The title of the invention: Heat stabilizer-free thermoplastic resin composition and a method of manufacturing the same
Art
[1]
The present invention relates to a heat stabilizing agent-free (thermalstabilizer free) thermoplastic resin composition and a method of manufacturing the same.
BACKGROUND
[2]
In general, ABS copolymer resin or a method as a way to improve the thermal stability and surface gloss of a similar resin is to increase the added amount of the heat stabilizer, apply the stripping step in the ABS copolymer latex to remove residual monomer, residual emulsifier and the like method to inject additional water when agglomeration / dehydrated being applied in order to minimize the content.
[3]
In addition, a method of increasing a method for increasing the content of acrylonitrile in the rubber component and the ABS copolymer is typically prepared during acrylic applied in order to improve the impact resistance and the falling ball impact strength. At this time there is a disadvantage that the coloring property is lowered in impact resistance and degree of whiteness are improved but the resin molecular weight and decreases geurapeuteuyul case of increasing the content of the rubber component. Furthermore impact resistance and coloring property within the case to increase the content of acrylonitrile in the acrylic resin has the disadvantage that a superior degree of whiteness is decreased.
[4]
Also, in general, ABS (acrylonitrile-butadiene-styrene), MBS (methacrylate-butadiene-styrene), ASA rubber-reinforced resins such as (acrylonitrile-styrene-acrylate) is typically a rubber by the emulsion polymerization making a reinforced resin, after manufacture it as agglomeration / drying to powder, this styrene-acrylonitrile (hereinafter, SAN, also known as quot;) and polycarbonate (PC) were charged into an extruder with a resin such as a primary processed in a pellet form after the step of manufacturing is presented. At this time it is common to put a rubber-reinforced resin of less than 1% water content in the extruder. The water content after dehydration, without a drying step in accordance with to Fig undergo a continuous process as a first processing step of SAN and kneading the PC in a powder containing 30% of the extruder case, where high water content is a physical property variation and productivity It will cause a problem of lowering.
[5]
Accordingly, it is to maintain the productivity and quality, to minimize the water content of the powder when added to water, including without the drying step in the extruder is an important factor. Got a conventional centrifugal dehydrator to reducing the water content has the same limitations.
[6]
These problems are overcome by using a pressure type dehydrator is possible, but since the same pressure type dehydration process, the processing step subjected to a high temperature, high pressure, a problem that may lead to deformation of the resin thermal stability and should also be considered.
Detailed Description of the Invention
SUMMARY
[7]
An object of the present invention is heat stabilizer-free thermoplastic resin composition and relates to a manufacturing method, the object of the specific invention is to improve the thermal stability and surface gloss without using the heat stabilizer, at the same time the impact resistance and the falling ball impact strength is excellent thermoplastic haryeoneunde may provide a resin composition.
[8]
It is another object of the present invention haryeoneunde provide a manufacturing method that can maintain high productivity without going through the drying process during manufacturing the thermoplastic resin composition.
Technical Solution
[9]
In order to achieve the above object,
[10]
Thermal stabilizer-free thermoplastic resin composition of the present invention a) comprises a rubber-reinforced resin and b) a matrix resin,
[11]
Wherein a) the rubber-reinforced resin is characterized in that the large-diameter rubber polymer latex, aromatic vinyl compound, vinyl cyanide compound and a reactive emulsifier (reactive surfactant) an ABS-based thermoplastic which contains as an active ingredient and obtained by the graft copolymer resin.
[12]
[13]
In addition, the present invention as described above to prepare a) the rubber-reinforced heat stabilizer, a water content of the ABS type thermoplastic resin of 45 to 70% as the resin-free graft copolymer latex;
[14]
Wherein the heat stabilizer to prevent oxidation pre-graft treatment, flocculation and dewatering with a water content of the copolymer latex to give a graft copolymer latex of 20 to 40%; And
[15]
It provides a method of producing a thermoplastic resin composition that is characterized by; the graft copolymer latex was adjusted to 2 to 20% in the next step the water content of the matrix resin and kneading the lubricant.
[16]
[17]
A detailed explanation follows below with respect to the present invention.
[18]
In the present invention, in which the technical features, and the impact resistance, falling ball impact, gloss is superior without using a heat stabilizer as the thermoplastic resin composition, particularly when applied to increase the production efficiency in the compression dehydrator not going through the manufacturing process during drying.
[19]
[20]
First, the heat stabilizer-free thermoplastic resin composition of the present invention a) comprises a rubber-reinforced resin and b) a matrix resin.
[21]
Pre-term stabilizers (thermalstabilizer free) thermoplastic resin composition used in the present invention, except where noted, it refers to a thermoplastic resin composition consisting of those without a thermal stabilizer.
[22]
[23]
Wherein a) the rubber-reinforced resin is available for the rubber-like polymer latex, aromatic vinyl compound, vinyl cyanide compound and a reaction containing the emulsifying agent as an active ingredient and an ABS-based thermoplastic resin obtained by the graft copolymerization.
