Detailed description of the invention
Technical challenge
[16]
In order to solve the problems of the prior art as described above, the present substrate is an acid coagulant 0.10 to 0.80 based on 100 parts by weight (solid content) of the graft copolymer latex obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound on a conjugated diene rubber latex. A first coagulation step of coagulating by adding a weight part; And a second agglomeration step of adding 0.96 to 1.85 parts by weight of a salt coagulant to agglomerate after the first coagulation step; including, but adjusting the total weight of the acid coagulant and the salt coagulant to 1.66 to 2.20 parts by weight, excellent cohesion efficiency and glossiness Is high and the b value measured using a Hunter Lab color meter and the b value measured after staying in the injection machine at 250°C for 15 minutes are low, so the color is excellent, while the heating loss is low and the scorch time is long. An object of the present invention is to provide a method for producing a graft copolymer having excellent properties.
[17]
[18]
The above and other objects of the present description can be achieved by the present description described below.
Means of solving the task
[19]
In order to achieve the above object, the present substrate is graft polymerization of 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyanide compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight. Preparing a graft copolymer latex; A first coagulation step of coagulating by adding 0.10 to 0.80 parts by weight of an acid coagulant to 100 parts by weight of the prepared graft copolymer latex (based on solid content); And a second agglomeration step of coagulating by adding 0.96 to 1.85 parts by weight of a salt coagulant after the first coagulation step; wherein the total of the acid coagulant and the salt coagulant is 1.66 to 2.20 parts by weight-conjugated diene It provides a method for preparing a compound-aromatic vinyl compound graft copolymer.
[20]
[21]
In addition, the present disclosure provides a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer prepared by the above production method.
[22]
[23]
In addition, the present disclosure includes a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 20 to 40% by weight and an aromatic vinyl compound-vinyl cyan compound copolymer 60 to 80% by weight according to the above production method. It provides a thermoplastic resin composition characterized by.
Effects of the Invention
[24]
According to the present description, the graft copolymer latex obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound on a conjugated diene rubber latex is agglomerated with 0.10 to 0.80 parts by weight of an acid coagulant, and then again coagulated with 0.96 to 1.85 parts by weight of a salt coagulant. When the total amount of the acid coagulant and salt coagulant is 1.66 to 2.20 parts by weight, the cohesive efficiency is excellent, the gloss is high, the b value measured using a Hunter Lab color meter and the b value measured after staying at 250°C for 15 minutes are low. This is excellent, the heating loss is low, and the scorch time is long, so the processing characteristics are excellent.
Best mode for carrying out the invention
[25]
The present inventors coagulate the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer latex with an acid coagulant and then again coagulate with a salt coagulant. After confirming the excellent effect of color and processing characteristics, based on this, the present invention was completed by further focusing on research.
[26]
[27]
A detailed method of preparing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer according to the present disclosure is as follows.
[28]
[29]
The method for producing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure includes 20 to 40% by weight of an aromatic vinyl compound and 20 to 40% by weight of an aromatic vinyl compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight. Graft polymerization of 1 to 20% by weight of a cyan compound to prepare a graft copolymer latex; A first coagulation step of coagulating by adding 0.10 to 0.80 parts by weight of an acid coagulant to 100 parts by weight of the prepared graft copolymer latex (based on solid content); And a second flocculation step of coagulating by adding 0.96 to 1.85 parts by weight of the salt coagulant after the first coagulation step, wherein the total weight of the acid coagulant and the salt coagulant is 1.66 to 2.20 parts by weight, in this case The aggregation efficiency is excellent, the b-value measured using a Hunter Lab color meter and the b-value measured after staying at 250°C for 15 minutes are low, and the gloss is high, so the color is excellent .
[30]
[31]
The manufacturing method of the present disclosure will be described step by step as follows.
[32]
[33]
Conjugated Diene Rubber Latex Preparation Step
[34]
The manufacturing method of the conjugated diene rubber latex is, for example, 100 parts by weight of a conjugated diene compound, 30 to 100 parts by weight of ion-exchanged water, 0.5 to 3 parts by weight of an emulsifier, 0.01 to 0.5 parts by weight of an electrolyte, 0.1 to 0.5 parts by weight of a molecular weight modifier, and 0.1 to 1 part by weight of the initiator may be added and polymerized to prepare a conjugated diene rubber latex, and in this case, there is an effect of excellent impact resistance.
[35]
[36]
In another example, the method of preparing a conjugated diene rubber latex includes 100 parts by weight of a conjugated diene compound, 40 to 70 parts by weight of ion-exchanged water, 1 to 2.5 parts by weight of an emulsifier, 0.05 to 0.3 parts by weight of an electrolyte, 0.2 to 0.4 parts by weight of a molecular weight modifier. And 0.3 to 0.8 parts by weight of the initiator may be added and polymerized to prepare a conjugated diene rubber latex, in which case there is an effect of excellent impact resistance.
