KR20000038612A - Process for producing heat-resistant thermoplastic resin with improve gloss properties - Google Patents

Abstract

PURPOSE: An acrylonitrile-butadiene-styrene(ABS) resin with improved chemical resistance, high impacts, processability, and gloss properties is provided. CONSTITUTION: A ABS resin is provided by mixing 22-37 pts.wt. of graft ABS polymer having less than 0.7% of solidification powder and more than 26% of graft rate, 37-47 pts.wt. of a maleimide-based heat-resistant copolymer prepared by massive polymerization, 20-37 pts.wt. of acrylonitrile-styrene copolymer, an activator, an antioxidant, and a light-stabilizer in the extruding mixer at 230-250°C. The ABS polymer is prepared by copolymerizing 40-70 pts.wt. of a large diameter conjugated diene having an average particle size of 2500-5000 angstrom, 70-95% of gel and a swelling index of 12-30, 15-40 pts.wt. of an aromatic vinyl compound, 5-20 pts.wt. of a cyanide vinyl compound, 0.2-0.6 pts.wt. of an emulsifier, 0.2-0.6 pts.wt. of a molecular weight control agent, 0.1-0.5 pts.wt. of a polymerization initiator.

Description

Manufacturing method of heat resistant thermoplastic resin excellent in gloss

[Industrial use]

The present invention relates to a method for producing a heat-resistant thermoplastic resin, and more particularly graft acrylonitrile-butadiene-conjugated diene rubber latex having an appropriate particle diameter and gel content, aromatic vinyl compound, vinyl cyanide compound, etc. The present invention relates to a method for producing a styrene (ABS) polymer and kneading together a heat resistant copolymer having excellent heat resistance to produce a heat resistant ABS resin having excellent heat resistance, impact resistance, processability and the like and excellent gloss.

[Prior art]

Recently, a research to add high functionality to acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resins having excellent impact resistance, chemical resistance, and processability for electronic products requiring light weight of automobiles and heat resistance such as microwave oven and microwave oven. A lot is going on.

Conventionally, the method of manufacturing a heat resistant ABS resin has been proposed a lot of methods of kneading a graft ABS polymer and a heat resistant copolymer to produce a heat resistant ABS resin.

Looking at these, US Patent Nos. 3,010,936 and 4,659,790 include a method for producing a heat resistant ABS resin by including a heat resistant copolymer in which part or all of styrene is replaced with α-methylstyrene, and Japanese Patent Application Laid-Open No. 58- 206657, S. 63-162708, S. 63-235350, and U.S. Patent No. 4,757,109 propose a method for producing a heat resistant ABS resin by kneading a heat resistant copolymer prepared by containing a maleimide compound with a graft ABS polymer. It is. However, these methods have a problem in that the economic stability is reduced while the heat stability is lowered during processing, so that a lot of gas is generated, and the glossiness is lowered.

In addition, a method of producing a heat resistant ABS resin is known, such as a method of kneading with a polycarbonate resin and a method of filling an inorganic material. However, these methods have a problem in that heat resistance and impact resistance are improved, but workability and chemical resistance are deteriorated and they are expensive and have limitations in use.

And until now, the research for improving glossiness in the manufacturing method of a heat resistant thermoplastic resin has not been performed.

It is an object of the present invention to solve the problems of the prior arts and to provide a method for producing a low cost heat resistant thermoplastic resin which is excellent in heat resistance and processability and particularly excellent in gloss.

A specific object of the present invention is to prepare a graft ABS polymer having an appropriate graft ratio with a conjugated diene rubber latex having an appropriate particle size and gel content together with an aromatic vinyl compound and a vinyl cyan compound, and kneading together a heat resistant copolymer having excellent heat resistance. It is to provide a method for producing a heat resistant ABS resin excellent in heat resistance, impact resistance, workability and the like and excellent in gloss.