[24]
[25]
More specifically, it may be a large-diameter rubber latex to give non particles using a small diameter, for preparing a rubber latex is Sure that the rubber polymer is limited to the following acid.
[26]
The small-diameter rubber latex 100 parts by weight of 1,3-butadiene, 1 to 4 parts by weight of an emulsifier, polymerization initiator, 0.1 to 0.6 parts by weight, 0.1 to 1 part by weight of an electrolyte, a molecular weight modifier and 0.1 to 0.5 parts by weight Ion-exchanged water 90 to 130 parts by weight, prepared by batch 7 was administered to reaction at 50 to 65 ℃ for 12 hours and then by adding 0.05 to 1.2 parts by weight of a molecular weight regulator in the reaction batch administered from 55 to 70 ℃ for 5 to 15 hours.
[27]
The thus obtained small-diameter rubber latex is in a gel content of an average particle size of 600 to 1500 Å is satisfied a range from 85 to 99% by weight. The gel content range is effectively formed a grafted copolymer rubber particles to the outside corresponds to the range that can give the excellent impact strength and thermal stability.
[28]
[29]
The small-diameter rubber latex 100 parts by weight of the non acid as added slowly while acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid or the polymer of 0.1 to 5 hours in a coagulant from 1 to 4 parts by weight of the content, or 0.5 to 2 hours, one more time in another example for to become non particles.
[30]
[31]
Obtained large-diameter rubber polymer latex particle size by the particle is non Specifically specifically is within the range 2500 to 3800 Å than the range 2500 to 5000 Å,, the gel content is to satisfy the range of 85 to 99% by weight. The particle size may be average particle size or number-average particle 10000000000000000 days.
[32]
Such large-diameter rubber-like polymer latex is contained in 60 to 75 parts by weight of the rubber-reinforced resin monomer based on 100 parts by weight of the total rubber provides a reinforced resin. By thus maximizing the content of the rubber it can be given the effect of minimizing the amount of the coarse resin to be added to the extruder the pressure type dehydration process.
[33]
[34]
The aromatic vinyl compound used in the present invention, but are not limited to, styrene, α- methyl styrene, p- methyl styrene, vinyl toluene, t- butylstyrene, chlorostyrene, or alone or in a mixture of these substituents, such as Due to the rubber-reinforced resin monomer based on 100 parts by weight of the total specifically, it may be within the 18 to 28 parts by weight, more specifically from 21 to 25 parts by weight.
[35]
In particular, for the polymerization stability and the optimization of the mechanical properties via the appropriate cell formation, ensure the thermal stability, to, as identified in the Examples, it is more preferable to split each input to an elevated temperature before and after the polymerization temperature.
[36]
[37]
With a vinyl cyanide compound to be used in the present invention is a rubber-reinforced resin monomer of 100 parts by weight alone or mixed with a nitrile, a nitrile or a substituent such as methacrylonitrile specifically from 5 to 15 parts by weight , more specifically from 9 to 10 parts by weight it may be used.
[38]
In particular, for optimization, the thermal stability of the mechanical properties obtained through the polymerization stability and proper cell formation, as identified in the following examples, it is more preferable that the polymerization temperature input to each partition before and after temperature rise.
[39]
[40]
The reaction used in the present invention emulsifying agent may act to enhance the thermal stability and surface gloss without further addition of the rubber-reinforced resin in minimizing residual emulsifier content thermal stabilizer being included in the rubber-reinforced resin, in the future, not yippun compatibility with the matrix resin to be blended may also serve to enhance the impact resistance and provides a falling ball impact strength is excellent ABS-based thermoplastic resin.
[41]
[42]
In order to perform this role, carbonate, sulfonate, and sulfate groups at least one member to be preferred to use an emulsifying agent containing the selected functional group from O, etc., without limitation, for example, sulfoethyl methacrylate rate (sulfoethyl methacrylate), 2-acrylamido-2 - methylpropane sulfonic acid (2-acrylamido-2-methylpropane sulfonic acid), sodium styrene sulfonate (sodium styrene sulfonate), sodium dodecyl allyl sulfosuccinate (sodium dodectyl allyl sulfosuccinate), styrene and allyl alcohol when sodium dodecyl posuk carbonate copolymers, polyoxyethylene alkylphenyl ether ammonium sulfate acids (polyoxyethylene alkylphenyl ether ammonium sulfate), C16-18 alkenyl succinic acid di-potassium salt (C16-18 alkenyl succinic acid, di-potassium salt) and sodium methallyl sulfonate can be used (at least one selected from sodium methallyl sulfonate).
[43]
Are included into said reactive emulsifiers are the rubber-reinforced resin monomer 100 parts by weight of the total 0.001 to standard two parts by weight, it is not easy to secure polymerization stability in less than 0.001 content, 2 parts by excess content of the residual emulsifier content this is because the high thermal stability resin worse.
