000 g/mol; And (H) α-methyl styrene-based compound-vinyl cyan compound copolymer 5 to 30% by weight; to 100 parts by weight of the base resin comprising, (F) a density of 0.9 to 1.5 g / cm 3 and a weight average molecular weight of 1,000 to It provides a method for producing a thermoplastic resin composition comprising 0.1 to 2.5 parts by weight of a high-density polyethylene resin of 6,500 g/mol, and kneading and extruding under the conditions of 200 to 300° C. and 200 to 300 rpm to prepare pellets. can do.
[28]
[29]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 50% by weight; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; (E) 1 to 20% by weight of a branched vinyl cyanide-aromatic vinyl compound copolymer having a weight average molecular weight of 300,000 to 800,000 g/mol; (G) 5 to 25% by weight of an aromatic vinyl compound-maleimide compound copolymer; And (H) α-methyl styrene-based compound-vinyl cyan compound copolymer 5 to 30% by weight; to 100 parts by weight of the base resin comprising, (F) a density of 0.9 to 1.5 g / cm 3 and a weight average molecular weight of 1,000 to It provides a method for producing a thermoplastic resin composition comprising 0.1 to 2.5 parts by weight of a high-density polyethylene resin of 6,500 g/mol, and kneading and extruding under the conditions of 200 to 300° C. and 200 to 300 rpm to prepare pellets. can do.
[30]
[31]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 50% by weight; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; And (E) a weight average molecular weight of 300,000 to 800,000 g / mol of branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer 1 to 20% by weight; (F) density is 0.9 in 100 parts by weight of the base resin comprising to 1.5 g/cm 3 and containing 0.1 to 2.5 parts by weight of a high-density polyethylene resin having a weight average molecular weight of 1,000 to 6,500 g/mol, and kneading and extruding under the conditions of 200 to 300 ° C and 200 to 300 rpm to prepare pellets, and , the prepared thermoplastic resin composition is a plate measuring the time it takes to stretch 1% or more of the total length by discharging a parison of 500 mm in length, 0.5 mm in thickness, and 500 g in weight at a barrel temperature of 220° C. of a blow molding machine. It is possible to provide a method for producing a thermoplastic resin composition, characterized in that the listening sag is 40 seconds or more.
[32]
[33]
In addition, the present invention provides a molded article comprising the thermoplastic resin composition.
Effects of the Invention
[34]
According to the present invention, even when a resin with a low molecular weight and a heat-resistant resin with a high glass transition temperature are used together, the thermoplastic resin composition has excellent blow moldability and can be molded in a wide temperature range, and thus has excellent productivity, a method for manufacturing the same, and a molded article manufactured therefrom has the effect of providing
Modes for carrying out the invention
[35]
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.
[36]
The present inventors have acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a predetermined graft rate and weight average molecular weight in ABS graft copolymer and ABS non-graft copolymer, vinyl cyanide compound having a predetermined weight average molecular weight - aromatic vinyl When the compound copolymer, the branched vinyl cyanide compound-aromatic vinyl compound copolymer having a predetermined weight average molecular weight, and the high density polyethylene resin having a predetermined density and weight average molecular weight are adjusted to a predetermined content, the blow moldability is excellent and a wide temperature range to confirm that molding is possible, and based on this, further research was made to complete the present invention.
[37]
[38]
The thermoplastic resin composition of the present invention comprises (A) 10 to 50 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; And (E) a weight average molecular weight of 300,000 to 800,000 g / mol of branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer 1 to 20% by weight; (F) density is 0.9 in 100 parts by weight of the base resin comprising to 1.5 g/cm 3 and 0.1 to 2.5 parts by weight of a high-density polyethylene resin having a weight average molecular weight of 1,000 to 6,500 g/mol. In this case, the blow moldability is excellent and the molding temperature range is extended.
[39]
[40]
Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each configuration.
[41]
[42]
(A) Vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer
[43]
The (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is, for example, 10 to 50 wt%, preferably 15 to 45 wt%, more preferably 20 to 42 wt%, based on the total weight of the base resin. % by weight, more preferably 20 to 35% by weight, even more preferably 20 to 30% by weight, there is an effect of excellent rigidity while excellent impact strength and impact strength at low temperature within this range.
[44]
[45]
The (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is, for example, 1 to 25 wt% of a vinyl cyan compound, 45 to 75 wt% of a conjugated diene rubber comprising a conjugated diene compound, and an aromatic vinyl compound It may be a graft polymerized graft copolymer including 15 to 45% by weight, and there is an effect of excellent rigidity while having excellent impact strength and impact strength at low temperature within this range.
[46]
As a preferred example, the (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is 1 to 20 wt% of a vinyl cyan compound, 50 to 70 wt% of a conjugated diene rubber comprising a conjugated diene compound, and an aromatic vinyl It may be a graft copolymer that is graft-polymerized by including 20 to 40% by weight of the compound, and has excellent rigidity while having excellent impact strength and impact strength at low temperatures within this range.
[47]
As a more preferred example, the (A) vinyl cyan compound-ball The liquid diene compound-aromatic vinyl compound graft copolymer contains 5 to 15 wt% of a vinyl cyan compound, 55 to 65 wt% of a conjugated diene rubber comprising a conjugated diene compound, and 25 to 35 wt% of an aromatic vinyl compound. It may be a polymerized graft copolymer, and within this range, the impact strength and impact strength at low temperature are excellent, and there is an effect of excellent rigidity.
[48]
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.
[49]
[50]
The (A) graft copolymer may have, for example, an average particle diameter of the conjugated diene rubber of 150 to 450 nm, preferably 200 to 400 nm, more preferably 250 to 350 nm, within this range, the impact strength, etc. There is an effect of excellent mechanical properties.
[51]
In the present description, the average particle diameter can be measured using a dynamic light scattering method, and in detail, the intensity (intensity) in Gaussian mode using a particle measuring instrument (product name: Nicomp 380, manufacturer: PSS) ) as a value. At this time, as a specific measurement example, the sample is prepared by diluting 0.1 g of Latex (TSC 35-50wt%) 1,000 to 5,000 times with deionized or distilled water, that is, diluting it appropriately so as not to significantly deviate from the Intensity Setpoint 300kHz, and putting it in a glass tube, and prepare and measure The method is auto-dilution and measured with a flow cell, the measurement mode is dynamic light scattering method/Intensity 300KHz/Intensity-weight Gaussian Analysis, and the setting value is temperature 23℃, measurement wavelength 632.8nm, channel width It can measure as 10 microseconds.
[52]
[53]
The (A) graft copolymer has, for example, a graft rate of 32 to 50%, preferably 35 to 45%, and the flow index of the thermoplastic resin composition can be properly maintained within this range, so that blow moldability This has an excellent effect.
[54]
In the present description, the graft rate can be calculated using the following Equation 1 after adding a certain amount of the graft copolymer to a solvent, dissolving it using a vibrator, centrifuging with a centrifugal separator, and drying to obtain an insoluble content .