[Means for solving the problem]

According to the present invention, in manufacturing the heat-resistant ABS resin, using a maleimide compound having excellent thermal stability, using a heat-resistant copolymer that minimizes gas generation during processing and rubber latex optimized particle size and gel content to improve the graft rate By kneading the graft ABS polymer prepared, there is provided a method for producing a heat resistant thermoplastic resin having excellent heat resistance and workability and particularly excellent gloss.

The above objects and features and advantages of the present invention will become apparent from the following detailed description of the invention.

The maleimide type heat resistant copolymer used for kneading in order to manufacture the heat resistant ABS resin of the present invention has an emulsion polymerization method and a bulk polymerization method in the manufacturing method thereof. It is preferable to use a system copolymer.

The process for producing the heat resistant ABS resin of the present invention can be divided into a process for producing a graft ABS polymer used for kneading, a process for producing a maleimide-based heat resistant copolymer, and a process for kneading them.

Graft ABS Polymer Manufacturing Process

In the process for producing the graft ABS polymer, the particle diameter and the gel content of the conjugated diene rubber latex used in the manufacture of the graft ABS polymer have a great influence on the impact strength, processability, glossiness, and the like of the resin. In general, the smaller the particle diameter of the rubber latex is excellent glossiness, but the impact resistance and workability is lowered, the larger the particle diameter is excellent impact resistance, but the glossiness is lowered. In addition, the lower the gel content, the more the monomer swells in the rubber latex and the polymerization occurs, so that the apparent particle size is increased and the impact strength is improved, but the gloss is lowered. In addition, the graft ratio greatly affects the physical properties of the graft ABS polymer. However, when the graft ratio is lowered, the graft ratio is not grafted and there are many bare rubber latexes. In addition, the higher the content of the rubber latex and the larger the particle size, the graft glass is reduced, so there is a limit of improving the glossiness.

Therefore, a method for producing conjugated diene rubber latex having an appropriate particle size and gel content is important, and a method for increasing the graft ratio when grafting aromatic vinyl compound and vinyl cyanide compound to large diameter rubber latex is important.

The process for preparing the graft ABS polymer is described in detail as follows.

The first is the process of manufacturing small diameter rubber latex.

The small-diameter rubber latex used in the present invention is a conjugated diene polymer, the particle diameter is preferably 600 Pa to 1500 Pa, the gel content is 70% to 95%, the swelling index is preferably 12 to 30. If the gel content is 95% or more, the impact strength is lowered, and if it is 70% or less, the glossiness is lowered.

The manufacturing process is 100 parts by weight of conjugated diene, 1 to 4 parts by weight of emulsifier, 0.1 to 0.6 parts by weight of polymerization initiator, 0.1 to 1.0 parts by weight of electrolyte, 0.1 to 0.5 parts by weight of molecular weight regulator, 90 to 130 parts by weight of ion-exchanged water. After reacting at 50 to 65 ° C. for 7 to 12 hours, and further adding 0.05 to 1.2 parts by weight of a molecular weight modifier, and reacting at 55 to 70 ° C. for 5 to 15 hours, the average particle size was 600 to 1500 Å and the gel content was 70 A small-diameter conjugated diene rubber latex having a swelling index of 12 to 30% and% to 95% is prepared.

The emulsifiers used in the above processes are alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, alkali salts of rosin acids, and the like, and can be used alone or in mixture of two or more thereof.

The polymerization initiator used in the above process may be a water-soluble persulfate or a peroxy compound, and an oxidation-reduction system may also be used. The most suitable water-soluble persulfates are sodium and potassium persulfates, and fat-soluble polymerization initiators include cumenehydro peroxide, diisopropyl benzenehydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide and paramethane hydroperoxide. , Benzoyl peroxide and the like are used alone or in a mixture of two or more.

The electrolyte used in the above process may be KCl, NaCl, KHCO ₃ , K ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , K ₂ HPO ₄ , Na ₂ HPO ₄ , or the like. It is used in mixture of 2 or more types. In addition to the molecular weight regulators, mercaptans may be mainly used.