[44]
For reference, in the present invention suitable residual emulsifier content ranges include, but are not limited to, 19,000 ppm or less (equivalent to an emulsifier usage basis, no more than about 65% by weight as emulsifier a total of 100% by weight based on committed as an example), or 1 to 19,000 ppm, preferably in another example, 17,500 ppm or less (equivalent to the reference amount emulsifier, emulsifier to total 100% by weight based on committed as an example about 55% or less by weight), or 1 to 17,500 ppm.
[45]
[46]
Further, in the present invention (a) the rubber-reinforced resin may contain a mercapto tanryu as a molecular weight-controlling agent, specifically a n- octyl mercaptan, n- dodecyl mercaptan, and t- dodecyl mercaptan, alone or 2 that can be used or more kinds, the amount may be used as a 0.1 to 1 part by weight of the rubber-reinforced resin 100 parts by weight of the total monomer basis.
[47]
[48]
Further, in the present invention (a) the rubber-reinforced resins are oil-soluble buffer, such as a polymerization initiator, cumene hydro peroxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, p-methane hydroperoxide, or benzoyl peroxide oxide-based a polymerization initiator and the metal salt to the iron (II), iron (III), cobalt (II) or cerium (IV), the oxidation-reduction agent composed of dextrose, glucose, flow monohydrate such as polysaccharides dihydroxyacetone or polyamines such as - a reducing-based polymerization initiator can be used alone or more, the amount may be 0.05 to 0.5 parts by weight of a rubber-reinforced resin 100 parts by weight of the total monomer basis.
[49]
[50]
Such a) the rubber-reinforced resin 20 to 40 parts by weight of the b) a matrix resin as a styrene-acrylonitrile copolymer and poly heat of polycarbonate resins present invention by blending one or more kinds of the matrix resin 60 to 80 parts by weight selected from the stabilizer-free It is completed the thermoplastic resin composition.
[51]
Specifically, the b) as the matrix resin of styrene-when using the acrylonitrile copolymer weight average molecular weight is within 60,000 to 200,000 g / mol range, the acrylonitrile content of the styrene 15 to 40 parts by weight in the acrylonitrile copolymer it is preferably included in%. This weight, the average molecular weight is less than 60,000 g / mol, mechanical properties of the resin is lowered, 200,000 g / mol in excess there is a surface physical property degradation due to poor compatibility with the ABS-based resin, and also a nitrile content of acrylic 15% by weight weight, because the impact resistance and chemical resistance are lowered, the acrylonitrile content in excess of 40% by weight to the acrylic resin is yellowed (yellowish).
[52]
[53]
As it explained in accordance with the present invention, the following Examples, in the case of Comparative Example 2 using the heat stabilizer Irganox series such as IR1076 determine the thermal stability improving effect of the degree similar to the case using no heat stabilizer in the present invention could.
[54]
[55]
By using the heat stabilizer-free thermoplastic resin composition thus provided Looking specifically a method for producing a thermoplastic resin composition as follows:
[56]
First, the above-described a) is a water content of the ABS resin as a rubber-reinforced thermoplastic resin is prepared as a latex 45 to 70% of heat stabilizer-free graft copolymer.
[57]
The graft copolymer when the monomer mixture is continuously added, the batch injection, or continuously introduced and the batch can optionally be used to mix the introduced, is not particularly limited batch input from 5 to 40% by weight of the total monomer mixture in the initial reaction and the remaining to continuously introduced monomer mixture is preferable considering the reaction efficiency.
[58]
This is to be identified in the following Examples, that is, when the aromatic vinyl compound and a vinyl cyanide compound the total monomers constituting the rubber-reinforced resin, 5 parts by weight and 20 parts by weight, respectively, under the following temperature rising condition 2 parts by weight first injected each with 8 wt. additional can be added.
[59]
[60]
It is desirable to continuously input within a polymerization conversion from 65 to 75% of the case of the reactive emulsifying agent, in this case, because the polymerization stability is not reduced coagulum (coagulum) amount is less effective (see Examples 1-4) .
[61]
[62]
The graft polymerization reaction time is preferably within 3 hours, the reaction after the polymerization conversion rate is more than 98.5%, a weight average molecular weight (Mw) of the polymer is preferably within the 50,000 to 150,000 g / mol range.
[63]
[64]
Then, the obtained thermal stabilizer-free graft copolymer latex to prevent oxidation and flocculation treatment to thereby obtain a water content of the graft copolymer latex is 45 to 70%.
[65]
The antioxidant treatment process by a phenol-based antioxidant The particle diameter of emulsion of 0.5 to 2 ㎛, phosphorus-or sulfur-based antioxidant slowly added to the graft rubber latex of 40 to 80 ℃ it is effective to continuously stirring to the previous coagulation process .