[55]
In detail, a certain amount of the graft copolymer is added to acetone and vibrated with a vibrator (trade name: SI-600R, manufacturer: Lab. companion) for 24 hours to dissolve the free graft copolymer, and 14,000 rpm with a centrifugal separator. After centrifugation for a period of time and dried at 140° C. for 2 hours with a vacuum dryer (trade name: DRV320DB, manufacturer: ADVANTEC), the insoluble content can be obtained, and it can be calculated using Equation 1 below.
[56]
[Equation 1]
[57]
Graft rate (%)=[(Y-(X*R)) / (X*R)] * 100
[58]
Y: weight of insoluble matter
[59]
X: weight of graft copolymer added when obtaining insoluble matter
[60]
R: Fraction of conjugated diene-based polymer in graft copolymer added when obtaining insoluble content
[61]
[62]
The (A) graft copolymer may have, for example, a weight average molecular weight of 50,000 to 200,000 g/mol, preferably 60,000 to 150,000 g/mol, more preferably 70,000 to 100,000 g/mol, and within this range, mechanical It has excellent physical properties.
[63]
The weight average molecular weight of the present disclosure can be measured as a relative value with respect to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent, and specifically, a gel This is a value obtained by applying a polystyrene reduced weight average molecular weight (Mw) obtained by permeation chromatography (GPC: gel permeation chromatography, PL GPC220, Agilent Technologies). More specifically, it is measured using GPC (Gel Permeation Chromatography, Waters 2410 RI Detector, 515 HPLC pump, 717 Auto Sampler). After dissolving 20ml of THF (tetrahydrofuran) in 0.02g of each polymer, filter through a 0.45㎛ filter and put in a GPC vial (4ml) to make each sample. From 1 hour before the measurement, the solvent (THF) is injected at a rate of 1.0 mL/min, and the measurement time is 25 minutes, the injection volume is 150 μL, the flow rate is 1.0 ml/min, the isocratic pump mode, and the RI detector is used for measurement under 40 conditions. At this time, it may have been calibrated using PS (Polystyrene) standard, and the data may have been processed using ChemStation.
[64]
[65]
In the present description, the conjugated diene compound is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene, and pyrelli. It may be at least one selected from the group consisting of ren, and may preferably be 1,3-butadiene.
[66]
In the present description, the vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methnitrolonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, and preferably acrylonitrile.
[67]
In the present description, the aromatic vinyl compound is, for example, styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brobo styrene, ρ -bromostyrene, m-bromostyrene, ο-chlorostyrene, ρ-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene and vinylnaphthalene may be at least one selected from the group consisting of, Preferably, it may be styrene.
[68]
[69]
The (A) graft copolymer may be prepared by known polymerization methods including, for example, emulsion polymerization, suspension polymerization, bulk polymerization, and the like, and may preferably be emulsion polymerization.
[70]
The (A) graft copolymer emulsion graft polymerization method is, for example, 45 to 75 wt% of a conjugated diene rubber, 0.1 to 5 parts by weight of an emulsifier, 0.1 to 3 parts by weight of a molecular weight regulator, and 0.05 to 1 part by weight of a polymerization initiator. It can be carried out by continuously or collectively adding a monomer mixture containing 1 to 25 wt% of a vinyl cyanide compound and 15 to 45 wt% of an aromatic vinyl compound to the mixed solution.
[71]
Here, the weight % is based on the total weight of the conjugated diene rubber, the vinyl cyan compound and the aromatic vinyl compound as 100 weight %, and the weight part is based on the total weight of the conjugated diene rubber, the vinyl cyan compound and the aromatic vinyl compound as 100 parts by weight.
[72]
The emulsifier may be, for example, at least one selected from the group consisting of allyl aryl sulfonate, alkali methyl alkyl sulfonate, sulfonated alkyl ester, fatty acid soap and rosin acid alkali salt, and in this case, excellent stability of polymerization reaction It works.
[73]
The molecular weight modifier may be, for example, at least one selected from the group consisting of t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan and carbon tetrachloride, and is preferably t-dodecyl mercaptan.
[74]
The polymerization initiator may be, for example, at least one selected from the group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate, and in this case, emulsion polymerization can be efficiently performed.
[75]
The latex obtained by the graft emulsion polymerization is, for example, agglomerated with one or more coagulants selected from the group consisting of sulfuric acid, MgSO 4, CaCl 2 and Al 2(SO 4) 3 It can be obtained in a powder state by dehydration and drying. have.
[76]
[77]
(B) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer
[78]
The (B) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer is, for example, 10 to 55% by weight, preferably 20 to 50% by weight, more preferably 25 to 47% by weight based on the total weight of the base resin. , more preferably 25 to 40% by weight, even more preferably 25 to 35% by weight, within this range, parison sag does not occur and has excellent rigidity, so blow formability is excellent and the molding temperature range is extended has been effective.
[79]
In the present description, parison refers to a tube-type molten preform for molding a container in direct blow molding. Specifically, parison refers to a molding material (mainly a thermoplastic resin) that is preformed in the shape of a tube or pipe before inhaling air in blow molding, inserted into a blow molded die, and uniformly inflated with intake air.
[80]
Parison sag in the present substrate is a phenomenon in which the parison sags due to gravity in the extrusion process, and in this case, a problem occurs in that the thickness of the molded article is changed.
[81]
[82]
(B) copolymer of the present disclosure is a bulk copolymer comprising a conjugated diene rubber comprising a conjugated diene compound, a vinyl cyan compound, and an aromatic vinyl compound, and (A) a non-grafted copolymer compared to the graft copolymer may be referred to as
[83]
[84]
The copolymer (B) may preferably include 5 to 20% by weight of a conjugated diene rubber including a conjugated diene compound, 55 to 85% by weight of an aromatic vinyl compound, and 5 to 25% by weight of a vinyl cyan compound. , more preferably 8 to 15% by weight of a conjugated diene rubber including a conjugated diene compound, 65 to 78% by weight of an aromatic vinyl compound, and 13 to 22% by weight of a vinyl cyan compound, within this range Parison sag does not occur and there is an effect of excellent rigidity.
[85]
[86]
(B) above The conjugated diene rubber contained in the copolymer may have, for example, an average particle diameter of 1,000 to 2,000 nm, preferably 1,000 to 1,800 nm, and has excellent mechanical properties within this range.
[87]
[88]
(C) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol
[89]
The (C) graft copolymer may be, for example, 4 to 11 wt%, preferably 4.5 to 10.5 wt%, more preferably 5 to 10 wt%, based on the total weight of the base resin, within this range It does not cause sagging and has excellent rigidity, so it has excellent blow formability and has the effect of extending the molding temperature range.
[90]
[91]
The graft copolymer (C) preferably has a graft ratio of 40 to 55%, and has excellent blow moldability within this range and an effect of extending the molding temperature range.
[92]
[93]
The (C) graft copolymer may preferably have a weight average molecular weight of 160,000 to 190,000 g/mol, and have excellent blow moldability within this range and the effect of extending the molding temperature range.
[94]
[95]
The (C) graft copolymer may be, for example, an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate-based rubber having an average particle diameter of 300 to 600 nm, and in this case, impact strength, tensile strength It has excellent mechanical properties such as strength, excellent blow moldability, and the effect of extending the molding temperature range.
