KR102130569B1 - Method for preparing abs resin powder and method for preparing abs resin composition improved surface quality - Google Patents

Abstract

The present invention relates to a method of manufacturing an ABS-based resin powder and a method of manufacturing an ABS-based resin composition with improved surface properties, and more specifically, by introducing an acid flocculant into an ABS-based resin latex produced by emulsion polymerization to aggregate. Acid aggregation step; Aging step of aging the acid-agglomerated slurry; A base treatment step of adjusting the pH to 8 to 12 by adding a base to the aged slurry; And dehydrating the base-treated slurry 1 to 3 times, followed by drying to obtain an ABS-based resin powder, wherein the ABS-based resin powder has a residual emulsifier content of 5,000 ppm or less and is acid-free -free) and a method for manufacturing an ABS-based resin powder, and a method for producing an ABS-based resin composition having improved surface properties, including the same.

Description

Manufacturing method of ABS resin powder and manufacturing method of ABS resin composition with improved surface properties{METHOD FOR PREPARING ABS RESIN POWDER AND METHOD FOR PREPARING ABS RESIN COMPOSITION IMPROVED SURFACE QUALITY}

The present invention relates to a method of manufacturing an ABS resin powder and a method of manufacturing an ABS resin fired material having improved surface properties, and more specifically, a pH of 8 to 12 is introduced by adding a base to an acid-aggregated ABS resin latex. After the base treatment by adjusting with dehydration, the acid-emulsifier binder is removed by 60% or more, and the residual emulsifier content is 5,000 ppm or less and an acid-free method for producing ABS resin powder and surface gloss including the same , Yellowness, whiteness, and the like.

Acrylonitrile-butadiene-styrene (ABS) copolymer resins have excellent mechanical properties such as impact resistance, chemical resistance, molding processability, and glossiness, and provide various electrical and electronic parts, office equipment, and automobiles. It is widely used for interior and exterior materials.

In general, when an ABS resin is prepared by grafting an aromatic vinyl compound and a vinyl cyan compound monomer on a conjugated diene rubber latex by an emulsion polymerization method, it exhibits a good physical property balance compared to that produced by a bulk polymerization method and has excellent gloss, etc. Due to its advantages, ABS resins are mainly produced by emulsion polymerization.

In addition, the ABS-based resin latex produced by the emulsion polymerization method is preferably processed into a powder for the reduction of volume, various utilization and ease of handling, and usually, the ABS-based resin latex is agglomerated, aged, dehydrated and dried. An ABS resin powder can be obtained.

The aggregation of the ABS-based resin latex prepared by the emulsion polymerization can chemically aggregate latex particles stabilized by the emulsifier used in the emulsion polymerization using various flocculants, and the flocculant may use acid or metal salt. have. Aggregation of latex using an acid has a disadvantage that the thermal stability of the ABS-based resin is reduced by the residual acid, and the yellowness of the resin is high due to a large amount of gas generated during the thermoforming process. In addition, agglomeration of latex using a metal salt has a relatively low gas generation amount and yellowness, but has a problem of low productivity.

In addition, the gas generated on the resin surface during the thermoforming process is generated from impurities such as emulsifiers used in emulsion polymerization, and in order to solve the problem of deterioration of the resin, the amount of emulsifier used during polymerization is reduced, or when washing the aggregated latex. A method of diluting the residual emulsifier by adding an excessive amount of water has been proposed, but this method has a disadvantage of lowering the physical property balance and productivity of the ABS resin.

Therefore, there is a need for a technique for manufacturing an ABS-based molded article having improved surface properties such as yellowness and gloss while maintaining excellent mechanical properties while maintaining the inherent mechanical properties of ABS-based resins and having low gas generation during the thermoforming process. Is doing.

Korean Registered Patent No. 10-0463482

In order to solve the problems of the prior art as described above, the present invention has high productivity, less gas generation during the thermoforming process, and improves mechanical properties such as impact strength and surface properties such as glossiness and yellowness after molding. An object of the present invention is to provide a method for manufacturing an ABS resin powder.