[66]
Its amount, it is sufficient to use 0.1 to 2 parts by weight relative to 100 parts by weight of a graft rubber latex.
[67]
[68]
In addition, the agglomeration step is to mean the process of maturing after the commitment with a metal salt or acid to the graft rubber latex, wherein a flocculating agent to be used is MgSO 4 , CaCl 2 , Al 2 (SO 4 ) 3 , sulfuric acid, phosphoric acid or hydrochloric acid, the polymer flocculant can be used such as 1 to 4 parts by weight relative to 100 parts by weight of a graft rubber latex.
[69]
[70]
Thus to a water content of 20 to 40% of a graft rubber latex is specifically the water content is 2 to 20%, more specifically from 2 and adjusted to 10% and then the matrix resin as a styrene-acrylonitrile copolymer and poly kneading the resin and the lubricant of one of polycarbonate resin, and carries out a subsequent process such as extrusion molding and / or injection molding. When having the same water content range it is possible to omit the drying step for the purpose of the present invention.
[71]
[72]
The adjustment of the water content is a dehydrator, and more particularly to a rear extruder manufactured in powder form dried by hot air drying method after removing the moisture using a compression dehydrator, separating the solid matter having a 20-40% moisture content input, or it can be adjusted to a commitment to the extruder in the solid matter of the water-containing state, and then 2 to 20% water through the dehydration and evaporation of water content in the extruder process.
[73]
[74]
The grafted with a water content of 2 to 20 Event copolymer 20 to the matrix resin 60 to blending 80 parts by weight to 40 parts by weight by a process productivity when after such that after extrusion and / or injection-molded to obtain a thermoplastic resin composition it is desirable to improve. In one example, as described in the example for carrying out the invention as obtained by extrusion molding or injection molding a thermoplastic resin composition molded article by the method of, both were superior thermal stability and gloss, impact strength and falling ball impact strength in the.
[75]
[76]
The active agent may be used, such as ethylene bis-stearyl Lama Id (EBA), magnesium stearate, its amount may be from 0.1 to 5 parts by weight based on 100 parts by weight of the total graft copolymer and the matrix resin.
Effects of the Invention
[77]
As it described above, and this maximizes the rubber content in accordance with the invention and the reactive emulsifier ABS graft copolymer when applied to increase the additional input without requiring thermal stability and surface gloss of the heat stabilizer to minimize the residual emulsifier content ABS resin , styrene-increase the compatibility with the copolymer of acrylonitrile was prepared the impact resistance and the falling ball impact strength, the thermoplastic resin composition is excellent.
Best Mode for Carrying out the Invention
[78]
Hereinafter, one presents a preferred embodiment in order to give an understanding of the invention, the following examples are intended as possible categories, and various changes and modifications within the technical scope of the present invention illustrating the present invention will be apparent to those skilled in the art, such modifications and it is obvious that belong to modified the appended claims.
[79]
[80]
Example 1
[81]
Preparation of graft rubber latex
[82]
First, the rubber particle size of 1,000 Å and a gel content of 97% by weight of small aperture rubber gradually 3,400 Å rubber particle size was added while the latex polymer 100 acetic acid aqueous solution 3 parts by weight of an hour to parts by weight and the gel content is 97% by weight of polybutadiene to give a rubber latex.
[83]
[84]
For reference, the particle size and particle size distribution is measured using a dynamic laser light schedule agent ringbeop Nicomp 370HPL devices (US, Nicomp Corporation).
[85]
Put also the rubber segment of the gel content is a coagulation using the dilute acid or metal salt to the rubber latex, and then washed with dried and finely the obtained rubber lumps cut while in a vacuum oven at 60 ℃ 24 hours and then 1g of toluene 100g for 48 hours It was stored in a dark room at room temperature, and then the sol and gel separation, and by using the following equation is a measure of the gel content.
[86]
[Equation 1]
[87]
Gel content (%) = weight of insoluble content (gel) / weight of sample x 100
[88]
[89]
Then a nitrogen-substituted polymerization reactor (autoclave) ion-exchanged with the polybutadiene rubber latex, 65 parts by weight (solids basis) to 140 parts by weight of styrene, 5 parts by weight, and one input acrylonitrile 2 parts by parts, and then the reactor temperature while being kept to 50 ℃ cumene hydro-peroxide, 0.05 parts by weight of sodium pyrophosphate and 0.09 part by weight, 0.12 parts by weight of dextrose, 0.002 parts by weight of iron and sulfur agent 1 were added in one step.
[90]
[91]
It was added followed by a continuous heated to 20 parts by weight of styrene and 8 parts by weight of acrylonitrile, tertiary dodecyl mercaptan, 0.4 part by weight of cumene hydroperoxide and 0.12 parts by weight of mixture 75 ℃ for 2 hours. After 2 hours the polymerization conversion rate was 93% is reached.