[37]
[38]
As a specific example, the method of manufacturing the conjugated diene rubber latex includes 30 to 100 parts by weight of ion-exchanged water, 0.3 to 2 parts by weight of emulsifier, 0.01 to 0.5 parts by weight of electrolyte, and molecular weight modifier in 75 to 90 parts by weight of 100 parts by weight of the conjugated diene compound. Introducing 0.1 to 0.5 parts by weight and 0.05 to 0.5 parts by weight of an initiator, and performing primary polymerization; 0.05 to 0.5 parts by weight of an initiator and 10 to 25 parts by weight of a conjugated diene compound are continuously added to a polymerization conversion rate of 35 to 45% after the first polymerization step, followed by secondary polymerization; Adding 0.2 to 1 parts by weight of an emulsifier and performing tertiary polymerization at a time when the polymerization conversion rate is 70 to 80% after the second polymerization step; After the tertiary polymerization step, terminating the polymerization at a polymerization conversion rate of 93 to 99% by weight; may include, and in this case, there is an effect of excellent impact resistance.
[39]
[40]
In the present description, the polymerization conversion rate may be defined as the weight% of the monomer converted to the polymer until measurement based on 100% of the total weight of the monomers added until the polymerization is completed, and the method of measuring the polymerization conversion rate is determined according to this definition. The method of measuring the polymerization conversion rate is not particularly limited, and as a specific example, 1.5 g of the prepared latex is dried in a hot air dryer at 150° C. for 15 minutes, and then the weight is measured and the total solid content (TSC) is calculated by Equation 1 below. It can be obtained and calculated using Equation 2 below. Equation 2 is based on the total weight of the added monomer is 100 parts by weight.
[41]
[42]
[Equation 1]
[43]
Total solid content (TSC; %) = (Weight after drying / Weight before drying) × 100
[44]
[45]
[Equation 2]
[46]
Polymerization conversion rate (%) = [Total solid content (TSC) × (total weight of added monomer, ion-exchanged water, and auxiliary raw materials) / 100]-(weight of auxiliary raw materials other than monomer and ion-exchanged water)
[47]
[48]
Sub-materials in Equation 2 refer to initiators, emulsifiers, electrolytes, and molecular weight modifiers.
[49]
The added monomer refers to a conjugated diene compound.
[50]
[51]
The conjugated diene compound is one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and isoprene, for example It can be more than that.
[52]
[53]
The emulsifier may be, for example, one or more selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, soaps of fatty acids, and alkali salts of rosin acids.
[54]
[55]
The electrolyte is for example KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7 , Na 4 P 2 O 7 , K 3 PO 4 , Na 3 PO 4 , K 2 HPO 4 and Na 2 HPO 4It may be one or more selected from the group consisting of.
[56]
[57]
The initiator may be, for example, a water-soluble persulfate polymerization initiator, a fat-soluble polymerization initiator, or an oxidation-reduction catalyst system, and the water-soluble persulfate polymerization initiator includes, for example, potassium persulfate, sodium persulfate, and ammonium persulfate. It may be one or more selected from, and the oil-soluble polymerization initiator is, for example, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, t-butyl hydroperoxide, paramethane hydroperoxide, and benzoyl. It may be one or more selected from the group consisting of peroxide, and examples of the oxidation-reduction catalyst system include sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, and sodium pyrrolate. It may be one or more selected from the group consisting of sodium sulfate.
[58]
When preparing the conjugated diene rubber latex, it may be most preferably potassium persulfate.
[59]
[60]
The molecular weight modifier may be, for example, a mercaptans-based molecular weight modifier, and a tertiary dodecyl mercaptan is particularly preferred.
[61]
[62]
The conjugated diene rubber latex of the present disclosure may be, for example, an average particle diameter of 1,800 to 5,000 Å, preferably 2,000 to 4,000 Å, more preferably 2,500 to 3,500 Å, and has excellent impact resistance within this range.
[63]
In this description, the average particle diameter is a sample prepared by diluting the conjugated diene rubber latex to a total solids content (TSC) of 0.1% or less, and then using a Nicomp TM 380 device (PSS, Nicomp, USA) by a dynamic laser light scattering method. It can be measured using.
[64]
[65]
Graft Copolymer Latex Manufacturing Step
[66]
The step of preparing the graft copolymer latex is, for example, grafting 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyan compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight. It is possible to perform graft polymerization, preferably 25 to 35% by weight of an aromatic vinyl compound and 5 to 15% by weight of a vinyl cyan compound in 55 to 65% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight. And within this range, there is an effect excellent in impact resistance, mechanical strength and moldability.
[67]
In this description, the solid content is defined as the content of the active ingredient remaining when all the moisture in the latex has been evaporated. After measuring 2.5 g of latex in an aluminum dish with a balance, heating at 150°C for 5 minutes to evaporate all the moisture. By measuring the weight, it can be obtained by Equation 3 below.
[68]
[69]
[Equation 3]
[70]
Solid content (% by weight) = 100-[(Weight of latex before moisture drying (g)-Weight of remaining powder after moisture drying (g)) / Weight of latex before moisture drying × 100]
[71]
[72]
The step of preparing the graft copolymer latex may include, for example, a conjugated diene rubber latex, an aromatic vinyl compound, and a vinyl cyan compound in a total of 100 parts by weight, 70 to 200 parts by weight of ion exchange water, 0.1 to 2 parts by weight of an initiator, 0.1 to 2 parts by weight of an emulsifier. After polymerization by adding 2 parts by weight and 0.05 to 1.5 parts by weight of a molecular weight control agent, the polymerization reaction may be terminated at a polymerization conversion rate of 93 to 99% by weight.