[96]
The (C) graft copolymer comprises, for example, 20 to 60% by weight of an acrylate-based rubber having an average particle diameter of 300 to 600 nm, 10 to 50% by weight of an aromatic vinyl compound, and 5 to 30% by weight of a vinyl cyanide compound. It may be a copolymer, and within this range, mechanical properties and heat resistance are excellent, blow moldability is excellent, and the molding temperature range is extended.
[97]
The (C) acrylate-based rubber contained in the graft copolymer may have, for example, an average particle diameter of 300 to 600 nm, preferably 300 to 500 nm, more preferably 350 to 450 nm, within this range. It has excellent mechanical properties such as impact strength and tensile strength.
[98]
The acrylate-based rubber contained in the (C) graft copolymer is, for example, 20 to 60% by weight, preferably 30 to 55% by weight, more preferably based on the total weight of the (C) graft copolymer. It may be 40 to 55% by weight, and there is an excellent effect in mechanical properties such as impact strength and tensile strength within this range.
[99]
The acrylate-based rubber may be prepared by emulsion polymerization of, for example, an acrylate-based monomer, and specific examples include emulsion polymerization by mixing an acrylate-based monomer, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte, and a solvent. , in this case, the grafting efficiency is excellent and there is an effect of excellent physical properties such as impact resistance.
[100]
In the present description, the acrylate-based monomer is defined as including both an acrylate and a compound in which one or two or more hydrogens contained therein are substituted with an alkyl group or a halogen.
[101]
The acrylate-based monomer may preferably be an alkyl acrylate-based monomer, and the alkyl acrylate-based monomer may be, for example, an acryl-based compound in which an alkyl group having 1 to 10 carbon atoms is substituted, a methacrylic compound, or a mixture thereof. Specific examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. It may be at least one selected from the group consisting of, in this case, there is an effect of improving impact resistance and weather resistance.
[102]
The emulsifier may be, for example, a fatty acid metal salt having 12 to 20 carbon atoms, a metal rosin acid salt having 12 to 20 carbon atoms, or a mixture thereof, and the fatty acid metal salt having 12 to 20 carbon atoms is, for example, sodium fatty acid, sodium laurate, oleic acid It may be one or more selected from sodium and potassium oleate, and the metal rosin acid salt having 12 to 20 carbon atoms may be, for example, sodium rosinate, potassium rosinate, or a mixture thereof.
[103]
The emulsifier may be, for example, 1 to 4 parts by weight, preferably 1.5 to 3 parts by weight, based on 100 parts by weight of the acrylate-based monomer, and within this range, the components of the acrylate-based rubber are easily mixed to form the composition of the present invention. Make the intended effect clear.
[104]
The initiator may be, for example, an inorganic peroxide, an organic peroxide, or a mixture thereof. Specifically, a water-soluble initiator such as potassium persulfate, sodium persulfate, or ammonium persulfate, or oil-soluble such as cumene hydroperoxide or benzoyl peroxide It may be an initiator, and in this case, the polymerization reaction is facilitated to reveal the desired effect of the present invention.
[105]
The initiator may be, for example, 0.05 to 1 parts by weight, preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the acrylate-based monomer, and within this range, the polymerization reaction is facilitated to reveal the desired effect of the present invention. do.
[106]
The crosslinking agent is, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neo It may be at least one selected from the group consisting of pentyl glycol dimethacrylate, trimethylolpropane trimethacrylate and trimethylolmethane triacrylate, and in this case, the elasticity of the acrylate-based rubber is further increased, impact strength, tensile strength, etc. has the effect of improving the mechanical properties of
[107]
The crosslinking agent may be, for example, 0.02 to 0.3 parts by weight based on 100 parts by weight of the acrylate-based monomer, and within this range, the elasticity of the acrylate-based rubber is further increased and the effect of improving mechanical properties such as impact strength and tensile strength is achieved. have.
[108]
The electrolyte may be, for example, at least one selected from the group consisting of sodium hydrogen carbonate (NaHCO 3), disodium disulfide (Na 2S 2O 7) and potassium carbonate (K 2CO 3).
[109]
The electrolyte may be, for example, 0.01 to 0.5 parts by weight based on 100 parts by weight of the acrylate-based monomer.
[110]
The acrylate-based rubber may further include, for example, a molecular weight control agent, and the molecular weight control agent may be, for example, t-dodecyl mercaptan, n-octyl mercaptan, or a mixture thereof. In this case, the acrylate-based rubber There is an effect of improving the impact resistance and weather resistance of the composition by controlling the weight average molecular weight of the composition.
[111]
The molecular weight modifier may be, for example, 0.01 to 1 parts by weight, preferably 0.01 to 0.3 parts by weight, based on 100 parts by weight of the acrylate-based monomer, and has an effect of improving impact resistance and weather resistance within this range.
[112]
The (C) graft copolymer may have, for example, a pH of 5 to 9, preferably 6 to 8, when in a latex state immediately after polymerization, and has excellent mechanical properties such as impact resistance and blow moldability within this range. It is excellent and has the effect of extending the molding temperature range.
[113]
In this description, unless otherwise stated, pH can be measured using a general pH measuring device at room temperature (20-25° C.), and specifically, can be measured using the Thermo Scientific Orion Star A Series.
[114]
[115]
The aromatic vinyl compound contained in the (C) graft copolymer is, for example, 10 to 50% by weight, preferably 20 to 45% by weight, more preferably 25 to 40% by weight based on the total weight of (C) the graft copolymer. It may be a weight %, and within this range, the blow moldability is excellent and the molding temperature range is extended.
[116]
The vinyl cyan compound included in the (C) graft copolymer is, for example, 5 to 30% by weight, preferably 5 to 25% by weight, more preferably 10 to 20% by weight based on the total weight of (C) the graft copolymer. It may be in weight %, and within this range, the blow moldability is excellent and the molding temperature range is extended.
[117]
[118]
(D) a vinyl cyan compound having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol-aromatic vinyl compound copolymer
[119]
The (D) copolymer may be, for example, 3.5 to 9 wt%, preferably 4 to 8.5 wt%, more preferably 4 to 8 wt%, based on the total weight of the base resin, within this range, It has excellent blow moldability because it does not cause sagging, and it has the effect of extending the molding temperature range as well as the effect of excellent surface quality.
[120]
[121]
The copolymer (D) may preferably have a weight average molecular weight of 1,200,000 to 2,300,000 g/mol, more preferably 1,500,000 to 2,000,000 g/mol, within this range, the blow moldability is excellent and the molding temperature range is extended. is excellent
[122]
[123]
The copolymer (D) is, for example, 10 to 40 wt% of a vinyl cyan compound and 60 to 90 wt% of an aromatic vinyl compound, preferably 15 to 35 wt% of a vinyl cyanide compound and 65 to 85 wt% of an aromatic vinyl compound, more preferably It may contain 20 to 30% by weight of a vinyl cyanide compound and 70 to 80% by weight of an aromatic vinyl compound, and in this case, the blow moldability is excellent and the molding temperature range is excellent.