[92]
[93]
In the continuous double-start after 30 minutes (polymerization conversion 65 to 75% of the time) as the emulsifier responsive 2-acrylamido-2-methylpropane sulfonic acid (2-acrylamido-2-methylpropane sulfonic acid), 0.3 parts by weight (solids basis, 20 % aqueous solution, the pH 9 (NaOH treatment)) was added continuously for 1.5 hours.
[94]
[95]
After the end of the continuous input (polymerization conversion 93% point), the input of cumene hydroperoxide 0.06 part by weight, Strauss sodium pyrophosphate 0.04 part by weight, the deck of 0.06 parts by weight and a sulfur agent ferrous 0.001 parts by weight for 30 minutes the temperature was raised to 80 ℃ and then it was maintained for 30 minutes to complete the reaction. The polymerization conversion rate was 99%, the solid solidified minutes (stability rating scale of the graft copolymer latex) content of 0.03%, was 27% was geurapeuteuyul residual emulsifier content was 18000 ppm.
[96]
[97]
For reference, a measure using the following coagulation minutes the solid content of expression.
[98]
[Equation 2]
[99]
Solid clot minutes (%) = [the reaction tank endogenous clot weight (g) / total weight of rubber and monomer (g)] x 100
[100]
When the solid-minute coagulation more than 0.5% extremely falls are latex stability can be judged to be difficult to obtain a graft polymer suitable for the present invention because of a large amount of coagulum.
[101]
[102]
In addition, using the geurapeuteuyul (%) of the above graft polymer is coagulated graft polymer latex, washing and drying to obtain a powder, stirred into 24 hours, this powder 2g in 300 ml of acetone a the following solutions ultracentrifuge separated and dropped off the separated acetone solution to methanol to obtain a section that has not been grafted. This drying is calculated according to the following formula by measuring the weight.
[103]
[Formula 3]
[104]
Geurapeuteuyul (%) = weight of grafted monomer (g) / rubber-like weight (g) x 100
[105]
If this time is less than 20% can geurapeuteuyul pyeonghal that is undesirable gloss decrease.
[106]
[107]
In addition, the graft copolymer the residual emulsifier content (ppm) and is sonicated to dissolve the sample for accurately taking a graft copolymer powder of 0.2g in 50 ml vial was added with 10ml of acetone, and then 2 hours, methanol was added slowly to 30ml thereby precipitating a polymer. 1 is a time after sonicated for extracting additives, and then the supernatant was taken out and filtered using a HPLC / DAD / MSD (Agilent 1100 system) measuring the residual emulsifier content (ppm).
[108]
The water content of the grafted rubber latex was in the range 50 to 60%.
[109]
[110]
Coagulation of the graft rubber latex
[111]
The reaction of an antioxidant (winstay-L / IR1076 = 0.8 / 0.2) exit grafted is 0.9 ㎛ average particle size of rubber latex emulsion were introduced into 0.5 parts by weight following 85 ℃, MgSO 4 1.3 agglomeration primary under parts by weight of the presence and 97 after the second aging at ℃ to give a powdery graft polymer of 30% moisture content level.
[112]
[113]
Producing a thermoplastic resin composition
[114]
The resulting moisture content in the 30% compression dehydrator powdery graft copolymer with a water content was primarily so that the 5% level.
[115]
To a water content of 5% of the graft copolymer, 25 parts by weight, a weight average molecular weight of 140,000 g / mol and a nitrile content of acrylic styrene 24% by weight of a copolymer of 75 parts by weight of a lubricant, an acrylonitrile-ethylene bis Ste Lama Id (EBA) was added 1.5 parts by weight, and kneaded and then extruded to the final rubber content are summarized in Table 1, and to measure the physical properties after the production so that the specimen is 15%.
[116]
[117]
Example 2
[118]
Example 1 Preparation of the rubber latex of the graft in the step 2-acrylamido-2 - methylpropane sulfonic acid (2-acrylamido-2-methylpropane sulfonic acid) instead of polyoxyethylene alkylphenyl ether ammonium sulfate (ammonium polyoxyethylene alkylphenyl ether the same procedure was repeated except that HITENOL BC-): sulfate, product name.
[119]
[120]
Example 3
[121]
Example 1 Preparation of the rubber latex of the graft in the step 2-acrylamido-2 - methylpropane sulfonic acid (2-acrylamido-2-methylpropane sulfonic acid) instead of 18-C16 alkenyl succinic acid di-potassium salt (C16-alkenyl succinic acid 18, di-potassium salt, product name: Latemul ASK) and the same process was repeated except that.