In this process, the polymerization temperature is very important for adjusting the gel content and swelling index of the rubber latex, and the selection of the initiator should also be considered.

Second is the process of manufacturing large diameter rubber latex, the process of fusion of small diameter rubber latex.

In general, since the large-diameter rubber latex particle diameter imparts a high impact to the thermoplastic resin, its preparation is very important and the particle diameter required to satisfy the physical properties in the present invention is 2500 kPa to 5000 kPa.

In the manufacturing process of the large-diameter rubber latex, that is, the small-diameter rubber latex fusion process, the particle diameter produced by the small-diameter rubber latex process is 600 kPa to 1500 kPa, the gel content is 70% to 95%, and the swelling index is 12 to 30. 2.5 parts to 4.5 parts by weight of acetic acid aqueous solution was slowly added to 100 parts by weight of phosphorus small-diameter rubber latex with stirring for 1 hour to enlarge the particles, and then the stirring was stopped, and the particle size was 2500 kPa to 5000 kPa, and the gel content was 70% to 95%. It is to prepare a large-diameter conjugated diene rubber latex for grafting copolymerization by fusing the swelling index to 12 to 30.

Third is the process for preparing the graft polymer.

Process for preparing the graft polymer is 15 to 40 parts by weight of an aromatic vinyl compound, 5 to 20 parts by weight of vinyl cyan compound, 0.2 to 0.6 parts by weight of an emulsifier, molecular weight modifier 40 to 70 parts by weight of the large diameter conjugated diene rubber latex prepared above 0.2 to 0.6 parts by weight and 0.1 to 0.5 parts by weight of the polymerization initiator are copolymerized. At this time, the polymerization temperature is 45 to 80 ℃, the polymerization time is preferably 3 to 5 hours.

The method of adding each component in the graft polymerization may include a batch method, a multi-step method, or a continuous method. In order to improve the graft rate and minimize the formation of coagulated products, a multi-step split method or a continuous method may be used. Preference method is preferred.

The emulsifiers used in the polymerization reaction are alkylaryl sulfonates, alkali methylalkyl sulfates, sulfonated alkyl esters, fatty acid soaps, alkali salts of rosin acids, and the like, and these may be used alone or as a mixture of two or more thereof.

As the molecular weight regulator, tertiary dodecyl mercaptan is mainly used.

Polymerization initiators include peroxides such as cumene hydroperoxide, diisopropylbenzenehydro peroxide, peranthate and the like, sodium formaldehyde succilate, sodium ethylenediamine tetraacetate, ferrous sulfate, textrose, sodium pyrrolate, sodium sulfite, and the like. An oxidation-reduction catalyst system consisting of a mixture with the same reducing agent can be used.

The polymerization conversion rate of the latex obtained after the completion of the polymerization was 96% or more. An antioxidant and a stabilizer were added to the latex to coagulate with an aqueous sulfuric acid solution at a temperature of 80 ° C. or higher, followed by dehydration and drying to obtain a powder. The stability of the graft copolymer latex prepared here is determined by measuring solid coagulation, as shown in Equation 1 below.

[Equation 1]

Solid Coagulation (%) = Product Coagulum in Reactor (g) / Weight of Total Rubber and Monomer x 100

When the solidified solid content is more than 0.7%, latex stability is extremely low, and it is difficult to obtain a graft polymer suitable for the present invention due to the large amount of coagulum.

The graft rate of the graft polymer is obtained by coagulating, washing and drying the graft polymer latex into powder form, adding 2 g of this powder to 300 ml of acetone, stirring for 24 hours, and then separating the solution from an ultracentrifuge and separating Check the graft rate by dropping the acetone solution into methanol to obtain the graft-free portion, drying it, and weighing it. The graft ratio is calculated by Equation 2 below.