[124]
[125]
(E) a branched vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 300,000 to 800,000 g/mol
[126]
The (E) branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer is, for example, 1 to 20% by weight based on the total weight of the base resin, preferably 1 to 17 % by weight, more preferably 2 to 15% by weight, more preferably 2 to 10% by weight, and within this range, parison sag does not occur, and rigidity and heat resistance are excellent.
[127]
[128]
The (E) branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer is an unbranched linear vinyl cyan compound-aromatic vinyl compound copolymer modified to branch, or a vinyl cyan compound and an aromatic vinyl compound copolymer It means that it was prepared using a polyfunctional initiator during copolymerization.
[129]
The (E) branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer may have, for example, a polydispersity index (PDI) of 3.5 to 6, preferably 4 to 5.5, within this range. It has excellent rigidity and heat resistance without causing sagging.
[130]
In the present description, the polydispersity index (PDI) means the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), and the smaller this value, the more uniform the molecular weight distribution.
[131]
The number average molecular weight of the present disclosure can be measured as a relative value with respect to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent, specifically, the gel This is a value obtained by applying the polystyrene reduced number average molecular weight (Mw) by permeation chromatography (GPC: gel permeation chromatography, PL GPC220, Agilent Technologies). More specifically, it is measured using GPC (Gel Permeation Chromatography, Waters 2410 RI Detector, 515 HPLC pump, 717 Auto Sampler). After dissolving 20ml of THF (tetrahydrofuran) in 0.02g of each polymer, filter through a 0.45㎛ filter and put in a GPC vial (4ml) to make each sample. From 1 hour before the measurement, the solvent (THF) is injected at a rate of 1.0 mL/min, and the measurement time is 25 minutes, the injection volume is 150 μL, the flow rate is 1.0 ml/min, the isocratic pump mode, and the RI detector is used for measurement under 40 conditions. At this time, it may have been calibrated using PS (Polystyrene) standard, and the data may have been processed using ChemStation.
[132]
[133]
The (E) branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer has an effect of improving the blow moldability due to excellent stretching properties.
[134]
The (E) branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer is, for example, 10 to 40 wt% of a vinyl cyan compound and 60 to 90 wt% of an aromatic vinyl compound, preferably 20 to 30 wt% of a vinyl cyanide compound and 70 to 80% by weight of an aromatic vinyl compound, and has excellent rigidity and heat resistance without causing parison sagging within this range.
[135]
[136]
The (E) branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer may have a weight average molecular weight of preferably 400,000 to 750,000 g/mol, more preferably 500,000 to 700,000 g/mol, within this range. has excellent mechanical properties.
[137]
[138]
(F) high density polyethylene resin
[139]
The (F) high-density polyethylene resin may be, for example, 0.1 to 2.5 parts by weight, preferably 0.5 to 2 parts by weight, more preferably 0.7 to 1.5 parts by weight, based on 100 parts by weight of the base resin, and the surface quality within this range This is excellent, and parison sag is prevented, so the blow moldability is excellent and the molding temperature range is extended.
[140]
[141]
The (F) high-density polyethylene resin has a density of 0.9 to 1.5 g/cm 3 , preferably 0.93 to 1.4 g/cm 3 , more preferably 0.95 to 1.3 g/cm 3 , as measured according to ASTM D1505, for example, More preferably, it may be 0.97 to 1.2 g/cm 3 , and moldability, workability and molding cycle are improved within this range.
[142]
[143]
The (F) high-density polyethylene resin may have, for example, a weight average molecular weight of 1,000 to 6,500 g/mol, preferably 1,500 to 5,500 g/mol, and moldability, workability and molding cycle within this range has an improving effect.
[144]
[145]
(G) Aromatic vinyl compound-maleimide compound copolymer
[146]
The (G) copolymer is, for example, (A) graft copolymer, (B) copolymer, (C) graft copolymer, (D) copolymer, (E) copolymer and (G) aromatic vinyl compound- It may be 5 to 25 wt%, preferably 10 to 20 wt%, based on the total weight of the maleimide compound copolymer, and within this range, the blow moldability is excellent and the molding temperature range is extended.
[147]
[148]
The (G) aromatic vinyl compound-maleimide compound copolymer may be, for example, a copolymer including an aromatic vinyl compound and a maleimide compound, preferably an aromatic vinyl compound, a maleimide compound, and an unsaturated dicarboxylic acid anhydride. It may be a modified aromatic vinyl compound containing a maleimide compound copolymer, and in this case, it has excellent blow moldability and has an effect of having a wide molding temperature range.
[149]
[150]
The unsaturated dicarboxylic acid anhydride may be, for example, at least one selected from the group consisting of maleic anhydride, methyl maleic anhydride, 1,2-dimethyl maleic anhydride, ethyl maleic anhydride and phenyl maleic anhydride, preferably may be maleic anhydride.
[151]
[152]
As a specific example, the aromatic vinyl compound-maleimide compound copolymer may include 30 to 60 wt% of an aromatic vinyl compound, 30 to 70 wt% of a maleimide compound, and 0 to 10 wt% of maleic anhydride, within this range While the resin composition has excellent heat resistance, mechanical strength such as impact strength and melt flow index are excellent.
[153]
[154]
As a preferred example, the aromatic vinyl compound-maleimide compound copolymer may include 40 to 55% by weight of an aromatic vinyl compound, 40 to 60% by weight of a maleimide compound, and 0 to 8% by weight of maleic anhydride, within this range. It has excellent heat resistance and excellent physical properties such as workability and impact resistance.
[155]
[156]
As a more preferred example, the aromatic vinyl compound-maleimide compound copolymer may include 43 to 51 wt% of an aromatic vinyl compound, 48 to 55 wt% of a maleimide compound, and 0.5 to 5 wt% of maleic anhydride, within this range In the final resin composition, there is an effect of excellent heat resistance, impact resistance, processability, and the like.
[157]
[158]
In the present description, the maleimide compound may be, for example, at least one selected from the group consisting of N-phenyl maleimide, N-methyl maleimide, N-ethyl maleimide, N-butyl maleimide and N-cyclohexyl maleimide, Preferably, it may be N-phenyl maleimide.
[159]
[160]
The (G) aromatic vinyl compound-maleimide compound copolymer may preferably have, for example, a glass transition temperature of 180° C. or higher, preferably 180 to 220° C., more preferably 190 to 220° C., within this range. There is an advantage in that the final resin composition has excellent heat resistance properties such as heat deformation temperature and excellent processability.
[161]
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.
[162]
[163]
The (G) aromatic vinyl compound-maleimide compound copolymer may have, for example, a weight average molecular weight of 80,000 to 200,000 g/mol, preferably 100,000 to 170,000 g/mol, more preferably 110,000 to 150,000 g/mol, , there is an advantage in that the resin composition has excellent mechanical properties such as impact strength and excellent heat resistance within this range.
[164]
[165]
As a preferred example, the (G) aromatic vinyl compound-maleimide compound copolymer may be a styrene-(N-phenylmaleimide)-maleic anhydride copolymer, and in this case, the balance of physical properties such as heat resistance and mechanical strength of the resin composition It has the advantage of excellent processability while being excellent.