[122]
[123]
Example 4
[124]
Of the Example 1 Preparation of graft rubber latex in the step, the polybutadiene rubber latex, 70 parts by weight (solids basis) and ion exchange water were introduced into 140 parts by weight of styrene 4.2 parts by weight, and acrylonitrile 1.8 wt parts of acrylonitrile, and then the reactor while maintaining the temperature at 50 ℃ cumene hydro-peroxide, 0.05 parts by weight of sodium pyrophosphate and 0.09 part by weight, 0.12 parts by weight of dextrose, 0.002 parts by weight of iron and sulfur agent 1 were added in one step.
[125]
[126]
It was added followed by continuous temperature increase and 16.8 parts by weight of styrene and acrylonitrile 7.2 wt parts of tert-dodecyl mercaptan, 0.4 part by weight of cumene hydroperoxide and 0.12 parts by weight of the mixture to 75 ℃ 1 hour 40 minutes. After one hour has elapsed 40 bun polymerization conversion rate reached 90%,
[127]
[128]
In the continuous double-start after 30 minutes (polymerization conversion 65 to 75% of the time) as the emulsifier responsive 2-acrylamido-2-methylpropane sulfonic acid (2-acrylamido-2-methylpropane sulfonic acid), 0.3 parts by weight (solids basis, 20 % aqueous solution, pH 9 (NaOH treatment)), a continuous input for 1 hour 10 minutes (1 hour and 10 minutes the polymerization conversion rate at a lapse of the time, except that a 70 to 80%) was repeated the same process as in example 1.
[129]
[130]
Example 5
[131]
Of the Example 1 Preparation of graft rubber latex in the step, starting after 30 min continuous input (polymerization conversion 65 to 75% of the time) as the emulsifier responsive 2-acrylamido-2-methylpropane sulfonic acid (2-acrylamido-2 methylpropane sulfonic acid-) 0.3 parts by weight (solids basis, 20% aqueous solution, pH 9 (NaOH treatment)) 0.001 parts by weight, except that the alternative is the same process as in example 1 was repeated.
[132]
[133]
Example 6
[134]
Of the Example 1 Preparation of graft rubber latex in the step, starting after 30 min continuous input (polymerization conversion 65 to 75% of the time) as the emulsifier responsive 2-acrylamido-2-methylpropane sulfonic acid (2-acrylamido-2 -methylpropane sulfonic acid), 0.3 parts by weight (solids basis, 20% aqueous solution, pH 9 (NaOH treatment), except that the alternative) 2 parts by weight the same procedure was repeated as in example 1.
[135]
[136]
Comparative Example 1
[137]
1 of the exemplary production of the graft rubber latex in step 2-acrylamido-2-methylpropane sulfonic acid (2-acrylamido-2-methylpropane sulfonic acid) instead of a non-reactive emulsifier as a fatty acid soap, 0.6 weight parts of one hour 30 minutes the same procedure was repeated except that during continuous infusion.
[138]
[139]
Comparative Example 2
[140]
In the prior art, except that as the heat stabilizer in accordance with the techniques IR1076 0.03 parts by weight in Example 1, and repeats the same experiment as in Example 1 and was compounded through a drying process.
[141]
[142]
Comparative Example 3
[143]
Of the Example 1 Preparation of graft rubber latex in step 2-acrylamido-2-methylpropane sulfonic acid (2-acrylamido-2-methylpropane sulfonic acid) and then heated to an elevated temperature before the reaction temperature of 50 rather than 30 inputs since the bun except for the time of input from ℃ it was repeated the same process as in example 1.
[144]
[145]
[Metric]
[146]
The physical properties of the ABS specimens prepared in Examples 1-6 and Comparative Examples 1-3 were measured in the same way.
[147]
* Izod impact strength : by a thickness of the specimen into 1/4 "inch was measured by the ASTM D256 method.
[148]
* Flow Index (MI: melt flow index): under 220 ℃ / 10kg were measured by the ASTM D1238 method.
[149]
* Tensile strength was measured by ASTM D638 method.
[150]
* Surface gloss: was measured by ASTM method D528 at 45 ° angle.
[151]
* Residence gloss: the 45 ° gloss as a was introduced into the pellet obtained in the extruder in the extruder residence 15 minutes under 270 ℃ condition gaining polished specimen, injection them without staying at 200 ℃ specimen was measured, and measures the variation thereof. The figures indicate that less excellent gloss retention.
[152]
* Residence discoloration ( △ E) : retention polished against a polished specimen obtained by the method for measuring sugar color computer (Suga color computer) to the equation to obtain the L, a, b values ​​for the retention before and after the specimen using according to degree of discoloration it was determined to stay.
[153]
[154]
[Equation 4]
[155]
[156]
* Falling Ball Impact strength: measured by ASTM method D3783.