[Equation 2]

Graft Rate (%) = Graft Monomer Weight / Rubber Weight x 100

At this time, if the graft ratio is 25% or less, the glossiness is lowered, which is not preferable in the present invention.

Maladei heat resistant copolymer

The maled heat resistant copolymer is prepared by bulk polymerization.

Kneading process

General SAN (acrylonitrile-styrene copolymer), a lubricant, an antioxidant, and an optical stabilizer were added to the graft ABS polymer and the maleimide heat-resistant copolymer prepared above as an extender, and kneaded, and then kneaded at 230 to 250 ° C. The heat resistant ABS resin of the pellets is prepared using a twin screw extruder at temperature.

The heat-resistant ABS resin thus prepared is injected into the prepared pellets to measure the physical properties it can be confirmed that the heat-resistant thermoplastic resin excellent in gloss of the present invention.

The present invention is described in detail by the following examples, these examples are intended to illustrate the invention, the invention is not limited to these.

EXAMPLE

Physical property measurement method used in the present invention is in accordance with the following standards and methods.

Notched Izod Impact Strength: ASTM D-256

Flow Index: ASTM D-1238

Heat Deflection Temperature (℃): ASTM D-648

Glossiness: Korean Industrial Standard KS A 0069

Drop size: Dynamic laser light skating method (device: Nicomp 370 HPL)

Gel content and swelling index: The rubber latex was solidified with dilute acid or metal salt, washed, dried in a vacuum oven at 60 ° C for 24 hours, and then chopped into pieces of rubber with scissors, and then 1 g of rubber was cut into 100 g of toluene. After storage in a dark room at room temperature for 48 hours, separated into sol and gel, and the gel content and swelling index are measured according to the following formula.

Gel content (%) = weight of insoluble content (gel) / weight of sample x 100

Swelling index = weight of swollen gel / weight of gel

Example 1

Small Diameter Rubber Latex Manufacturing

Small diameter rubber latex was prepared as follows. 100 parts by weight of ion-exchanged water, 100 parts by weight of 1,3-butadiene as monomer, 1.2 parts by weight of potassium rosin salt as emulsifier, 1.5 parts by weight of potassium oleate salt, and sodium carbonate (Na ₂ as electrolyte) in a nitrogen-substituted polymerization reactor (autoclave). 0.1 parts by weight of CO ₃ ), 0.5 parts by weight of potassium hydrogen carbonate (KHCO ₃ ), and 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator were added at once, and the reaction temperature was raised to 55 ° C. as an initiator. 0.3 parts by weight of potassium persulfate is added at once to initiate the reaction. After reacting for 10 hours, 0.05 part by weight of tertiary dodecyl mercaptan was further added again, and the reaction was terminated after adding the reaction at 65 ° C. for 8 hours. The rubber latex thus obtained had a particle size of 1000 GP, a gel content of 90%, and an swelling index of 18.

Large Diameter Rubber Latex Manufacturing (Small Diameter Rubber Latex Fusion Process)

Large diameter rubber latex was prepared as follows. 100 parts by weight of the small-diameter rubber latex prepared above was added to the reactor, the stirring speed was adjusted to 10 rpm, the temperature was adjusted to 30 ° C., 3.0 parts by weight of 7% acetic acid aqueous solution was gradually added for 1 hour, and then the stirring was stopped. And left for 30 minutes to fuse small diameter rubber latex. The rubber latex obtained by this fusion process had a particle size of 3100 mm 3, a gel content of 90% and a swelling index of 17.