[73]
In this step, the polymerization conversion rate follows the definition and measurement method of the polymerization conversion rate described above in the preparation of the conjugated diene rubber latex, but the added monomer refers to a conjugated diene compound, an aromatic vinyl compound, and a vinyl cyan compound contained in the rubber latex.
[74]
[75]
In another example, the step of preparing the graft copolymer latex includes a total of 100 parts by weight of a conjugated diene rubber latex, an aromatic vinyl compound and a vinyl cyan compound, 100 to 170 parts by weight of ion exchange water, 0.3 to 1 part by weight of an initiator, and an emulsifier. After the polymerization reaction is carried out by adding 0.5 to 1.5 parts by weight and 0.1 to 1.0 parts by weight of a molecular weight control agent, the polymerization reaction can be terminated at a polymerization conversion ratio of 95 to 98% by weight.
[76]
[77]
As a specific example, the step of preparing the graft copolymer latex includes 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight based on a total of 100 parts by weight of a conjugated diene rubber, an aromatic vinyl compound, and a vinyl cyan compound. 60 to 150 parts by weight of exchange water, 20 to 40 parts by weight of an aromatic vinyl compound mixed in a separate mixing device, 1 to 20 parts by weight of a vinyl cyanide compound, 10 to 50 parts by weight of ion-exchanged water, 0.09 to 1.5 parts by weight of an initiator, A mixed solution containing 0.1 to 2 parts by weight of an emulsifier and 0.05 to 1.5 parts by weight of a molecular weight control agent was added at 65 to 75°C for 2 to 4 hours, and then 0.01 to 0.5 parts by weight of an initiator was added, and 75 to 80 over 30 to 90 minutes. After raising the temperature to °C, the graft polymerization can be terminated at a polymerization conversion rate of 93 to 99% by weight, and in this case, there is an effect of excellent impact resistance, mechanical strength and moldability.
[78]
[79]
The conjugated diene rubber latex may be, for example, a solid content of 30 to 65% by weight, preferably 40 to 60% by weight, more preferably 55 to 60% by weight, and in this case, the polymerization reaction proceeds uniformly. There is.
[80]
[81]
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-bro It may be one or more selected from the group consisting of parent styrene, m-bromo styrene, o-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyl toluene, vinyl xylene, fluorostyrene, and vinyl naphthalene.
[82]
The vinyl cyan compound may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof.
[83]
[84]
The emulsifier, initiator, and molecular weight modifier may be used within the range used in the preparation step of the conjugated diene rubber latex, for example.
[85]
[86]
Other additives, such as electrolytes not specifically mentioned in the present description, may be appropriately selected as necessary, and are particularly limited if they are within the range generally applied to the production of vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer latex. It doesn't work.
[87]
[88]
In addition to the above description, other reaction conditions such as reaction time, reaction temperature, pressure, and addition time of reactants in the method for preparing the graft copolymer are not particularly limited if they are within the range commonly used in the technical field to which the present invention belongs. It can be appropriately selected and implemented according to.
[89]
[90]
Aggregation step of graft copolymer latex
[91]
The graft copolymer latex prepared above is agglomerated by a coagulant to form a graft copolymer slurry.
[92]
The agglomeration step may include a first agglomeration step of adding 0.10 to 0.80 parts by weight of an acid coagulant to 100 parts by weight of the graft copolymer latex (based on solid content) as an example and agglomerating; And a second flocculation step of coagulating by adding 0.96 to 1.85 parts by weight of a salt coagulant after the first coagulation step; but, the total amount of the acid coagulant and the salt coagulant may be 1.66 to 2.20 parts by weight, and in some cases, while having excellent flocculation efficiency The gloss is high and the b-value measured using a Hunter Lab color meter and the b-value measured after staying at 250°C for 15 minutes are low, so the color is excellent, the heating loss is low, and the scorch time is long, so the processing characteristics are excellent.
[93]
[94]
The first coagulation step may be, for example, a step of adding an acid coagulant to the graft copolymer latex at 75 to 85°C and then raising the temperature by 5 to 10°C over 5 to 35 minutes, and preferably acid After the flocculant is added at 78 to 82° C., it may be a step of raising the temperature by 6 to 8° C. over 10 to 30 minutes. In this case, the agglomeration is uniform and the agglomeration efficiency is excellent.
[95]
[96]
In the second agglomeration step, as an example, a salt coagulant is added at 80 to 95°C, and the temperature can be increased by 5 to 10°C over 5 to 35 minutes, preferably a salt coagulant is added at 84 to 90°C. In this case, the temperature can be increased by a temperature of 6 to 8° C. over 10 to 30 minutes, and in this case, agglomeration is uniformly achieved, agglomeration efficiency is excellent, and there is an effect of aging.
[97]
[98]
As a specific example, the temperature at which the first coagulation step ends and the temperature at which the second coagulation step starts may be the same.