In addition, an object of the present invention is to provide a method for producing an ABS-based resin composition excellent in heat resistance, mechanical properties, and surface properties, including the ABS-based resin powder according to the above manufacturing method.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention is an acid aggregation step of agglomeration by introducing an acid flocculant into an ABS resin latex prepared by emulsion polymerization of a rubber polymer, an aromatic vinyl compound, and a vinyl cyan compound; Aging the acid-agglomerated slurry; A base treatment step of adjusting the pH to 8 to 12 by adding a base to the aged slurry; Dehydration of the base-treated slurry, followed by drying to obtain a resin powder to obtain an ABS-based resin powder; includes, wherein the ABS-based resin powder has a residual emulsifier content of 5,000 ppm or less, acid-free (acid-fee It provides a method for producing an ABS-based resin powder, characterized in that.

In addition, the present invention comprises the steps of kneading and extruding 10 to 50% by weight of ABS-based resin powder and 50 to 90% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer according to the above production method. Provides a method for preparing a composition.

According to the present invention, after acid-agglomerating the ABS resin latex prepared by emulsion polymerization, the base is introduced and treated with base to dehydrate it to effectively remove the acid-emulsifier complex and residual acid, resulting in a residual content of 5,000 ppm. Below, an acid-free ABS-based resin powder can be produced with excellent yield.

In addition, the ABS-based resin powder according to the present invention is neutralized acid when preparing an ABS-based resin composition by mixing the ABS-based resin powder and the aromatic vinyl compound-vinyl cyan compound copolymer as no residual acid is present. It has the advantage that the addition of additives such as antacids can be omitted.

In addition, when the ABS-based resin composition is thermally molded by reducing the content of the residual emulsifier, the amount of gas generated is reduced to produce an ABS-based resin composition having excellent mechanical properties and improved surface properties such as gloss, yellowness and whiteness. have.

1 is a graph showing the results of measuring the temperature increase and loss in Example 1, Comparative Example 1 and Reference Example 1.

Hereinafter, the method of manufacturing the ABS-based resin powder and the method of manufacturing the ABS-based resin composition containing the same will be described in detail.

The present inventors can remove the acid-emulsifier conjugate by more than 60% by acid-agglomerating the ABS-based resin latex prepared through emulsion polymerization, and then adding a base to the acid-aggregated slurry, followed by base treatment and dehydration. By doing so, it is possible to manufacture an ABS resin powder having a reduced residue content of an emulsifier, etc., and confirming that the surface properties such as glossiness, yellowness, and whiteness of the ABS resin composition prepared therewith are improved. Based on this, the present invention has been completed.

In the present description, a powder refers to an object in a state in which a large number of solid particles are aggregated, and for example, an object having an average particle diameter in a state in which a large number of solid particles are aggregated is 1 to 10,000 μm or 10 to 2,000 μm. .

Acid in the base-emulsifier combination is meant a composite product formed by the combination of an emulsifier with an acid (acid) injected from the acid coagulation phase used in the emulsion polymerization, and carboxylates (RCOO ^-) for example formed by a combination of emulsifier and acid It may be a complex comprising a compound in the form of RCOO-H.

In the present disclosure, the complex may be, for example, a mixture containing a carboxylic acid metal salt, a carboxylic acid, an inorganic acid, and an inorganic acid metal salt.

In the present description, a slurry means a multi-particle assemblage formed by agglomeration of polymer particles in a latex as the electrostatic stabilization of the polymer latex by an emulsifier is broken, for example, a resin prepared by emulsion polymerization. It may be a resin aggregate formed by adding an acid coagulant to latex.

The ABS resin powder manufacturing method of the present invention comprises an acid aggregation step of agglomeration by adding an acid flocculant to an ABS resin latex prepared by emulsion polymerization of a rubber polymer, an aromatic vinyl compound, and a vinyl cyan compound; Aging step of aging the acid-agglomerated slurry; A base treatment step of adjusting the pH to 8 to 12 by adding a base to the aged slurry; After dehydrating the base-treated slurry, drying to obtain a resin powder to obtain an ABS-based resin powder; including, but, the ABS-based resin powder has a residual emulsifier content of 5,000ppm or less, acid-free (acid-fee It is characterized by being.