Graft Polymerization

50 parts by weight of large-diameter rubber latex prepared by the fusion process in a nitrogen-substituted polymerization reactor, 65 parts by weight of ion-exchanged water, 0.35 parts by weight of potassium rosinate emulsifier, 0.1 parts by weight of sodium ethylenediaminetetraacetate, 0.005 parts by weight of ferrous sulfate And 0.23 parts by weight of formaldehyde sodium sulfoxylate were added at once to raise the temperature to 70 ° C. Here, 50 parts by weight of ion-exchanged water, 0.65 parts by weight of potassium rosinate, 35 parts by weight of styrene, 15 parts by weight of acrylonitrile, 0.4 parts by weight of T-dodecyl mercaptan, and 0.4 parts by weight of diisopropylene hydroperoxide were mixed. After continuously inputting for 3 hours, the temperature was raised to 80 ° C., aged for 1 hour, and the reaction was terminated. The latex thus obtained had a polymerization conversion of 97.5%, a solid coagulum of 0.2%, and a graft rate of 37%.

The latex was coagulated with an aqueous sulfuric acid solution, washed and powdered.

Maleimide Heat Resistant Copolymer

As the maleimide-based heat resistant copolymer, SAM 2 (manufactured by Nitto, Japan) manufactured by a bulk polymerization method was used.

Kneading process

30 parts by weight of the graft ABS polymer prepared above, 42 parts by weight of the maleimide-based heat-resistant copolymer, 28 parts by weight of 92 HR (LG Chemical), a general acrylonitrile-styrene copolymer (SAN), 0.5 parts by weight of lubricant, and oxidation 0.3 parts by weight of the inhibitor and 0.1 parts by weight of the light stabilizer were kneaded, and a heat resistant ABS resin of pellets was prepared at 240 ° C using a twin screw extruder. The pellets were injected to measure physical properties, and are shown in Table 1.

Example 2

After preparing small-diameter rubber latex and large-diameter rubber latex in the same manner as in Example 1, except that 60 parts by weight of rubber latex, 28 parts by weight of styrene, 12 parts by weight of acryronitrile were changed to the same as in Example 1 The graft polymer was prepared in the same manner. At this time, the graft polymer produced had a graft rate of 30% and a solid coagulant content of 0.3%.

In the kneading process, 26 parts by weight of the graft polymer, 42 parts by weight of the maleimide-based heat-resistant copolymer as in Example 1, and 32 parts by weight of the common acrylonitrile-styrene copolymer (SAN) as in Example 1 Except for changing the kneading and extrusion in the same manner as in Example 1 to prepare a heat-resistant ABS resin of the pellets. The pellets were injected to measure physical properties, and are shown in Table 1.

Example 3

After preparing small-diameter rubber latex and large-diameter rubber latex in the same manner as in Example 1, except that 45 parts by weight of rubber latex, 38 parts by weight of styrene, and 17 parts by weight of acrironitrile, respectively, The graft polymer was prepared in the same manner. At this time, the graft polymer produced had a graft rate of 45% and a solid coagulum content of 0.1%.

In the kneading process, 33 parts by weight of the graft polymer, 42 parts by weight of the maleimide heat-resistant copolymer as in Example 1, and 25 parts by weight of the general acrylonitrile-styrene copolymer (SAN) as in Example 1 Except for changing the kneading and extrusion in the same manner as in Example 1 to prepare a heat-resistant ABS resin of the pellets. The pellets were injected to measure physical properties, and are shown in Table 1.

Example 4

A small diameter rubber latex was produced in the same manner as in Example 1 except that the monomer was changed to 99 parts by weight of butadiene and 1 part by weight of styrene. The gel content of this small-diameter rubber latex was 94%. From the small-diameter rubber latex, a large-diameter rubber latex and a graft polymer were prepared in the same manner as in Example 1.

In addition, in the kneading process, the blending ratio of 30 parts by weight of the graft polymer, 42 parts by weight of the maleimide-based heat-resistant copolymer as in Example 1, and 28 parts by weight of the general SAN as in Example 1 and kneading by the same method as in Example 1 And extruded to produce a heat resistant ABS resin of the pellets. The pellets were injected to measure physical properties, and are shown in Table 1.