[99]
[100]
The first coagulation step and the second coagulation step may be carried out under conditions of, for example, a stirring speed of 5 to 450 rpm, or 10 to 400 rpm, preferably 30 to 300 rpm, more preferably 30 to 100 rpm, , But is not limited thereto. Within the stirring speed range, productivity is excellent, aggregation efficiency is high, and physical property balance is excellent.
[101]
[102]
The acid flocculant is, for example, 0.10 to 0.80 parts by weight, preferably 0.15 to 0.75 parts by weight, more preferably 0.20 to 0.70 parts by weight, even more preferably based on 100 parts by weight of the graft copolymer latex (based on solid content). It can be agglomerated by including 0.20 to 0.50 parts by weight, or 0.50 to 0.70 parts by weight, and within this range, the agglomeration efficiency is excellent, the gloss is high, the b value measured using a Hunter Lab color meter and the injection machine at 250°C for 15 minutes The b value measured after staying at is excellent, so the color is excellent, the heating loss is low, and the scorch time is long, so the processing characteristics are excellent.
[103]
[104]
The salt coagulant is, for example, 0.96 to 1.85 parts by weight, or 0.96 to 1.80 parts by weight, preferably 1.00 to 1.80 parts by weight, more preferably 1.25 to 1.80 parts by weight, based on 100 parts by weight of the graft copolymer latex (based on solid content) Parts, more preferably 1.30 to 1.50 parts by weight may be included to aggregate, and within this range, the glossiness is excellent, the heating loss is low, and the scorch time is long, so that the processing characteristics are excellent.
[105]
[106]
The total sum of the acid coagulant and the salt coagulant is, for example, 1.66 to 2.20 parts by weight, or 1.70 to 2.10 parts by weight, preferably 1.70 to 2.00 parts by weight, more preferably based on 100 parts by weight of the graft copolymer latex (based on solid content). In this range, 1.75 to 2.00 parts by weight can be added, and within this range, the cohesive efficiency is excellent, the gloss is high, the b value measured using a Hunter Lab color meter and the b value measured after staying at 250°C for 15 minutes are low. This is excellent, the heating loss is low, and the scorch time is long, so the processing characteristics are excellent.
[107]
[108]
The acid coagulant may be one or more selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid, and acetic acid as an example, and preferably sulfuric acid. The b value measured after staying for 15 minutes has an excellent effect.
[109]
The salt coagulant may be one or more selected from the group consisting of magnesium sulfate, calcium sulfate, aluminum sulfate, magnesium chloride, calcium chloride and aluminum chloride, for example, and preferably magnesium sulfate, and in this case, the coagulant efficiency is good. It has an excellent gloss effect.
[110]
[111]
When the acid coagulant and the salt coagulant contain a solvent such as water, the weight thereof refers to the weight excluding the solvent.
[112]
[113]
The agglomeration step may further include an antioxidant, a stabilizer, or a mixture thereof, for example, and in this case, there is an effect of having an excellent balance of physical properties after extrusion.
[114]
[115]
The agglomerated graft copolymer latex may be dehydrated and dried to obtain a graft copolymer powder.
[116]
[117]
In the present description, powder means an object in a state in which a large number of solid particles are aggregated, for example, an object having an average particle diameter of 1 to 10,000 μm, or 10 to 2,000 μm in a state in which a large number of solid particles are aggregated. have.
[118]
In the present description, the average particle diameter of the powder can be measured by the DP caking test. In the DP caking test, 10 g of powder was compressed with a weight of 20 kg for 10 minutes, and then a layer of #8 mesh (2380 μm) to #625 mesh (20 μm) was stacked on a sieve vibrator (Analysette 3) of Fritsch, Germany, and # After installing a stainless steel container that can collect the powder passing through the 625 mesh at the bottom of the #625 mesh, vibrating the sieve vibrator for 20 minutes, and then checking the particle size distribution of the powder remaining in the mesh and accumulating from the particle size distribution. The diameter of the particles passing through 50% by weight of the weight is taken as the average particle diameter of the powder.
[119]
[120]
The dehydration and drying step is not particularly limited if it is a method generally used in the art.
[121]
The slurry obtained after the agglomeration may be dehydrated using a centrifugal dehydrator, a compression dehydrator, or the like, to obtain a graft copolymer in a wet powder state.
[122]
The dehydration may be preferably carried out one or more times, preferably 1 to 3 times, more preferably 2 to 3 times as an example, and in this case, the residual emulsifier content is reduced to improve surface properties such as glossiness. Has the effect of being.
[123]
The graft copolymer in the wet powder state obtained after the dehydration has a water content of, for example, 40% by weight or less, preferably 10 to 40% by weight, more preferably 10 to 35% by weight or 10 to 30% by weight. %, and in this case, there is an advantage of excellent productivity by increasing the efficiency in the drying step, which is a post process.
[124]
[125]
The drying is not particularly limited in the case of a known drying process commonly carried out in the technical field to which the present invention belongs, but as an example, the graft copolymer in a wet powder state is aired using a fluidized bed dryer. After supplying and drying, the graft copolymer powder can be obtained.