In the present invention, ABS-based resin latex is, for example, based on 100 parts by weight of a monomer mixture comprising 40 to 70% by weight of a rubber polymer (based on solids), 15 to 35% by weight of an aromatic vinyl compound and 5 to 25% by weight of a vinyl cyan compound, Emulsifier 0.01 to 5 parts by weight, including the initiator 0.001 to 3 parts by weight may be prepared by emulsion polymerization.

Other additives, such as polymerization water, electrolyte, etc., which are not specifically mentioned in the present description, polymerization reaction conditions, such as reaction temperature and reaction time, can be appropriately selected as needed, and are a range generally applied to the production of ABS resin latex. The case is not particularly limited.

In the present invention, the rubber polymer may be a polymer of a diene-based compound, and as a specific example, one type selected from the group including butadiene polymer, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene copolymer, and the like. It may be the above, but is not limited thereto.

In the present invention, the aromatic vinyl compound may be one or more selected from the group containing styrene, α-methylstyrene and p-methylstyrene, but is not limited thereto.

In the present invention, the vinyl cyan compound may be at least one selected from the group containing acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, but is not limited thereto.

In the present invention, the emulsifier is, for example, alkylaryl sulfonate salt, alkali methyl alkyl sulfate salt, sulfonated alkyl ester salt, alkyl (alkenyl) carboxylate, alkyl (alkenyl) succinate, fatty acid salt, rosin acid salt , Oleate, and the like, but may be one or more selected from the group including, but not limited to.

The acid aggregation step of the present invention is a step of agglutinating the ABS resin latex by adding an acid coagulant to the ABS resin latex prepared by emulsion polymerization, and the acid with respect to 100 parts by weight of ABS resin latex (based on solid content) It may be desirable to add the flocculant at 0.5 to 4 parts by weight, 0.5 to 3 parts by weight, 0.7 to 2.5 parts by weight or 1.5 to 2.2 parts by weight. Acid-free resin powder can be produced within the above-described range, and has an advantage of excellent surface properties such as glossiness and whiteness.

The acid agglutination step may be performed at a temperature of 60 to 90°C, for example, preferably at 75 to 85°C, and more preferably 70 to 80°C. In the temperature range, there is an advantage of high cohesion and excellent productivity.

In addition, the acid agglutination step may be performed for 5 to 20 minutes or 10 to 15 minutes under an agitation condition of 150 to 400 rpm or 250 to 350 rpm or 300 to 350 rpm, but is not limited thereto. Within the above-described range, there is an advantage that the productivity is excellent, the degree of aggregation is high, and the physical property balance is excellent.

The acid coagulant introduced in the acid aggregation step may be, for example, one or more selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid, and acetic acid, preferably sulfuric acid, and high cohesion when using it. There is an advantage of excellent productivity.

In the acid agglutination step, it may be possible to mix water with the acid coagulant or to respectively input them, and preferably, the acid coagulant and water are mixed to be added in the form of an acid aqueous solution.

The acid aqueous solution may be an aqueous solution of 0.01 to 1M (molar concentration), preferably 0.03 to 0.8M (molar concentration) or 0.1 to 0.7M (molar concentration). In addition, when each of the acid and water is added, it may be preferable to add water in an amount such that the concentration of the acid coagulant is 0.01 to 1 M (molar concentration). Within this range, an acid-free resin powder having high cohesiveness and productivity and free of residual acid can be obtained.

In the acid aggregation step, the pH of the slurr can be adjusted to 1 to 4.5, 1.5 to 4, or 2.5 to 4, and the cohesiveness within this range is high, so that the productivity of the ABS resin powder is excellent.

The present invention may further include a aging step of aging the acid-aggregated slurry at a temperature of 80 to 140°C or 100 to 140°C before base treatment of the acid-aggregated slurry, in which case the productivity of the resin powder is improved. It has the advantage of excellent surface properties such as glossiness, whiteness, heat resistance, mechanical strength, and the like.