Comparative Example 1

After preparing the small-diameter rubber latex in the same manner as in Example 1, except that the acetic acid content was changed to 2.5 parts by weight, the large-diameter rubber latex was prepared in the same manner as in Example 1. At this time, the particle diameter of the large-diameter rubber latex was 2200 mm 3. From this large-diameter rubber latex, a graft polymer was prepared in the same manner as in Example 1.

In addition, in the kneading process, the blending ratio of 30 parts by weight of the graft polymer, 42 parts by weight of the maleimide-based heat-resistant copolymer as in Example 1, and 28 parts by weight of the general SAN as in Example 1 and kneading by the same method as in Example 1 And extruded to produce a heat resistant ABS resin of the pellets. The pellets were injected to measure physical properties, and are shown in Table 1.

Comparative Example 2

100 parts by weight of ion-exchanged water, 100 parts by weight of 1,3-butadiene as monomer, 1.2 parts by weight of potassium rosin salt as emulsifier, 1.5 parts by weight of potassium oleate salt, sodium carbonate (Na ₂₎ as an electrolyte in a nitrogen-substituted polymerization reactor (autoclave) CO ₃ ) 0.1 parts by weight, 0.5 parts by weight of potassium hydrogen carbonate (KHCO ₃ ) and 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator were added at once, and the reaction temperature was raised to 52 ° C. as an initiator. 0.3 parts by weight of potassium persulfate is added at once to initiate the reaction. After reacting for 10 hours, 0.05 part by weight of tertiary dodecyl mercaptan was further added again, and the reaction was terminated after adding the reaction at 62 ° C. for 8 hours. The small-diameter rubber latex thus obtained had a gel content of 65%.

Thus, a large diameter rubber latex and a graft polymer were prepared in the same manner as in Example 1 from the small diameter rubber latex prepared by lowering the polymerization temperature by 3 ° C. as compared to Example 1.

In addition, in the kneading process, the blending ratio of 30 parts by weight of the graft polymer, 42 parts by weight of the maleimide-based heat-resistant copolymer as in Example 1, and 28 parts by weight of the general SAN as in Example 1 and kneading by the same method as in Example 1 And extruded to produce a heat resistant ABS resin of the pellets. The pellets were injected to measure physical properties, and are shown in Table 1.

Comparative Example 3

After preparing small-diameter rubber latex and large-diameter rubber latex in the same manner as in Example 1, except that 71 parts by weight of rubber latex, 20 parts by weight of styrene, 9 parts by weight of acryronitrile were changed to the same as in Example 1 The graft polymer was prepared in the same manner. At this time, the graft polymer produced had a graft rate of 20% and a solid coagulum content of 0.4%.

In addition, in the kneading process, 22 parts by weight of the graft polymer, 42 parts by weight of the maleimide-based heat-resistant copolymer as in Example 1, and 36 parts by weight of a general SAN as in Example 1 were changed, except that the blending ratio of the polymers was changed. Kneading and extrusion were carried out in the same manner to prepare a heat resistant ABS resin of pellets. The pellets were injected to measure physical properties, and are shown in Table 1.

Comparative Example 4

After preparing small diameter rubber latex, large diameter rubber latex and graft in the same manner as in Example 1, 22 parts by weight of the graft polymer in the kneading process, α-methylstyrene instead of the maleimide-based heat-resistant copolymer as in Example 1 50 parts by weight of the system heat-resistant copolymer (LG Chemical Products PW633), 36 parts by weight of the general SAN as in Example 1, except that the blending ratio of the polymers was kneaded and extruded in the same manner as in Example 1 to heat-resistant ABS resin of the pellet Prepared. The pellets were injected to measure physical properties, and are shown in Table 1.