[126]
In addition, the graft copolymer powder obtained by drying the graft copolymer in the wet powder state may have a water content of 2% by weight or less, preferably 0.1 to 2% by weight, more preferably 0.1 to 1% by weight. And, within this range, there are advantages of excellent productivity of the copolymer and excellent physical properties such as mechanical strength, heat resistance, and surface gloss.
[127]
In the present description, the moisture content can be measured using a moisture analyzer, and specifically, a moisture analyzer of METTLER TOLEDO, Switzerland.
[128]
[129]
The graft copolymer powder can be extruded after melt-kneading with an aromatic vinyl compound-vinyl cyan compound copolymer as an example, and in this case, it has excellent impact resistance, chemical resistance, molding processability, etc. The b-value measured using a meter and the b-value measured after staying at 250° C. for 15 minutes are low, so that a thermoplastic resin composition having a beautiful color can be prepared.
[130]
The melt-kneading and extrusion steps may be performed under 220 to 240°C and 250 to 400 rpm, preferably at 225 to 235°C and 300 to 400 rpm, but are not limited thereto.
[131]
[132]
The melt-kneading may be performed using, for example, a Banbari mixer, a single screw extruder, a twin screw extruder, a kneader, etc., and is not particularly limited.
[133]
During the melt-kneading, 0.1 to 10 parts by weight or 0.1 to 5 parts by weight of one or more additives selected from the group consisting of a colorant, a heat stabilizer, a light stabilizer, a reinforcing agent, a filler, a flame retardant, a lubricant, a plasticizer, an antistatic agent, and a processing aid It can be input within the sub-range.
[134]
[135]
In addition, the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure is characterized in that it is prepared by the above production method, and in this case, the b value and 250 measured using a Hunter Lab color meter The b-value measured after staying at °C for 15 minutes is low and the gloss is high, so the color is excellent .
[136]
[137]
In addition, the thermoplastic resin composition of the present invention is the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 20 to 40% by weight, preferably 25 to 35% by weight, and aromatic vinyl compound-vinyl cyan compound copolymer 60 To 80% by weight, preferably 65 to 75% by weight. The b value measured after staying at 250°C for 15 minutes is low, so the color is beautiful.
[138]
[139]
The thermoplastic resin composition has, for example, the glossiness of a specimen having a thickness of 1/8 inch (3.2mm), measured at a 45° angle with a gloss meter according to ASTM D523, of 90 or more, or 90 To 110, preferably 92 to 102, more preferably 96 to 100, there is an excellent effect of the physical property balance and color within this range.
[140]
[141]
The thermoplastic resin composition may have a b value of 3.6 or less, preferably 3.0 to 3.6, more preferably 3.2 to 3.5, measured using a Hunter Lab color meter as an example, and has excellent physical property balance and color within this range. It works.
[142]
[143]
For example, the thermoplastic resin composition has a b value of 9 or less, preferably 3 to 9, more preferably 5 to 9, more preferably 5 to 9, as measured using a Hunter Lab calimeter after staying at 250°C for 15 minutes. It may be 8, and within this range, there is an excellent effect of physical property balance and color.
[144]
[145]
The thermoplastic resin composition may have a scorch time of 60 minutes or more, or 80 minutes or more, preferably 80 to 180 minutes, more preferably 80 to 150 minutes, by a scorch test at 190°C. In addition, there is an effect of excellent balance of processing characteristics and physical properties within this range.
[146]
In the present description, the scorch time is the time when the flow stops in the mold and the rubber begins to ripen. If the scorch time is short, the unvulcanized compound is vulcanized during molding at a high temperature, resulting in a high frequency of forming defects.
[147]
In this description, the scorch time refers to the scorch time by placing the thermoplastic resin composition powder having a moisture content of 1% by weight or less in an aluminum foil in a state capable of contacting oxygen in the atmosphere, leaving it in a hot air oven at 190°C, and measuring the time at which carbonization begins. . The longer the scorch time is, the better the thermal stability is evaluated.
[148]
In the present description, the moisture content can be measured using a moisture analyzer, and specifically, a moisture analyzer of METTLER TOLEDO, Switzerland.
[149]
[150]
The thermoplastic resin composition may have a heating loss of 0.8% by weight or less, or 0.1 to 0.8% by weight, preferably 0.1 to 0.6% by weight, more preferably 0.4 to 0.6% by weight, and processing properties within this range. And there is an effect of excellent balance of properties.
[151]
In the present description, the loss of heating is a decrease in weight that occurs when heating the material under certain conditions, and after increasing the heating rate from 80℃ to 250℃ at a rate of 20℃/min under a nitrogen atmosphere, heating under the condition of maintaining at 250℃ for 60 minutes Then, the weight of the resin before and after heating can be measured and determined by the following equation (4). In addition, the weight before and after heating can be determined by measuring by thermogravimetric analysis (TGA). The lower the heating loss is, the better the processing characteristics are.
