KR20200074565A - Method for preparing vinylcyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer - Google Patents

Abstract

The present invention relates to a method for preparing a vinylcyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer and, more particularly, to a method for preparing a vinylcyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, comprising the steps of: a) preparing a conjugated diene rubber latex by polymerizing 100 parts by weight of a conjugated diene monomer, 0.1 to 1.4 parts by weight of multimer of unsaturated fatty acid or metal salt thereof as an emulsifier, and 0.02 to 6 parts by weight of a water-soluble polymerization initiator; b) preparing a graft copolymer latex by carrying out a graft polymerization of 20 to 40 wt% of an aromatic vinyl compound and 1 to 20 wt% of a vinylcyan compound in 50 to 70 wt% of the prepared conjugated diene rubber latex (based on a solid content); and c) carrying out an aggregation by adding 0.1 to 1.0 parts by weight of a polymer coagulant and 0.5 to 1.6 parts by weight of an acid coagulant into 100 parts by weight of the prepared graft copolymer latex (based on a solid content). According to the present invention, there is an effect of providing a method for preparing a vinylcyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, which is easy to work due to a small amount of gas generated during injection molding, has excellent appearance quality of a molded product, and has excellent thermal stability and surface clarity.

Description

Manufacturing method of vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer {METHOD FOR PREPARING VINYLCYAN COMPOUND-CONJUGATED DIENE COMPOUND-AROMATIC VINYL COMPOUND GRAFT COPOLYMER}

The present invention relates to a method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, more specifically, less gas generation during injection molding, easy work, excellent appearance quality of the injection, excellent thermal stability and It relates to a method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer having excellent surface clarity.

Acrylonitrile-butadiene-styrene copolymers (hereinafter referred to as “ABS graft copolymers”) represented by vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymers have impact resistance, mechanical strength, moldability, It has good properties such as glossiness, and is widely used in various fields such as electric parts, electronic parts, office equipment, and automobile parts.

ABS graft copolymers can be usually produced by emulsion polymerization, bulk polymerization, etc. When produced by emulsion polymerization, they have a relatively good physical property balance and excellent gloss. Therefore, ABS graft copolymers are mainly produced by emulsion polymerization rather than bulk polymerization. The ABS graft copolymer prepared by emulsion polymerization is mixed with a styrene-acrylonitrile (SAN) copolymer to make the most of the properties of the composition of the SAN resin to diversify the product and create high added value. have.

On the other hand, in the production of the ABS graft copolymer, the impact resistance of the resin is greatly influenced by the particle size and the particle size distribution of the dispersed rubbery polymer, so to obtain an ABS graft copolymer having excellent impact resistance, the particle size of the dispersed rubbery polymer is required. You have to get something big.

In addition, the glossiness or clarity of the ABS graft copolymer is affected not only by the particle size and particle distribution of the dispersed rubbery polymer, but also by emulsifiers, residual monomers, oligomers, heat stabilizers, SAN, etc. that remain after polymerization during the high temperature injection process. The gas generated on the surface of the resin is affected by the impurities. In particular, the gas generated on the surface of the resin during the high-temperature injection process is known to affect the roughness of the surface, thereby significantly reducing the glossiness or clarity of the resin, thereby inhibiting the quality of the resin.

Korean Registered Patent No. 0179314

In order to solve the problems of the prior art as described above, the present invention is easy to work due to a small amount of gas generated during injection molding, the appearance quality of the injection material is excellent, and the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound excellent in thermal stability and surface clarity It is an object to provide a method for producing a graft copolymer.

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 includes a) 100 parts by weight of a conjugated diene monomer, 0.1 to 1.4 parts by weight of a multimer acid of an unsaturated fatty acid as an emulsifier or a metal salt thereof, and 0.02 to 6 parts by weight of a water-soluble polymerization initiator. Step of preparing a conjugated diene rubber latex by polymerization reaction, b) Graft 50 to 70% by weight of the prepared conjugated diene rubber latex (based on solid content), 20 to 40% by weight of the aromatic vinyl compound and 1 to 20% by weight of the vinyl cyan compound Step to prepare a graft copolymer latex by polymerization, and c) 0.1 to 1.0 parts by weight of a polymer flocculant and 0.5 to 1.6 parts by weight of an acid flocculant are added to 100 parts by weight of the prepared graft copolymer latex (based on solid content). It provides a method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer comprising the step of.

The sum of the total weight of the polymer flocculant and the acid flocculant in step c) may be, for example, 1.0 to 1.7 parts by weight.

The unsaturated fatty acid of step a) may be, for example, a straight chain or branched or cyclic unsaturated fatty acid having 8 to 22 carbon atoms.

The step a) may include, for example, 0.1 to 1.5 parts by weight of at least one emulsifier selected from the group consisting of a metal salt of a rosin acid metal salt, an alkyl aryl sulfonate, an alkali methyl alkyl sulfate, a sulfonated alkyl ester, and an unsaturated fatty acid. have.

The conjugated diene monomer of step a) may be, for example, one or more selected from the group consisting of 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene and chloroprene.

The water-soluble polymerization initiator of step a) may be, for example, one or more selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate.