The aged slurry contains an acid-emulsifier combination formed by combining the emulsifier used during emulsion polymerization with the acid introduced in the acid aggregation step, which vaporizes on the resin surface during the thermoforming process at 200 to 300°C to improve the surface properties of the resin. It can decrease.

Accordingly, the present invention includes a base treatment step of adjusting the pH to 8 to 12 by adding a base to the aged slurry, preferably the pH can be adjusted to 9.5 to 11.5, more preferably 10 to 11 It is. Within the above range, the residual emulsifier content is reduced, and since it does not contain residual acid, the amount of gas generated during thermoforming is reduced, and there is an advantage of excellent surface properties such as glossiness, yellowness, and whiteness.

The base treatment step may be performed at a temperature of 0 to 100°C, for example, preferably 30 to 90°C, more preferably 50 to 90°C or 70 to 80°C. Within the above range, the residual emulsifier content is more effectively reduced, and there is an effect of excellent surface properties such as glossiness and whiteness.

In addition, the base treatment step can be carried out for 1 to 60 minutes or 30 to 60 minutes under conditions of a stirring speed of 10 to 500 rpm or 300 to 500 rpm, and within this range is excellent in productivity, and prevents side reactions, thereby preventing physical deviations It is possible to manufacture resins with low mechanical strength, heat resistance, and surface properties.

The base to be introduced into the base treatment step may be, for example, one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate and sodium hydrogen carbonate, and preferably sodium hydroxide.

In the base treatment step, water may be mixed with the salt or may be respectively added, and preferably, a base and water are mixed to be added in the form of an aqueous base solution.

The base aqueous solution may be an aqueous solution of 0.01 to 5M (molar concentration), preferably 0.5 to 4M (molar concentration) or 2 to 4M (molar concentration). In addition, when salt and water are respectively added, it may be desirable to add water in an amount such that the concentration of the base is 0.01 to 5M (molar concentration). Within the above range, the residual emulsifier content is reduced, and since it does not contain residual acid, it has the advantage of excellent surface properties such as surface gloss and whiteness.

The step of obtaining the resin powder of the present invention is a step of obtaining the ABS-based resin in a powder form by dehydrating and drying the base-treated slurry.

The dehydration is not particularly limited when it is within a range that is generally practiced in the technical field to which the present invention belongs, and for example, the base-treated slurry can be dehydrated using a centrifugal dehydrator, a compression type dehydrator, or the like.

The dehydration may be preferably performed one or more times, 1 to 3 times, or 2 to 3 times repeatedly, in which case the acid-emulsifier combination is removed by 60% or more or 60 to 70% to reduce the residual emulsifier content in the final resin. Ultimately, there is an effect of improving the surface properties such as glossiness and whiteness of the resin.

The removal rate of the acid-emulsifier combination in the present description, after dissolving 0.3 g of ABS-based resin powder in 10 ml of THF, 30 ml of methanol was added to precipitate the polymer, and the supernatant was filtered, and liquid chromatography mass spectrometry (LC/MSD) It can be measured by quantitative analysis of the emulsifier component using.

The drying is not particularly limited in the case of a known drying process commonly performed in the technical field to which the present invention pertains, but for example, the dehydrated resin powder is supplied with air using a fluidized bed dryer to dry the resin powder. Can.

The wet powder resin obtained after dehydration may have a water content of 40% by weight or less, 10 to 40% by weight, 10 to 35% by weight, or 10 to 30% by weight, for example, in a post-process. There is an advantage in that productivity is increased by increasing the efficiency in the drying step.

In addition, the resin powder obtained by drying the resin in the wet powder state may preferably have a water content of, for example, 1% by weight or less or 0.1 to 0.5% by weight, excellent productivity of the resin within this range, and mechanical strength, It has the advantage of excellent physical properties such as heat resistance and surface gloss.

As described above, the ABS resin powder according to the manufacturing method of the present invention has an residual emulsifier content of 5,000 ppm or less, 4,800 ppm or less, 4,500 ppm or less, or 4,000 to 4,800 ppm, and does not contain residual acid. -free), and may have improved surface properties such as glossiness, whiteness, and yellowness by reducing the content of the residual emulsifier.