[152]
[153]
[Equation 4]
[154]
Heating loss (% by weight)={(Weight before heating-Weight after heating)/Weight before heating}×100
[155]
[156]
Hereinafter, preferred embodiments are presented to aid in the understanding of the present description, but the following examples are only illustrative of the present description, and that various changes and modifications are possible within the scope of the present description and the scope of the technical idea will be apparent to those skilled in the art, It is natural that such modifications and modifications fall within the appended claims.
[157]
[158]
[Example]
[159]
Components used in the following Examples and Comparative Examples are as follows.
[160]
* Acid flocculant: sulfuric acid
[161]
* Salt flocculant: magnesium sulfate
[162]
[163]

[164]
55 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 85 parts by weight of 100 parts by weight of 1,3-butadiene as a monomer, 1.5 parts by weight of a fatty acid metal salt of C16 to C18 as an emulsifier, potassium carbonate (K 2 CO 3 ) as an electrolyte 0.15 parts by weight, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight control agent, and 0.3 parts by weight of potassium persulfate as an initiator were batch-administered, and polymerization was carried out at a reaction temperature of 70°C. At a polymerization conversion rate of 35 to 45%, 0.3 parts by weight of potassium persulfate was added at once, and the remaining amount of 1,3-butadiene was continuously added to react. After reacting to a polymerization conversion rate of 70 to 80%, 0.3 parts by weight of a saponified rosin acid was added and reacted, and the reaction was terminated at a conversion rate of 93% to prepare a conjugated diene rubber latex.
[165]
The average particle diameter of the prepared conjugated diene rubber latex was 3,000 Å, and the solid content was 55 to 60% by weight.
[166]
[167]

[168]
In a nitrogen-substituted polymerization reactor, 60 parts by weight of the conjugated diene rubber latex having a solid content of 55 to 60% by weight prepared above and 100 parts by weight of ion-exchanged water, 10 parts by weight of acrylonitrile, styrene 30 mixed in a separate mixing device A mixed solution consisting of parts by weight, 25 parts by weight of ion-exchanged water, 0.12 parts by weight of t-butyl hydroperoxide, 0.9 parts by weight of potassium rosinate, and 0.35 parts by weight of tertiary dodecyl mercaptan, and 0.054 parts by weight of dextrose, sodium pyrrophosphate 0.004 parts by weight and 0.002 parts by weight of ferrous sulfate were added together at 70° C. for 3 hours. After the addition is complete, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrrophosphate, 0.001 parts by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide are collectively added to the polymerization reactor, and the temperature is raised to 80°C. After raising the temperature over 1 hour, the reaction was terminated to prepare an ABS graft copolymer latex. At this time, the polymerization conversion rate was 97%.
[169]
[170]
Example 1
[171]
After adding 0.20 parts by weight of sulfuric acid to 100 parts by weight of the ABS graft copolymer latex (based on solid content) prepared above at 80° C., heating up to 87° C. over 20 minutes to agglomerate (first aggregation step), and then at 87° C. After adding 1.80 parts by weight of magnesium sulfate, the temperature was raised to 93° C. over 15 minutes to cause aggregation (second aggregation step). The aggregated ABS graft copolymer was dehydrated and dried to prepare an ABS graft copolymer powder. 27 parts by weight of the prepared ABS graft copolymer powder and 73 parts by weight of an acrylonitrile-styrene copolymer (LG Chemical, 92HR) were mixed into a mixer, and then melt-kneaded at 210°C using an extruder and pelletized, A specimen for measuring physical properties was prepared using an injection machine.
[172]
[173]
Examples 2 to 6
[174]
In Example 1, except that the contents of sulfuric acid and magnesium sulfate were changed as shown in Table 1 below, it was carried out in the same manner as in Example 1.
[175]
[176]
Comparative Example 1
[177]
After adding 2.0 parts by weight of sulfuric acid to 100 parts by weight of the ABS graft copolymer latex (based on solid content) prepared above at 80°C, heating up to 93°C over 30 minutes to coagulate and mature, and then aggregate and mature ABS graft aerial The polymer was dehydrated and dried to prepare an ABS graft copolymer powder. 27 parts by weight of the prepared ABS graft copolymer powder and 73 parts by weight of an acrylonitrile-styrene copolymer (LG Chemical, 92HR) were mixed into a mixer, and then melt-kneaded at 210°C using an extruder and pelletized, A specimen for measuring physical properties was prepared using an injection machine.
[178]
[179]
Comparative Example 2
[180]
In Comparative Example 1, it was carried out in the same manner as in Comparative Example 1, except that 2 parts by weight of magnesium sulfate was added instead of 2 parts by weight of sulfuric acid.
[181]
[182]
Comparative Example 3
[183]
In Comparative Example 1, it was carried out in the same manner as in Comparative Example 1, except that 1 part by weight of sulfuric acid and 1 part by weight of magnesium sulfate were mixed and added instead of 2 parts by weight of sulfuric acid.
[184]
[185]
Comparative Examples 4 to 7
[186]
It was carried out in the same manner as in Comparative Example 1, except that in Comparative Example 1, sulfuric acid and magnesium sulfate were mixed and added in the amounts shown in Table 2 below.
[187]
[188]
Comparative Examples 8 to 17
[189]
Example 1 was carried out in the same manner as in Example 1, except that the order and contents of sulfuric acid and magnesium sulfate were changed as shown in Table 3 below.