[166]
[167]
(H) α-methyl styrene compound-vinyl cyan compound copolymer
[168]
The (H) copolymer is, for example, (A) graft copolymer, (B) copolymer, (C) graft copolymer, (D) copolymer, (E) copolymer and (H) α-methyl styrene. Based on the total weight of the compound-based compound-vinyl cyan compound copolymer, it may be 5 to 30% by weight, preferably 5 to 25% by weight, more preferably 10 to 22% by weight, and within this range, the blow moldability is It has the advantage of being excellent and the molding temperature range is extended.
[169]
[170]
The (H) α-methyl styrene-based compound-vinyl cyan compound copolymer is, for example, a copolymer of an α-methyl styrene-based monomer and a vinyl cyan compound; or a copolymer of an α-methylstyrene-based monomer, a vinyl cyan compound, and an aromatic vinyl compound excluding α-methylstyrene, preferably a copolymer of α-methylstyrene, acrylonitrile, and styrene .
[171]
Specifically, the (H) α-methyl styrene-based compound-vinyl cyan compound copolymer excludes 50 to 80% by weight of α-methylstyrene-based monomer, 20 to 50% by weight of the vinylcyanide compound, and α-methylstyrene It may be a copolymer comprising 0 to 10% by weight of an aromatic vinyl compound, and in this case, the impact strength is maintained, the heat resistance is excellent, and the blow moldability is excellent.
[172]
Preferably, the (H) α-methyl styrene-based compound-vinyl cyan compound copolymer comprises 70 to 80% by weight of α-methylstyrene, 20 to 30% by weight of acrylonitrile, and 0 to 8% by weight of styrene. It may be a copolymer, and in this case, the impact strength is maintained, the heat resistance is excellent, and the blow moldability is excellent.
[173]
In the present description, “0 to 10% by weight of styrene” may preferably mean 0% by weight or more than 0% to 10% by weight of styrene.
[174]
[175]
The α-methyl styrene-based monomer may be, for example, at least one selected from the group consisting of α-methyl styrene and derivatives thereof, and in this case, excellent heat resistance is obtained. Preferably, the derivative of α-methyl styrene may be a compound in which one or two or more of its hydrogens are substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms or a halogen group, and more preferably an aromatic ring thereof It may be a compound in which one or two or more of the hydrogens are substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogen group, or the like.
[176]
[177]
The (H) α-methyl styrene compound-vinyl cyan compound copolymer may have, for example, a weight average molecular weight of 60,000 to 180,000 g/mol, preferably 80,000 to 120,000 g/mol, and impact strength within this range. While maintaining the heat resistance, it has an excellent effect.
[178]
[179]
Thermoplastic resin composition
[180]
The thermoplastic resin composition may have a flow index ratio (240° C. flow index / 220° C. flow index) measured at 240° C. to the flow index measured at 220° C. according to ISO 1133, for example, 4.5 or less, preferably 4 or less And within this range, the physical property balance is excellent, the blow moldability is excellent, and the molding temperature range is widened.
[181]
[182]
The thermoplastic resin composition is, for example, a plate measuring the time it takes to stretch 1% or more of the total length by discharging a parison of 500 mm in length, 0.5 mm in thickness, and 500 g in weight at a barrel temperature of 220° C. of a blow molding machine. The listen sag may be 40 seconds or more, preferably 50 seconds or more, more preferably 60 seconds or more, still more preferably 60 to 120 seconds, even more preferably 60 to 100 seconds, and within this range, blow moldability This has an excellent effect.
[183]
Parison sag in this substrate is measured by shooting an image with a camera while discharging a parison of 500 mm in length, 0.5 mm in thickness, and 500 g in weight at a barrel temperature of 220° C. time can be measured.
[184]
[185]
The thermoplastic resin composition is, for example, a plate measuring the time it takes to stretch 1% or more of the total length by discharging a parison of 500 mm in length, 0.5 mm in thickness, and 500 g in weight at a barrel temperature of 240° C. of a blow molding machine. The listen sag may be 40 seconds or more, preferably 50 seconds or more, more preferably 60 seconds or more, still more preferably 60 to 120 seconds, even more preferably 60 to 100 seconds, and within this range, blow moldability This has an excellent effect.
[186]
[187]
For the thermoplastic resin composition, for example, melt-fracture may not occur by visually observing whether or not melt-fracture occurs on the surface of an injection-molded specimen (size 40 * 80 mm). and, in this case, the surface quality is excellent.
[188]
[189]
The thermoplastic resin composition has, for example, a thermal deformation temperature of 89° C. or higher, preferably 90 to 100° C., measured with a specimen thickness of 4 mm under a load of 1.8 MPa in accordance with ISO 075, and has an excellent effect of property balance within this range. .
[190]
[191]
The thermoplastic resin composition has, for example, a Charpy impact strength of 17 kJ/m 2 or more, preferably 17 to 27 kJ/m 2 , measured at 23° C. in accordance with ISO 179, and has an excellent effect of property balance within this range. have.
[192]
[193]
The thermoplastic resin composition has, for example, a flow index of 0.6 g/10min or more, preferably 0.6 to 1.5 g/10min, measured under 220°C and 10 kg/cm 3 according to ISO 1133, and a balance of physical properties within this range and It has an excellent moldability effect.
[194]
[195]
The thermoplastic resin composition has, for example, a tensile strength of 37 MPa or more, preferably 37 to 47 MPa, more preferably 37 to 43 MPa, measured with a specimen thickness of 2 mm under a condition of 200 mm/min according to ISO 527, and Within the range, there is an excellent effect of the physical property balance.
[196]
[197]
The thermoplastic resin composition may include, for example, at least one selected from the group consisting of antioxidants, lubricants, and molding aids, and in this case, necessary physical properties are well realized without reducing the original properties of the thermoplastic resin composition of the present invention has the effect of being
[198]
[199]
The antioxidant may be, for example, a hindered phenol-based antioxidant, a phosphite-based antioxidant, or a mixture thereof, and in this case, light resistance and weather resistance are improved.
[200]
The hindered phenolic antioxidant is, for example, 4,4'-methylene-bis(2,6-di-t-butylphenol), octadecyl-3-(3,5-di-t-butyl-4-hydro Roxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and 3,9-bis[2-[3-(3) -tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] one selected from the group consisting of undecane or more, preferably pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].
[201]
The hindered phenolic antioxidant is, for example, 0.1 to 2 parts by weight, preferably 0.3 to 1.5 parts by weight, more preferably 0.3 to 1 parts by weight, based on 100 parts by weight of the thermoplastic resin composition comprising (A) to (H). It may be included in parts by weight, and there is an effect of contributing to the improvement of heat aging resistance within this range.
[202]
The phosphite-based antioxidant is, for example, tris-(2,4-di-t-butylphenyl)phosphite, bis-(2,4-di-t-butylphenyl)pentaerythritol-diphosphite, bis-( 2,6-di-t-butyl-4-methylphenyl)pentaerythritol-diphosphite, distearyl-pentaerythritol-diphosphite and [bis(2,4-di-t-butyl-5-methylphenoxy) )phosphino]biphenyl, N,N-bis[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]di It may be at least one selected from the group consisting of oxyphosphepin-6-yl]oxy]-ethyl]ethanamine, preferably bis-(2,6-di-t-butyl-4-methylphenyl)pentaerythritol- It may be a diphosphite.