[157]
[158]
Table 1 [Table 1]
division Example Comparative Example
1 2 1 2 3 4 5 6 1 2 3
Rubber Latex Particle diameter (Å) / Gel content (% by weight) 3400/97
Content (parts by weight) 65 65 65 70 65 65 65 65 65
* In the monomer mixture method Batch (Phase 1) / Continuous (step 2) 7/28 7/28 7/28 6/24 7/28 7/28 7/28 7/28 7/28
(Non) reactive emulsifier Parts by weight 0.3 0.3 0.3 0.3 0.001 2 0.6 0.3 0.3
Polymerization results Polymerization conversion rate (%) 99 98.9 98.9 99.2 98.5 99.1 97.5 98 97.5
Solid clot minutes (%) 0.03 0.02 0.03 0.05 0.05 0.02 0.12 0.05 0.8
Geurapeuteuyul (%) 27 26.5 27 25 26.5 27 19 26 22
Residual emulsifier content (ppm) 18000 18500 19000 17500 17000 19000 23000 18500 18200
Properties Impact strength (kg.cm/cm) 23.5 24.0 23.8 23.2 23.0 23.5 21.0 22.5 21.0
Fluidity (g / 10min) 21 20.8 21.3 21.3 20 22 20 21 20
Tensile strength (kg / cm 2 ) 515 512 510 508 510 516 515 513 505
Glossy surface 109.5 108.5 108.8 108.2 106.5 107.5 106.5 108.0 106.0
Whiteness 57 57 56 58 58 56 55 54 53
Gloss retention 2.5 2.6 2.8 2.1 2.5 4.0 5.5 3.8 2.7
Thermochromic stay 3.5 3.6 3.8 3.3 3.4 3.8 6.2 4.0 3.8
Falling ball impact (F, N) 4020 4025 4030 4000 4030 3960 3880 3800 3750
Falling ball impact (E, J) 32 33 33 31 30 29 28 30 28

[159]
* Total amount of styrene and acrylonitrile
[160]
[161]
As shown in Table 1, not going through the embodiment 1-6 separate without using a heat stabilizer, and thermal stability during the drying process the gloss as well as excellent production For the production according to the present invention, the impact resistance of the ABS resin and this was confirmed that excellent falling ball impact strength and the like.
[162]
[163]
On the other hand, in the case of the comparative example using the non-reactive emulsifying agent non-reactive emulsifying agent 1 has performed over the whole measurement field, such as impact strength, flowability, surface gloss, whiteness, gloss retention, residence thermochromic, falling ball impact strength Example 1-6 This confirmed the results than the poor.
[164]
In addition, it could be the case of Comparative Example 2 were introduced into a conventional heat stabilizer was introduced similar to the embodiment 1-6 are not added separately, or the heat stabilizer to be seen determine the equivalent physical properties measured.
[165]
Moreover, further use the reactive emulsifying agent, in the case of a Comparative Example 3 In contrast to the time that has also has a poor result than the embodiment 1-6 in the field of measuring the impact strength, flowability, surface gloss, whiteness, falling ball impact strength, etc. It could be confirmed.
Claims
[Claim 1]
a) the rubber-reinforced resin and b) comprising a matrix resin, wherein a) the rubber-reinforced resin is rubber-like polymer latex, aromatic vinyl compound, vinyl cyanide compound and including a reactive emulsifying agent and a thermoplastic ABS system obtained by the graft copolymer resin thermal stabilizer-free thermoplastic resin composition characterized in that the.
[Claim 2]
According to claim 1, wherein b) the matrix resin is a styrene-acrylonitrile copolymer and polycarbonate thermal stabilizer-free thermoplastic resin composition, characterized in that said at least one resin selected from the resin.
[Claim 3]
According to claim 2, wherein b) the matrix resin has a weight average molecular weight of 60,000 and to 200,000 g / mol range, the acrylonitrile content of the acrylic 15 to 40% by weight of a styrene-characterized in that using the acrylonitrile copolymer thermal stabilizer-free thermoplastic resin composition.
[[4]
According to claim 1, wherein the rubber-like polymer and is 5000 Å the particle diameter 2500 to, gel content is characterized in that comprises 85 to be the 99% by weight, the rubber-reinforced resin monomers total as 100 parts by weight based on 60 to 75 parts by weight thermal stabilizer-free thermoplastic resin composition.
[Claim 5]
According to claim 1, wherein the aromatic vinyl compound is styrene, α- methyl styrene, p- methyl styrene, vinyl toluene, t- butylstyrene, chlorostyrene or a rubber can be enhanced alone or in mixture of two or more kinds thereof and the like substituents resin thermal stabilizer-free thermoplastic resin composition which comprises 100 parts by weight based on total used monomer into the 18 to 28 parts by weight.
[6.]
According to claim 1, wherein into the said vinyl cyanide compound is acrylonitrile, methacrylonitrile, acrylonitrile or the rubber-reinforced alone, or two or more kinds of these substituents resin monomer of 100 parts by weight from 5 to 15 parts by weight thermal stabilizer-free thermoplastic resin composition characterized in that it uses.
[7.]