In addition, the ABS-based resin powder according to the manufacturing method of the present invention may be characterized in that the heat loss value calculated by the following Equation 1 is 0.4% by weight or less, 0.36% by weight or less, or 0.35% by weight or less.

[Equation 1]

Loss of heating (% by weight) = [1-(Weight after 60 minutes at 250℃)]/(Initial weight of sample) X 100

Other conditions that are not explicitly described in the ABS resin powder manufacturing method of the present invention described above are not particularly limited when they are within a range that is generally practiced in the technical field to which the present invention belongs, and can be appropriately selected and carried out do.

The ABS-based resin powder produced by the production method of the present invention may be mixed with an aromatic vinyl compound-vinyl cyan compound copolymer to be prepared as an ABS-based resin composition, hereinafter, a method for manufacturing an ABS-based resin composition according to the present disclosure. It will be described in detail.

The ABS-based resin composition manufacturing method of the present invention is, for example, mixing the ABS-based resin powder 10 to 60% by weight and the aromatic vinyl compound-vinyl cyan compound copolymer 40 to 90% by weight and extruding it according to the above manufacturing method It may be characterized by including.

In another example, the ABS-based resin composition of the present invention may be prepared by mixing and extruding 20 to 50% by weight of the ABS-based resin powder and 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer. .

When the content of the aromatic vinyl compound-vinyl cyan compound copolymer is within the above range, there is an advantage of excellent heat resistance, processability, and the like.

The aromatic vinyl compound-vinyl cyan compound copolymer may be, for example, a copolymer comprising 50 to 90% by weight of an aromatic vinyl compound and 10 to 50% by weight of a vinyl cyan compound, and as an example, 60 to 80% by weight of an aromatic vinyl compound And it may be a copolymer containing 20 to 40% by weight of a vinyl cyan compound. Within the above range, mechanical properties such as impact strength are excellent, and surface properties such as whiteness and glossiness are excellent.

The aromatic vinyl compound and the vinyl cyan compound may use one or more of the aromatic vinyl compound and the vinyl cyan compound used in the production of ABS resin latex, preferably the aromatic vinyl compound may be styrene, and the vinyl cyan compound is acrylic Nitrile.

In addition, the ABS-based resin composition may further include one or more additives selectively selected from lubricants, antioxidants, thermal stabilizers, and light stabilizers, if necessary.

The kneading and extrusion are not particularly limited, and for example, a composition may be uniformly dispersed using a single screw extruder, a twin screw extruder, or a Banbury mixer, and the composition may be uniformly kneaded and then extruded to produce pellets. .

The kneading and extrusion may be performed under conditions of, for example, 150 to 300°C and 100 to 500 rpm or 200 to 300°C and 200 to 300 rpm, but is not limited thereto.

The ABS-based resin composition according to the manufacturing method of the present invention may be characterized in that the glossiness is 99 or more, 100 or more, or 101 or more, and the whiteness is 47 or more or 47.5 or more, and the yellowness is 4 or less or 3.8 or less. can do.

In addition, the ABS-based resin composition has a flow index (220°C, 10 kg load) of 5 to 35 g/10min, 10 to 30 g/10min, or 20 to 30 g/10min, and thus has excellent molding processability and impact. The impact resistance is also excellent because the strength is 27 kgcm/cm or more.

Hereinafter, a preferred embodiment is provided to help the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is apparent to those skilled in the art that various changes and modifications are possible within the scope and technical scope of the present invention. It is no wonder that such variations and modifications fall within the scope of the appended claims.