[203]
The phosphite-based antioxidant is, for example, 0.1 to 2 parts by weight, preferably 0.3 to 1.5 parts by weight, more preferably 0.3 to 1 parts by weight, based on 100 parts by weight of the thermoplastic resin composition comprising (A) to (H). It can be included as a part, and has an effect of contributing to the improvement of heat aging resistance within this range.
[204]
[205]
The lubricant may be, for example, at least one selected from the group consisting of an ester lubricant, a metal salt lubricant, a carboxylic acid lubricant, a hydrocarbon lubricant, and an amide lubricant, preferably a metal salt lubricant, an amide lubricant, or a mixture thereof. In this case, there is an advantage in that the original effect of the lubricant is well expressed without degrading the mechanical properties and thermal stability of the resin.
[206]
The amide lubricant is more preferably a steramide lubricant, even more preferably an alkylene bis (steramide) having 1 to 10 carbon atoms in the alkylene, and most preferably an ethylene bis stearamide. In this case, there is an advantage in that the original effect of the lubricant is well expressed without degrading the mechanical properties and thermal stability of the resin.
[207]
The amide-based lubricant may be, for example, 0.05 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, more preferably 0.2 to 1 parts by weight based on 100 parts by weight of the thermoplastic resin composition comprising (A) to (H). There is an advantage in that the original effect of the lubricant is well expressed without degrading the mechanical properties and thermal stability of the resin within this range.
[208]
[209]
The metal salt-based lubricant is more preferably a stearic acid-based metal salt-based lubricant, and even more preferably at least one selected from the group consisting of calcium stearate, magnesium stearate, aluminum stearate, potassium stearate and barium stearate. and most preferably calcium stearate. In this case, there is an advantage in that the original effect of the lubricant is well expressed without degrading the mechanical properties and thermal stability of the resin.
[210]
The metal salt-based lubricant may be, for example, 0.05 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, more preferably 0.2 to 1 parts by weight, based on 100 parts by weight of the thermoplastic resin composition composed of (A) to (H). , there is an advantage in that the original effect of the lubricant is well expressed without degrading the mechanical properties and thermal stability of the resin within this range.
[211]
[212]
The molding aid may be, for example, at least one selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, hexafluoroethylene/tetrafluoroethylene copolymer, and tetrafluoroethylene/ethylene copolymer, preferably It may be polytetrafluoroethylene, and in this case, there is an effect that the moldability is further improved.
[213]
The molding aid is, for example, to 100 parts by weight of the thermoplastic resin composition composed of (A) to (H) It may be 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, and there is an effect that the moldability is more improved within this range.
[214]
[215]
The thermoplastic resin composition optionally includes at least one selected from the group consisting of a flame retardant, a hydrolysis stabilizer, a dye, a pigment, a colorant, an antistatic agent, a crosslinking agent, an antibacterial agent, a processing aid, and a carbon black masterbatch (A) to ( H), each of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, even more preferably 0.5 to 1 parts by weight based on 100 parts by weight of the thermoplastic resin composition composed of H). and within this range, there is an effect that the necessary physical properties are well implemented without reducing the original physical properties of the thermoplastic resin composition of the present invention.
[216]
[217]
Method for producing a thermoplastic resin composition
[218]
The method for preparing the thermoplastic resin composition of the present invention includes (A) 10 to 50 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; And (E) a weight average molecular weight of 300,000 to 800,000 g / mol of branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer 1 to 20% by weight; (F) density is 0.9 in 100 parts by weight of the base resin comprising to 1.5 g/cm 3 and containing 0.1 to 2.5 parts by weight of a high-density polyethylene resin having a weight average molecular weight of 1,000 to 6,500 g/mol, and kneading and extruding under the conditions of 200 to 300 ° C and 200 to 300 rpm to prepare pellets characterized in that In this case, the blow moldability is excellent and the molding temperature range is extended.
[219]
[220]
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.
[221]
[222]
The kneading and extrusion is, for example, a barrel temperature of 200 to 300 ° C., preferably 210 to 290 ° C., more preferably 210 to 280 ° C., more preferably 220 to 250 ° C. , in this case, sufficient melt-kneading may be possible while adequate throughput per unit time, and there is an effect that does not cause problems such as thermal decomposition of the resin component.
[223]
The kneading and extrusion may be performed under the condition that, for example, the screw rotation speed is 200 to 300 rpm, preferably 220 to 280 rpm, more preferably 230 to 270 rpm, and in this case, the throughput per unit time is appropriate and the process efficiency is high While excellent, it has an effect of suppressing excessive cutting.
[224]
[225]
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.
[226]
[227]
molded product
[228]
The molded article of the present substrate may include the thermoplastic resin composition of the present substrate, and in this case, there is an advantage that both heat aging resistance are excellent.
[229]
The molded article may be, for example, a molded article for automobiles, specifically, a spoiler for a vehicle, a trunk garnish, or a bumper guard. .
[230]
[231]
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.
[232]
[233]
[Example]
[234]
* (A) ABS graft copolymer: DP280 of LG Chem
[235]
* (B) ABS copolymer: Block-polymerized ABS copolymer, LG Chem’s ER400
[236]
* (C-1) ASA graft copolymer: SA927 from LG Chem (graft rate 40 to 55%, weight average molecular weight 150,000 to 200,000 g/mol)
[237]
* (C-2) ASA graft copolymer: SA130 from LG Chem (graft rate 35 to 44%, weight average molecular weight 80,000 to 100,000 g/mol)
[238]
* (C-3) ASA graft copolymer: SA928 of LG Chem (graft rate 20 to 39%, weight average molecular weight 130,000 to 160,000 g/mol)
[239]
* (C-4) ASA graft copolymer: SA100 of LG Chem (graft rate 15 to 30%, weight average molecular weight 100,000 to 120,000 g/mol)
[240]
* (D) High molecular weight SAN: ZB869 from ZIBO HUAXING (weight average molecular weight of 1,500,000 to 2,000,000 g/mol, acrylonitrile 25% by weight and styrene 75% by weight)
[241]
* (E) Branched SAN: Fine-blend's EMI-230B (polydispersity index 4.2, acrylonitrile 25% by weight and styrene 75% by weight)
[242]
* (F) High-density polyethylene resin (HDPE): Mitsui's HI-WAX 400P (density 0.98 g/cm 3, weight average molecular weight 1,500 to 5,500 g/mol)
[243]
* (G) Aromatic vinyl compound-maleimide compound copolymer (PMI-PS): Denka's MSBB (PMI 52 wt%, styrene 46 wt%, MAH 2 wt%; weight average molecular weight 120,000 g/mol)
[244]
* (H) α-methyl styrene-based compound-vinyl cyan compound copolymer (AMSAN): 99UH of LG Chem (acrylonitrile 28 wt%, α-methyl styrene 72 wt%; weight average molecular weight 100,000 g/mol)
[245]
* Hindered phenolic antioxidant: IR1010 from BASF
[246]
* Phosphite-based antioxidant: PEP-36 from ADEKA
[247]
* Lubricant: EBA (Japan Oil Company)
[248]
* Molding aid: POCERA's XFlon-G
[249]
[250]
Examples 1 to 6 and Comparative Examples 1 to 11
[251]
Pellets were prepared by kneading and extruding the components and contents shown in Tables 1 to 3, respectively, in an extruder (SM Twin screw extruder, 25Φ) at an extrusion temperature of 230°C, a feed rate of 90 kg/hr, and a screw speed of 250 rpm. The flow index was measured with the prepared pellets. In addition, injection specimens were prepared using the pellets produced under the conditions of injection temperature of 250°C, mold temperature of 60°C, and injection speed of 30 mm/min using an injection machine (ENGEL 120MT).