According to claim 1, wherein the reactive emulsifier is carbonate, sulfonate, and sulfate can rubber-emulsifier containing at least one species selected functional group from the group consisting of a resin monomer of 100 parts by weight of 0.001 to 2 parts by weight based on thermal stabilizer-free thermoplastic resin composition characterized by the use within.
[8.]
According to claim 6, wherein the reactive emulsifier is sulfoethyl methacrylate (sulfoethyl methacrylate), 2-acrylamido-2 - methylpropane sulfonic acid (2-acrylamido-2-methylpropane sulfonic acid), sodium styrene sulfonate (sodium when styrene sulfonate), sodium dodecyl allyl alcohol posuk carbonate (sodium dodectyl allyl sulfosuccinate), styrene and sodium dodecyl allyl alcohol posuk when carbonate copolymers, polyoxyethylene alkylphenyl ether ammonium sulfate (polyoxyethylene alkylphenyl ether ammonium sulfate), Al alkenyl C16-18 acid di-potassium salt (alkenyl C16-18 succinic acid, di-potassium salt) and sodium methallyl sulfonate (sodium methallyl sulfonate) selected from at least one member characterized in that heat stabilizer-free thermoplastic resin composition.
[9.]
According to claim 1, wherein a) the rubber-reinforced resin is heat stabilizer-free thermoplastic resin composition comprising the molecular weight controlling agent into the rubber-reinforced resin to 100 parts by weight based on total monomer of 0.1 to 1 parts by weight.
[10.]
According to claim 1, wherein a) the rubber-reinforced resin is heat stabilizer-free thermoplastic resin composition characterized in that it comprises a polymerization initiator into the rubber-reinforced resin monomer based on 100 parts by weight of the total of 0.05 to 0.5 parts by weight.
[11.]
According to claim 1, wherein a) in the rubber-reinforced resin 20 to 40 parts by weight, b) a matrix resin of 60 to 80 heat stabilizer-free thermoplastic resin composition characterized in that the formulation by weight.
[12.]
According to claim 1, wherein a) the rubber-reinforced residual emulsifier content is injected emulsifier thermal stabilizer-free thermoplastic resin composition characterized in that a total of not more than 100% by weight to 65% by weight based on the resin.
[13.]
a) a step for preparing a 1 to Claim 12 wherein the thermal stabilizer of any one of the free rubber-reinforced resin of the thermoplastic resin composition with a water content of 45 to 70% of heat stabilizer-free graft copolymer latex; b) step of the water content of the obtained graft copolymer latex 20 to 40% by the heat stabilizer-free graft prevent oxidation treatment and the aggregation copolymer latex; And c) kneading the graft to adjust the copolymer latex by 2 to 20% water content, and then the first term thermal stabilizer-free thermoplastic resin composition of the matrix resin and a lubricant; Preparation of thermoplastic resin composition that is characterized by Way.
[14.]
15. The method of claim 13, wherein step a) method for producing a thermoplastic resin composition characterized in that the batch input from 5 to 40% by weight of the total monomer constituting the rubber-reinforced resin in the initial reaction and the continuous input a remainder glass.
[15.]
15. The method of claim 13, wherein a) reactive emulsifier of the first term thermal stabilizer-free thermoplastic resin composition used in the step is the manufacturing method of the thermoplastic resin composition characterized in that the polymerization conversion 65 to a continuous input at 75%.
[16.]
The method of claim 13, wherein the step b), oxidation-preventing process is particle size is 0.5 emulsified phenolic by 2 ㎛ to antioxidants, phosphorus or sulfur-based antioxidant, a graft rubber latex 100 parts by weight of 0.1 to 2 parts by weight with respect to the in gradually put in the graft rubber latex of 40 to 80 ℃ by the manufacturing method of the thermoplastic resin composition characterized in that prior to the continuous stirred coagulation process.
[17.]
15. The method of claim 13, wherein b) MgSO the aggregation process are graft rubber latex in step 4 , CaCl 2 , Al 2 (SO 4 ) 3 , sulfuric acid, phosphoric acid, grafted to one or more or a polymer flocculant selected from the hydrochloric acid agent rubber method of producing a thermoplastic resin composition characterized in that after the input of 1 to 4 parts by weight based on 100 parts by weight of the latex content in the fermentation.
[18.]
14. The method of claim 13 wherein the c) method for producing a thermoplastic resin composition characterized in that the control is performed through the squeezing process to the water content of 2 to 20% in the step.
[19.]
14. The method of claim 13 wherein the c) method for producing a thermoplastic resin composition in the step wherein the blending the matrix resin 60 to 80 parts by weight of a graft copolymer of 20 to 40 parts by weight adjusted to a 2-20% water content .
[20.]
14. The method of claim 13 wherein the c) a lubricant is added to the phase of the graft copolymer and the method of manufacturing a matrix based on a total of 100 parts by weight thermoplastic resin composition, characterized in that 0.1 to 5 parts by weight of the resin.