[190]
[191]
[Test Example]
[192]
The properties of the specimens prepared in Examples 1 to 6 and Comparative Examples 1 to 17 were measured by the following method, and the results are shown in Tables 1 to 3 below.
[193]
[194]
How to measure
[195]
* Glossiness: The glossiness of a specimen having a thickness of 1/8 inch (3.2 mm) was measured at a 45° angle according to ASTM D523.
[196]
* b value: The b value was measured using a Hunter Lab color meter.
[197]
* B value after stay: After staying in the injection machine at 250° C. for 15 minutes, the b value was measured using a Hunter Lab color meter.
[198]
* Scorch test (min.): A thermoplastic resin composition powder having a moisture content of 1% by weight or less was put in an aluminum foil in a state capable of contacting with oxygen in the atmosphere, and the time at which the hot air oven at 190°C was left to start carbonization was measured.
[199]
* Loss of heating (% by weight): After increasing the heating rate from 80℃ to 250℃ at 20℃/min in a nitrogen atmosphere, heating it under the condition of maintaining it at 250℃ for 60 minutes to analyze the weight of the resin before and after heating (TGA ) Was measured and calculated by the following equation (4).
[200]
[Equation 4]
[201]
Heating loss (% by weight)={(Weight before heating-Weight after heating)/Weight before heating}Х100
[202]
[203]
[Table 1]
division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
How to add flocculant Addition of the first coagulant and then the second coagulant
First flocculant (parts by weight) H 2 SO 4 0.2 H 2 SO 4 0.3 H 2 SO 4 0.5 H 2 SO 4 0.7 H 2 SO 4 0.7 H 2 SO 4 0.45
Second flocculant (parts by weight) MgSO 4 1.8 MgSO 4 1.7 MgSO 4 1.5 MgSO 4 1.3 MgSO 4 1.0 MgSO 4 1.4
Total coagulant (parts by weight) 2.0 2.0 2.0 2.0 1.7 1.85
b value 3.2 3.2 3.2 3.2 3.3 3.2
B value after stay 9 9 8 8 8 8
Gloss 97 97 97 97 96 97
Scorch Time (min.) 80 minutes or more 80 minutes or more 80 minutes or more 80 minutes or more 80 minutes or more 80 minutes or more
Heating loss (% by weight) 0.4 0.4 0.5 0.4 0.6 0.5
[204]
[Table 2]
division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7
Coagulant input method The first coagulant and the second coagulant are mixed and added
First flocculant (parts by weight) H 2 SO 4 2.0 - H 2 SO 4 1.0 H 2 SO 4 0.5 H 2 SO 4 0.5 H 2 SO 4 0.2 H 2 SO 4 1.0
Second flocculant (parts by weight) - MgSO 4 2.0 MgSO 4 1.0 MgSO 4 1.5 MgSO 4 1.0 MgSO 4 1.0 MgSO 4 0.2
Total coagulant (parts by weight) 2 2 2 2 1.5 1.2 1.2
b value 6.2 3.2 4.8 3.9 4.5 3.3 4.9
B value after stay 8 14 11 13 13 14 9
Gloss 85 95 90 93 90 93 89
Scorch Time (min.) More than 80 minutes 15 25 20 24 17 70
Heating loss (% by weight) 3.2 0.2 1.8 0.9 1.1 0.5 2.9
[205]
[Table 3]
division Comparative example
8 9 10 11 12 13 14 15 16 17
How to add flocculant Addition of the first coagulant and then the second coagulant
First flocculant (parts by weight) MgSO 4 0.2 MgSO 4 1.3 MgSO 4 1.8 MgSO 4 1.0 MgSO 4 0.2 H 2 SO 4 0.7 H 2 SO 4 0.2 H 2 SO 4 0.2 H 2 SO 4 0.7 H 2 SO 4 1.3
Second flocculant (parts by weight) H 2 SO 4 1.8 H 2 SO 4 0.7 H 2 SO 4 0.2 H 2 SO 4 0.2 H 2 SO 4 1.0 MgSO 4 0.9 MgSO 4 1.9 MgSO 4 1.0 MgSO 4 1.8 MgSO 4 0.7
Total coagulant (parts by weight) 2.0 2.0 2.0 1.2 1.2 1.6 2.1 1.2 2.5 2.0
b value 5.9 3.3 3.3 3.4 4.7 3.7 3.3 3.3 3.7 4.7
B value after stay 9 11 12 11 9 8 12 12 9 8
Gloss 86 90 93 91 88 89 94 92 89 91
Scorch Time (min.) More than 80 minutes 55 25 33 70 80 minutes or more 40 45 58 80
Heating loss (% by weight) 3 1.0 0.4 0.5 2.2 0.9 0.4 0.4 0.9 1.6
[206]
As shown in Tables 1 to 3, Examples 1 to 6 according to the present invention have high gloss, b-value measured using a Hunter Lab color meter and low b-value measured after staying at 250°C for 15 minutes. Not only the color was excellent, but the scorch time was long and the heating loss was low, so the processing characteristics were excellent.