[252]
[253]
[Test Example]
[254]
The properties of the pellets and injection specimens prepared in Examples 1 to 6 and Comparative Examples 1 to 11 were measured by the following method, and the results are shown in Tables 1 to 3 below.
[255]
[256]
* Flow index (MI): measured in accordance with ISO 1133 under 220 ℃, 10 kg/cm 3 . Here, the unit of melt index is g/10min.
[257]
* Flow index ratio: According to ISO 1133, the flow index ratio measured at 240 ° C to the flow index measured at 220 ° C was calculated and evaluated according to the following criteria.
[258]
Phase: Flow ratio of 4 or less
[259]
Medium: Flow index ratio greater than 4 and less than 4.5
[260]
Bottom: Flow index ratio exceeds 4.5
[261]
* Parison sag: Measure the time it takes to stretch more than 1% of the total length by discharging a parison with a length of 500 mm, a thickness of 0.5 mm, and a weight of 500 g at each of the barrel temperatures of 220°C and 240°C of the blow molding machine. Thus, it was evaluated based on the following criteria.
[262]
Phase: 60 seconds or more
[263]
Medium: 40 seconds or more to less than 60 seconds
[264]
Lower: less than 40 seconds
[265]
* Surface characteristics: The presence or absence of melt-fracture on the surface of the specimen (size 40 × 80 mm) was observed and evaluated according to the following criteria.
[266]
Phase: 0 occurrences
[267]
Bottom: 1 or more occurrences
[268]
* Charpy impact strength (kJ/m 2): It was measured at 23 ℃ according to ISO 179.
[269]
* Tensile strength (MPa): In accordance with ISO 527, the tensile strength was measured with a specimen thickness of 2 mm under the condition of 200 mm/min.
[270]
* Thermal deformation temperature (℃): The thermal deformation temperature was measured with a specimen thickness of 4 mm under a load of 1.8 MPa in accordance with ISO 075.
[271]
[272]
[Table 1]
Classification Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
(A) ABS graft copolymer 22 22 22 22 22 22 22
(B) ABS copolymer 28 28 28 28 28 28
(C-1) ASA graft copolymer 5 8 10 8 8 10
(C-2) ASA graft copolymer
(C-3) ASA graft copolymer
(C-4) ASA graft copolymer
(D) high molecular weight SAN 7 7 7 4 8 7
(E) Branched SAN 5 5 5 5 5 5
(G) PMI-PS 15 15 15 15 15 15
(H) AMSAN 18 15 13 18 14 13
(F) HDPE (parts by weight) 1 1 1 1 1 1.5
IR1010 (parts by weight) 0.3 0.3 0.3 0.3 0.3 0.3 0.3
PEP-36 (parts by weight) 0.3 0.3 0.3 0.3 0.3 0.3 0.3
EBA (parts by weight) 0.2 0.2 0.2 0.2 0.2 0.2
LPCA (parts by weight) 0.5 0.5 0.5 0.5 0.5 0.5
XFlon-G (parts by weight) 0.15 0.15 0.15 0.1 5 0.15 0.15
Properties
Charpy impact strength 19 20 21 20 20 21
Flow Index (MI) 0.9 0.7 0.6 1.5 0.6 0.7
Tensile strength 40 39 38 39 39 39
Heat deflection temperature 92 92 91 93 92 92
Flow Index Ratio Middle High High Medium High
Parison deflection (220℃)
Parison deflection (240℃) Upper Middle Upper Middle Upper Upper
On the surface properties
[273]
[Table 2]
Category Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5
(A) ABS graft copolymer 22 22 22 22 22
(B) ABS copolymer 28 28 28 28 28
(C-1) ASA graft copolymer 3 12
(C-2) ASA graft copolymer 8
(C-3) ASA graft copolymer 8
(C-4) ASA graft copolymer 8
(D) high molecular weight SAN 7 7 7 7 7
(E) Branched SAN 5 5 5 5 5
(G) PMI-PS 15 15 15 15 15
(H) AMSAN 20 11 15 15 15
(F) HDPE (parts by weight) 1 1 1 1 1
IR1010 (parts by weight) 0.3 0.3 0.3 0.3 0.3 0.3
PEP-36 (parts by weight) 0.3 0.3 0.3 0.3 0.3 0.3
EBA (parts by weight) 0.2 0.2 0.2 0.2 0.2
LPCA (parts by weight) 0.5 0.5 0.5 0.5 0.5
XFlon-G (parts by weight) 0.15 0.15 0.15 0.15 0.15
Properties
Charpy Impact Strength 18 22 17 19 23
Flow Index (MI) 1.1 0.6 0.9 1.2 1.2
Tensile strength 41 37 42 40 38
Heat deflection temperature 93 90 93 93 90
Flow Index Ratio Low High Medium Low
Parison Sag (220) Upper Upper Middle Upper Middle
Parison deflection (240℃)
Surface Characteristics Upper Lower Upper Upper Upper
[274]
[Table 3]
Category Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11
(A) ABS graft copolymer 22 22 22 22 22 22 22
(B) ABS non-grafted copolymer 28 28 28 28 28 20
(C-1) ASA graft copolymer 8 8 8 8 8 8
(C-2) ASA graft copolymer
(C-3) ASA graft copolymer
(C-4) ASA graft copolymer
(D) high molecular weight SAN 3 10 7 7 7 4
(E) Branched SAN 5 5 5 5 0.5 25
(G) PMI-PS 15 15 15 15 15 10
(H) AMSAN 19 12 15 15 19.5 10
(F) HDPE (parts by weight) 1 1 0.05 3 1 1
IR1010 (parts by weight) 0.3 0.3 0.3 0.3 0.3 0.3 0.3
PEP-36 (parts by weight) 0.3 0.3 0.3 0.3 0.3 0.3 0.3
EBA (parts by weight) 0.2 0.2 0.2 0.2 0.2 0.2
LPCA (parts by weight) 0.5 0.5 0.5 0.5 0.5 0.5
XFlon-G (parts by weight) 0.15 0.15 0.15 0.15 0.15 0.15
Properties
Charpy impact strength 20 20 20 20 20 18
Flow Index (MI) 1.8 0.4 0.7 0.7 0.7 1.5
Tensile strength 40 41 39 39 39 41
Heat deflection temperature 92 92 92 92 93 89
Flow Index Ratio Middle High High Medium High Medium
Parison deflection (220℃) Middle Upper Upper Middle Lower Upper
Parison deflection (240℃) medium high medium load
Surface Characteristics
[275]
(In Tables 1 to 3, each content of (A), (B), (C), (D), (E), (G) and (H) is a weight percent based on their total weight, ( The content of F) is parts by weight based on 100 parts by weight of the total weight of (A), (B), (C), (D), (E), (G) and (H).)