[Example]

Example One

Preparation of ABS resin latex

90 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 60 parts by weight of polybutadiene rubber latex (average particle size: 3,000Å), 15 parts by weight of styrene, 7.5 parts by weight of acrylonitrile, alkenyl C16-18 succinate as an emulsifier 0.1 parts by weight of potassium salt (ELOPLA AS100) and 0.3 parts by weight of potassium fatty acid salt, 0.04 parts by weight of tert-butyl hydroperoxide as initiator and 0.4 parts by weight of tertiary dodecyl mercaptan, 0.05 parts by weight of sodium pyrophosphate, dextrose 0.05 Weight part, 0.001 part by weight of ferrous sulfide was batch-dosed and heated to 70° C. for one hour to perform polymerization. After polymerization for one hour, 10 parts by weight of ion-exchanged water, 15 parts by weight of styrene, 7.5 parts by weight of acrylonitrile, 0.1 parts by weight of alkenyl C16-18 succinate potassium salt (ELOPLA AS100) and 1.0 parts by weight of potassium fatty acid salt, tert -Continuous administration of mixed emulsifying solution mixture containing 0.04 parts by weight of butyl hydroperoxide, 0.05 parts by weight of sodium pyrophosphate, 0.05 parts by weight of dextrose, 0.001 parts by weight of ferrous sulfide, and 0.1 parts by weight of cumene hydroperoxide for 60 minutes After that, the temperature was raised to 80°C, aged for 1 hour, and the reaction was terminated.

ABS resin Powder Produce

By adding 2.0 parts by weight of a 5% sulfuric acid aqueous solution to 100 parts by weight of the ABS latex (solid content 45% by weight, average particle size 3,400 Å) prepared above, the aggregation temperature was solidified at 80°C for 15 minutes and aged at 95°C for 10 minutes. The aged latex was added with 1.4 parts by weight of a 10% aqueous sodium hydroxide solution and subjected to base treatment for 10 minutes. Subsequently, the base-treated slurry is put into a centrifugal dehydrator, dewatered using a centrifugal dehydrator for 90 seconds by adding the same amount of water as the base-treated slurry, washed, and then dried in a hot air dryer at 90°C for 30 minutes for ABS resin powder. Was obtained.

ABS resin composition production

27 parts by weight of the ABS resin powder prepared above, 73 parts by weight of a styrene-acrylonitrile copolymer, 1.2 parts by weight of a lubricant, and 0.2 parts by weight of an antioxidant are kneaded and extruded (temperature 210° C., 250 rpm) to prepare a pelletized ABS resin composition Did.

Example 2

It was carried out in the same manner as in Example 1, except that the aqueous solution of potassium hydroxide was used instead of the aqueous sodium hydroxide solution in Example 1.

Example 3

It was carried out in the same manner as in Example 1, except that the aqueous solution of formic acid was used instead of the sulfuric acid aqueous solution in Example 1.

Example 4

It was carried out in the same manner as in Example 1, except that the dehydration process in Example 1 was repeated twice.

Comparative example One

It was carried out in the same manner as in Example 1, except that the step of base treatment in Example 1 was omitted.

Comparative example 2

It was carried out in the same manner as in Example 1, except that the pH of the slurry was adjusted to 7 by adding an aqueous sodium hydroxide solution in the base treatment step of Example 1.

Reference example One

In the process of manufacturing the ABS resin powder of Comparative Example 1, it was carried out in the same manner, except that an aqueous solution of magnesium sulfate, which is a metal salt coagulant, was used instead of an aqueous sulfuric acid solution.

[Test Example]

The properties of the ABS resin powder and the ABS resin composition prepared in the above Examples, Comparative Examples and Reference Examples were measured by the following methods, and the results are shown in Table 1 and FIG. 1 below.

Izod Impact strength

The thickness of the specimen was 1/4" and measured by the ASTM D256 method.

Melt flow index (MI)

It was measured by ASTM D1238 method at a temperature of 220°C and a load of 10 kg.

Surface glossiness (45°)

Measured by ASTM D528 method at 45° angle.

Heat deflection temperature ( HDT : Heat Distortion Temperature)

By the method of ASTM D648, the heat deflection temperature of the specimen having a thickness of 1/4" was measured under the condition that the load was 18.6 kg/cm ² .

Yellowness

It was measured using a color meter (trade name: Color-eye 7000A, Gretamacbeth) by the method of ASTM E313.

Whiteness

The whiteness of the specimen was measured according to the CIE Lab method.