TABLE 1

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Graft ABS Polymer 30 parts by weight 26 parts by weight 33 parts by weight 30 parts by weight 30 parts by weight 30 parts by weight 22 parts by weight 30 parts by weight Heat Resistant Copolymer 42 parts by weight 42 parts by weight 42 parts by weight 42 parts by weight 42 parts by weight 42 parts by weight 42 parts by weight 50 parts by weight General SAN (92HR) 28 parts by weight 32 parts by weight 25 parts by weight 28 parts by weight 28 parts by weight 28 parts by weight 36 parts by weight 20 parts by weight Notched Izod Impact Strength 15 16 15 13 7 17 13 16 Flow index 11 10 10 12 9 10 8 8 Heat deflection temperature (℃) 107 106 107 108 108 106 105 105 Glossiness 96 95 96 97 95 86 80 78

ABS resin prepared by kneading the graft ABS polymer prepared by controlling the graft rate from the rubber latex optimized particle size and gel content and the maleimide-based heat-resistant copolymer prepared by bulk polymerization according to the present invention is heat-resistant, impact resistance and It is a high performance ABS resin with excellent workability and extremely excellent gloss.

Claims (11)

Polymer comprising 22 to 37 parts by weight of graft acrylonitrile-butadiene-styrene (ABS) polymer, 37 to 47 parts by weight of maleimide-based heat resistant copolymer, and 20 to 37 parts by weight of general acrylonitrile-styrene copolymer (SAN) Kneading, antioxidant, and light stabilizer were added to the mixture of these mixtures, and they were kneaded, and these were prepared as pellets in a twin screw extruder at a temperature of 230 to 250 ° C. Method for producing styrene (ABS) resin. The method of claim 1, Graft acrylonitrile-butadiene-styrene (ABS) polymer is a polymer having a solid coagulation content of 0.7% or less and a graft ratio of 26% or more, 40 to 70 parts by weight of conjugated diene rubber latex, 15 to 40 parts by weight of aromatic vinyl compound, vinyl A polymer produced by a method of emulsion polymerization comprising an emulsifier, a molecular weight regulator, and a polymerization initiator in a monomer mixture containing 5 to 20 parts by weight of a cyan compound. The method of claim 1, The maleimide copolymer is a copolymer produced by the bulk polymerization method. The method of claim 2, The conjugated diene rubber latex has an average particle diameter of 2500 to 5000 mm 3, a gel content of 70 to 95% and a swelling index of 12 to 30. The method of claim 2, Conjugated diene rubber latex is selected from aliphatic conjugated dienes or mixtures of aliphatic conjugated diene compounds and ethylenically unsaturated monomers. The method of claim 2, Wherein the aromatic vinyl compound is selected from the group consisting of styrene, α-methylstyrene, ο-etherylene, and ρ-vinyltoluene. The method of claim 2, The vinyl cyan compound is selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile. The method of claim 2, Wherein the emulsifier is selected from the group consisting of alkylaryl sulfonates, alkali methylalkyl sulfates, sulfonated alkyl esters, fatty acid soaps, rosinates. The method of claim 2, The molecular weight modifier is tertiary dodecyl mercaptan. The method of claim 2, Wherein the polymerization initiator is at least one selected from the group consisting of cumene hydroperoxide, diisopropylbenzene hydroperoxide, and persulfate. In the method for producing a heat resistant thermoplastic resin excellent in glossiness, a) 600-1500 kPa of particle diameters and 70-95% of gel content by emulsion polymerization containing conjugated diene. Preparing a small diameter conjugated diene rubber latex having a swelling index of 12 to 30; b) preparing a large-diameter rubber latex having a mean particle size of 2500-5000 mm, gel content of 70-95%, and swelling index of 12-30 by a fusion process from the prepared small-diameter conjugated diene rubber latex; c) preparing a graft acrylonitrile-butadiene-styrene (ABS) polymer having a solid coagulation content of 0.7% or less and a graft ratio of 26% or more from the prepared large-diameter latex; And d) preparing a heat-resistant acrylonitrile-butadiene-styrene (ABS) resin by kneading the graft ABS polymer prepared above by kneading the maleimide heat-resistant copolymer prepared by bulk polymerization. How to include.