[276]
As shown in Tables 1 to 3, the thermoplastic resin compositions (Examples 1 to 6) according to the present invention have excellent mechanical properties such as impact strength and tensile strength, compared to Comparative Examples 1 to 11, while having excellent flow rate ratio and parison It was confirmed that the effect was excellent in blow moldability due to excellent deflection and not only the effect of widening the molding temperature range but also excellent surface properties.
[277]
Specifically, (C) in the case of Comparative Examples 1 and 2, in which the content of the ASA graft copolymer was outside the scope of the present invention, Comparative Example 1 included in a small amount had a lower flow index ratio and Parison sag (240° C.) , Comparative Example 2 included in excess had poor surface properties.
[278]
In addition, (C) Comparative Examples 3 to 5, in which the graft rate and weight average molecular weight of the ASA graft copolymer were outside the range of the present invention, had poor flow index ratio, parison sag at 220°C, and particularly parison sag at 240°C. .
[279]
In addition, (D) Comparative Example 6, in which the content of high molecular weight SAN is less than the range of the present invention, the flow index ratio and Parison sag (220 ℃, 240 ℃) was lowered, (D) the content of the high molecular weight SAN of the present invention Comparative Example 7 exceeding the range had poor surface properties.
[280]
In addition, (F) Comparative Example 8 including HDPE below the range of the present invention had poor surface properties, and (F) Comparative Example 9 including HDPE exceeding the range of the present invention had lower flow index ratio and Parison deflection. .
[281]
In addition, (E) Comparative Example 10 containing the branched SAN resin below the scope of the present invention had poor parison sag (220 ℃, 240 ℃), (E) the branched SAN resin exceeding the scope of the present invention. Comparative Example 11 had poor surface properties.
[282]
[283]
In conclusion, an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol in the ABS graft copolymer and the ABS copolymer according to the present invention, A vinyl cyan compound having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol-aromatic vinyl compound copolymer, a branched vinyl cyan compound having a weight average molecular weight of 300,000 to 800,000 g/mol-aromatic vinyl compound copolymer, and a density of 0.9 to It was confirmed that the thermoplastic resin composition prepared by adjusting a high-density polyethylene resin having a weight average molecular weight of 1,000 to 6,500 g/mol with a predetermined content of 1.5 g/cm 3 has excellent blow moldability and can be molded in a wide temperature range.
Claims
[Claim 1]
(A) 10 to 50% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9% by weight of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; And (E) a weight average molecular weight of 300,000 to 800,000 g / mol of branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer 1 to 20% by weight; (F) density is 0.9 in 100 parts by weight of the base resin comprising A thermoplastic resin composition comprising 0.1 to 2.5 parts by weight of a high density polyethylene resin having a weight average molecular weight of 1,000 to 6,500 g/mol and a weight average molecular weight of 1,000 to 6,500 g/mol.
[Claim 2]
The method according to claim 1, wherein the (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer comprises 1 to 25 wt% of a vinyl cyan compound and 45 to 75 wt% of a conjugated diene rubber comprising a conjugated diene compound and 15 to 45% by weight of an aromatic vinyl compound, wherein the thermoplastic resin composition is a graft copolymer obtained by graft polymerization.
[Claim 3]
The method according to claim 1, wherein the (B) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer comprises 5 to 20 wt% of a conjugated diene rubber including a conjugated diene compound, 55 to 85 wt% of an aromatic vinyl compound, and vinyl A thermoplastic resin composition comprising 5 to 25 wt% of a cyanide compound.
[Claim 4]
According to claim 1, wherein the (C) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer has an average particle diameter of 300 to 600 nm acrylate-based rubber 20 to 60 wt%, 10 to 50 wt% of the aromatic vinyl compound % and 5 to 30% by weight of a vinyl cyan compound.
[Claim 5]
The thermoplastic resin composition according to claim 1, wherein the (D) vinyl cyan compound-aromatic vinyl compound copolymer comprises 10 to 40 wt % of the vinyl cyan compound and 60 to 90 wt % of the aromatic vinyl compound.
[Claim 6]
According to claim 1, wherein the (E) a weight average molecular weight of 300,000 to 800,000 g / mol branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer has a polydispersity index (Polydispersity index, PDI) of 3.5 to 6 Thermoplastic resin composition characterized in that.
[Claim 7]
According to claim 1, wherein the base resin is (A), (B), (C), (D), (E) and (G) based on the total weight of the aromatic vinyl compound-maleimide compound copolymer (G) ) A thermoplastic resin composition comprising 5 to 25% by weight of the copolymer.
[Claim 8]
According to claim 1, wherein the base resin is (A), (B), (C), (D), (E) and (H) α-methyl styrenic compound-vinyl cyanide compound in the total weight of the copolymer (H) A thermoplastic resin composition comprising 5 to 30% by weight of the copolymer.
[Claim 9]
The method according to claim 1, wherein the thermoplastic resin composition has a flow index ratio (240° C. flow index / 220° C. flow index) measured at 240° C. to the flow index measured at 220° C. according to ISO 1133 is 4.5 or less. A thermoplastic resin composition.
[Claim 10]
The method according to claim 1, wherein the thermoplastic resin composition has a length of 500 mm, a thickness of 0.5 mm, and a barrel temperature of 220°C of a blow molding machine.A thermoplastic resin composition, characterized in that the parison sag measured by discharging a parison weighing 500 g to extend 1% or more of the total length is 40 seconds or more.
[Claim 11]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises at least one selected from the group consisting of antioxidants, lubricants, and molding aids.
[Claim 12]
(A) 10 to 50% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; (B) 10 to 55 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (C) 4 to 11 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a graft ratio of 40 to 60% and a weight average molecular weight of 150,000 to 200,000 g/mol; (D) 3.5 to 9% by weight of a vinyl cyanide compound-aromatic vinyl compound copolymer having a weight average molecular weight of 1,000,000 to 2,500,000 g/mol; And (E) a weight average molecular weight of 300,000 to 800,000 g / mol of branched (branched) vinyl cyan compound-aromatic vinyl compound copolymer 1 to 20% by weight; (F) density is 0.9 in 100 parts by weight of the base resin comprising to 1.5 g/cm 3 and containing 0.1 to 2.5 parts by weight of a high-density polyethylene resin having a weight average molecular weight of 1,000 to 6,500 g/mol, and kneading and extruding under the conditions of 200 to 300 ° C and 200 to 300 rpm to prepare pellets Method for producing a thermoplastic resin composition, characterized in that.
[Claim 13]
A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 11.