Residual acid analysis

After stirring and adding 10 ml of distilled water to a solution of 10 g of ABS resin powder dissolved in 100 ml of MEK (Methyl Ethyl Ketone), after separating the upper layer (MEK+resin) and lower layer (distilled water + residual acid), separate the lower layer to separate the lower layer 80 ml The remaining acid component was analyzed by titration with 0.01 M sodium hydroxide aqueous solution.

Residual emulsifier analysis

After dissolving 0.3 g of ABS resin powder in 10 ml of THF, 30 ml of methanol was added to precipitate the polymer, and the supernatant was filtered, and the emulsifier component was analyzed using a liquid chromatography mass spectrometer (LC/MSD).

Isothermal heating loss

The sample was heated at 250° C. for 60 minutes using a thermogravimetric analysis (TGA), and the weight changed was calculated, and the heating loss was calculated according to Equation 1 below.

[Equation 1]

Loss of heating (% by weight) = [1-(Weight after 60 minutes at 250℃)]/(Initial weight of sample) X 100

Elevated temperature Heating loss

TGA (Thermogravimetric Analysis) the sample was heated at a rate of 20 ℃ / min was measured by changing weight. The graph of the result of the heating loss was shown in FIG. 1.

Water content measurement

The moisture content of the wet powder obtained after the dehydration process was measured, and the weight change was measured after complete drying at 150°C using a moisture meter (METTLER/TOLEDO HR83-P).

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Reference Example 1 Flocculant Sulfuric acid Sulfuric acid Formic acid Sulfuric acid Sulfuric acid Sulfuric acid Sulfuric acid
magnesium Base treatment Hydroxide
salt Hydroxide
potassium Hydroxide
salt Hydroxide
salt - Hydroxide
salt - Dehydration frequency One One One 2 One One One Impact strength
(kgcm/cm) 27.7 27.7 27.7 27.8 26.2 26.3 27.4 Glossiness 101 99.7 100.5 100.1 98.4 98.2 101.3 Flow index (g/10min) 23.9 23.9 23.7 23.8 24.1 24 22.2 Heat deflection temperature (℃) 82.7 82.8 82.6 82.8 82.8 82.6 84.4 Yellowness 3.8 3.6 2.9 3.5 8.5 8.5 2.6 Whiteness 47 47.5 48.1 47.9 40.2 40 48.4 Residual acid (ppm) 0 0 0 0 270 50 0 Residual emulsifier (ppm) 4,300 4,800 4,800 3,800 16,100 16,000 13,200 Isothermal heating loss (% by weight) 0.35 0.36 0.35 0.35 1.15 1.17 0.34 Water content
(weight%) 26 26 29 27 26 26 37

As shown in Table 1, the ABS resin powders of Examples 1 to 4 prepared by including the base treatment step according to the present disclosure are excellent in gloss, yellowness, and whiteness compared to Comparative Examples 1 and 2 not according to the present description. It was confirmed that the impact strength, the flow index and the thermal strain temperature were similar to those of Comparative Examples 1 and 2.

In addition, when comparing the results of Examples 1 to 4, it can be seen that when the dehydration process is repeatedly performed, the effect of removing the residual emulsifier is more excellent. Could. On the other hand, in the case of the reference example using a metal salt coagulant, the surface properties of the resin were excellent, but it was confirmed that the water content was higher than in the examples and comparative examples.

In addition, Examples 1 to 4 according to the present disclosure can be confirmed that the acid coagulant is an acid-free resin that does not remain, and comparative examples and references as the acid-emulsifier binder is removed through a base treatment step It was confirmed that the residual emulsifier content was significantly lower than in the example.

Particularly, in the case of Comparative Example 2, the residual amount of the emulsifier was very high compared to Example 1, and the yellowness, whiteness, etc. It was confirmed that the surface properties were inferior to the examples.

Normally, the heating loss of the ABS-based resin powder is generated at a temperature of 300° C. or higher, but the emulsifier used in the production of the ABS-based resin latex generates a heating loss at 200 to 300° C. During the molding process, gas is generated on the surface of the resin to degrade the quality of the resin.

However, the resin powder according to the present invention can be confirmed that the reduction in the amount of heating and loss of isothermal heating compared to Comparative Examples 1 and 2 due to the reduction in the content of the residual emulsifier, and thus occurs on the resin surface when thermoforming at 200 to 300°C. The amount of gas to be reduced is to improve the surface properties of the resin.