[207]
On the other hand, Comparative Examples 1 and 2 including an acid coagulant or a salt coagulant alone and Comparative Examples 3 to 7 in which an acid coagulant and a salt coagulant were mixed and added collectively were the glossiness, the b value measured using a Hunter Lab color meter, and After staying at 250° C. for 15 minutes, the measured b value, scorch time, and heating loss were poor.
[208]
In addition, in Comparative Examples 8 to 12 in which a salt coagulant was added to coagulate and then an acid coagulant was added, the glossiness, the b value measured using a Hunter Lab color meter, and the b value measured after staying at 50°C for 15 minutes, and the scorch time Or the heating loss was poor.
[209]
In addition, the acid coagulant was added and then the salt coagulant was added to coagulate, but the total amount of the coagulant was small or excessive; Comparative Examples 13, 15 and 16; And Comparative Example 14 in which the salt coagulant was excessive was poor in gloss, b-value measured using a Hunter Lab color meter, b-value measured after staying at 250°C for 15 minutes, scorch time, or heating loss.
[210]
In addition, Comparative Example 17 in which the acid coagulant was included in an excessive amount was inferior in b value and heating loss measured using a Hunter Lab color meter.
[211]

Claims
[Claim 1]
Graft polymerization of 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyan compound to 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight to prepare a graft copolymer latex; A first coagulation step of coagulating by adding 0.10 to 0.80 parts by weight of an acid coagulant to 100 parts by weight of the prepared graft copolymer latex (based on solid content); And a second agglomeration step of coagulating by adding 0.96 to 1.85 parts by weight of a salt coagulant after the first coagulation step; wherein the total of the acid coagulant and the salt coagulant is 1.66 to 2.20 parts by weight-conjugated diene A method for preparing a compound-aromatic vinyl compound graft copolymer.
[Claim 2]
The method of claim 1, wherein the acid coagulant is at least one selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid and acetic acid.
[Claim 3]
The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graph according to claim 1, wherein the salt coagulant is at least one selected from the group consisting of magnesium sulfate, calcium sulfate, aluminum sulfate, magnesium chloride, calcium chloride, and aluminum chloride. Method for producing a T copolymer.
[Claim 4]
The vinyl cyan compound-conjugated diene compound- according to claim 1, wherein in the first aggregation step, an acid flocculant is added at 75 to 85°C, and the temperature is raised therefrom by a temperature of 5 to 10°C over 5 to 35 minutes. A method for producing an aromatic vinyl compound graft copolymer.
[Claim 5]
The vinyl cyan compound-conjugated diene compound- according to claim 1, wherein in the second agglomeration step, a salt coagulant is added at 80 to 95°C, and the temperature is increased by 5 to 10°C over 5 to 35 minutes. A method for producing an aromatic vinyl compound graft copolymer.
[Claim 6]
The method of claim 1, wherein the preparing of the graft copolymer latex comprises a total of 100 parts by weight of a conjugated diene rubber latex, an aromatic vinyl compound, and a vinyl cyan compound, 70 to 200 parts by weight of ion-exchanged water, and 0.1 to 2 parts by weight of an initiator. , 0.1 to 2 parts by weight of an emulsifier and 0.05 to 1.5 parts by weight of a molecular weight control agent are added to perform the polymerization reaction, and then the polymerization reaction is terminated at a polymerization conversion rate of 93 to 99% by weight. Method for producing a T copolymer.
[Claim 7]
The method of claim 1, wherein the preparing of the graft copolymer latex comprises 100 parts by weight of the conjugated diene compound, 30 to 100 parts by weight of ion-exchanged water, 0.5 to 3 parts by weight of emulsifier, 0.01 to 0.5 parts by weight of electrolyte, and molecular weight modifier. A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, comprising the step of preparing a conjugated diene rubber latex by adding 0.1 to 0.5 parts by weight and 0.1 to 1 part by weight of an initiator and polymerizing.
[Claim 8]
The vinyl cyan compound-conjugated diene compound-aromatic vinyl according to claim 1, wherein the method for preparing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer comprises a dehydration and drying step after an aggregation step. Method for producing a compound graft copolymer.
[Claim 9]
A vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, characterized in that produced by the production method according to any one of claims 1 to 8.
[Claim 10]
A thermoplastic resin composition comprising 20 to 40% by weight of the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of claim 9 and 60 to 80% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer.
[Claim 11]
The thermoplastic resin composition of claim 10, wherein the thermoplastic resin composition has a b value measured after staying at 250° C. for 15 minutes using a Hunter Lab calorimeter of 9 or less.
[Claim 12]
The thermoplastic resin composition of claim 10, wherein the thermoplastic resin composition has a glossiness of 90 or more as measured at a 45° angle by a gloss meter according to ASTM D523.
[Claim 13]
The method of claim 10, wherein the thermoplastic resin composition includes a thermoplastic resin composition powder having a moisture content of 1% by weight or less in an aluminum foil in a state capable of contacting oxygen in the atmosphere, leaving it in a hot air oven at 190°C, and measuring the time when carbonization starts. Thermoplastic resin composition, characterized in that the scorch time (scorch time) by the scorch test is 60 minutes or more.