Summarizing the above results, the ABS resin powder according to the present disclosure has surface properties such as glossiness, yellowness, and whiteness due to reduction of residual acid and residual emulsifier, while having mechanical properties and heat resistance equivalent to or higher than conventional ABS resin powder. It can be seen that this is improved and the physical property balance is excellent.

Claims (18)

Acid aggregation step of agglomeration by adding an acid flocculant to an ABS resin latex prepared by emulsion polymerization of a rubber polymer, an aromatic vinyl compound, and a vinyl cyan compound; Aging step of aging the acid-agglomerated slurry; A base treatment step of adjusting the pH to 8 to 12 by adding a base to the aged slurry; And a step of dewatering the base-treated slurry, followed by drying to obtain a resin powder to obtain an ABS-based resin powder.
The ABS resin powder has a residual emulsifier content of 5,000 ppm or less, and is acid-fee,
The pH of the acid-agglomerated slurry is 2.5 to 4,
The method of producing an ABS-based resin powder, characterized in that the water content of the resin powder is 0.1 to 0.5% by weight. According to claim 1,
The base treatment step is a method for producing an ABS-based resin powder, characterized in that is performed at a temperature of 30 to 90 ℃. According to claim 1,
The base is a method of producing an ABS-based resin powder, characterized in that at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate and sodium hydrogen carbonate. According to claim 3,
The base is a method of producing an ABS-based resin powder, characterized in that the aqueous solution of a concentration of 0.01 to 5M (molar concentration). According to claim 1,
The acid agglutination step, the ABS-based resin latex 100 parts by weight (based on solids), the method of producing an ABS-based resin powder characterized in that the acid flocculant is added in 0.5 to 4.0 parts by weight. According to claim 1,
The acid aggregation step is a method for producing an ABS-based resin powder, characterized in that is performed at a temperature of 60 to 90 ℃. According to claim 1,
The acid coagulant is a method for producing an ABS-based resin powder, characterized in that at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid and acetic acid. The method of claim 7,
The acid coagulant is a method for producing an ABS-based resin powder, characterized in that the aqueous solution of a concentration of 0.01 to 1.0M (molar concentration). delete According to claim 1,
The aging step is a method for producing an ABS-based resin powder, characterized in that is performed at a temperature of 80 to 140 ℃. According to claim 1,
The ABS-based resin powder is a method for producing an ABS-based resin powder, characterized in that the heating loss calculated by Equation 1 below is 0.4% by weight or less.
[Equation 1]
Loss of heating (% by weight) = [1-(Weight after 60 minutes at 250℃)]/(Initial weight of sample) X 100 10 to 60% by weight of ABS-based resin powder and 40 to 90% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer prepared according to any one of claims 1 to 8, 10 and 11, and Method of producing an ABS-based resin composition comprising the step of extruding. The method of claim 12,
The ABS-based resin composition is characterized in that it further comprises at least one additive selected from lubricants, antioxidants, thermal stabilizers and light stabilizers
Method for producing ABS resin composition. The method of claim 12,
The ABS-based resin composition is a method for producing an ABS-based resin composition, characterized in that the glossiness (45 °) measured in accordance with ASTM D528 is 99 or more. The method of claim 12,
The ABS-based resin composition is a method of manufacturing an ABS-based resin composition, characterized in that the whiteness is 47 or more measured according to the CIE Lab method. The method of claim 12,
The ABS-based resin composition according to ASTM E313, a color meter (trade name: Color-eye 7000A, Gretamacbeth Co., Ltd.) yellowness measured using a method of producing an ABS-based resin composition, characterized in that 4 or less. The method of claim 12,
The ABS resin composition has a flow index (220 ℃, 10kg load) of 5 to 35 g/10min, characterized in that the manufacturing method of the ABS resin composition. The method of claim 11,
The ABS-based resin composition is a method of manufacturing an ABS-based resin composition, characterized in that the impact strength is 27 kgcm / cm or more.

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