The conjugated diene rubber latex of step a) may have, for example, an average particle diameter of 2700 to 3300 mm 2.

The graft polymerization of step b) is 100 parts by weight of a reaction mixture comprising a conjugated diene rubber latex (based on solid content), an aromatic vinyl monomer, and a vinyl cyan monomer prepared as an example, 0.05 to 1 part by weight of an emulsifier and 0.01 to 1 of an initiator. It can be carried out by adding parts by weight.

The polymer flocculant in step c) includes, for example, an unsaturated carboxylic acid, an ester monomer thereof, or a mixture thereof, 10 to 30% by weight of a polymerized core; And 65 to 85% by weight of the unsaturated carboxylic acid, an ester monomer thereof, or a mixture thereof, surrounding the core; And it may be a polymeric flocculant comprising a graft polymerization formed shell containing 5 to 15% by weight of a comonomer having an amide group.

The acid coagulant in step c) may be one or more selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid, nitric acid, phosphoric acid and acetic acid.

The c) step of aggregation may be that the polymer coagulant and the acid coagulant are separately added at 75 to 85° C. to the prepared graft copolymer latex.

For example, the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer may have a gas generation amount of 1,900 ppm or less during injection.

The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer may have, for example, a residual metal content of 765 ppm or less, and a reflection haze of 1.1 or less.

According to the present invention provides a method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer which is easy to work due to a small amount of gas generated during injection molding, has excellent appearance quality of an injection material, and has excellent thermal stability and surface clarity. It works.

Hereinafter, a method for producing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (hereinafter referred to as "ABS graft copolymer") of the present disclosure will be described in detail.

The present inventors reduce the total emulsifier use amount including a predetermined emulsifier when manufacturing the conjugated diene rubber latex, and then introduce a predetermined amount of the polymer flocculant during the agglomeration process of the latex during the production of the ABS graft copolymer gas during injection molding. It was confirmed that the amount of occurrence was reduced and the surface clarity of the manufactured injection material was greatly improved, and based on this, more research was conducted to complete the present invention.

The method for preparing the ABS graft copolymer of the present invention includes a) 100 parts by weight of a conjugated diene monomer, 0.1 to 1.4 parts by weight of a multimer acid of an unsaturated fatty acid as an emulsifier or a metal salt thereof, and 0.02 to 6 parts by weight of a water-soluble polymerization initiator. Step of preparing a conjugated diene rubber latex by polymerization reaction, b) 50 to 70% by weight of the prepared conjugated diene rubber latex (based on solid content), 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyan compound Preparing a graft copolymer latex by graft polymerization, and c) adding 0.1 to 1.0 parts by weight of a polymer flocculant and 0.5 to 1.6 parts by weight of an acid flocculant to 100 parts by weight of the prepared graft copolymer latex (based on solid content). It characterized in that it comprises a step of agglomeration. In this case, there is an effect of providing an ABS graft copolymer that is easy to work due to a small amount of gas generated during injection molding, has excellent appearance quality of the injection, and has excellent thermal stability and surface clarity.

Hereinafter, the present invention will be described in detail step by step.

a) Preparation of conjugated diene rubber latex

The manufacturing step of the conjugated diene rubber latex according to the present disclosure includes a) 100 parts by weight of a conjugated diene monomer, 0.1 to 1.4 parts by weight of a multimer acid of an unsaturated fatty acid as an emulsifier or a metal salt thereof, and 0.02 to 6 parts by weight of a water-soluble polymerization initiator. It may be a step of preparing a conjugated diene rubber latex by polymerization reaction, and in this case, an amount of gas generated during injection molding is reduced, thereby preventing deterioration of the appearance characteristics of the molded product, that is, improving the appearance characteristics.

In one example, the conjugated diene rubber latex production step is iii) 45 to 90 parts by weight of 100 parts by weight of the conjugated diene monomer used, 0.1 to 1.4 parts by weight of a multimer of unsaturated fatty acids or metal salts thereof, and 0.01 to soluble polymerization initiator 0.01 to The polymerization reaction including 3 parts by weight; Ii) 10) to 55 parts by weight of the conjugated diene monomer and 0.01 to 3 parts by weight of a water-soluble polymerization initiator at the time of polymerization conversion of 25 to 55% after the step iii), and in this case, conjugated diene rubber latex and ABS When preparing a graft copolymer, polymerization stability is improved, and furthermore, an ABS graft copolymer having good mechanical properties is obtained in a high yield due to a decrease in coagulant content.

In the present description, the multimer acid of an unsaturated fatty acid is a polyvalent carboxylic acid obtained by polymerization of two or more unsaturated fatty acids, and in the present invention, the unsaturated fatty acid is a linear, branched, cyclic, polycyclic unsaturated fatty acid or its It is assumed that a derivative is included.

In the present description, a derivative means a compound in which one or two or more of hydrogen of the original compound is substituted with an alkyl group, a halogen group or a hydroxy group.

In the present description, the compound cyclic type means that at least two saturated or unsaturated cycloalkyl groups having 5 to 15 carbon atoms are included in the molecule.

Polymerization conversion rate in the present disclosure can be calculated by using the prepared latex 1.5 g in a 150° C. hot air dryer for 15 minutes, measuring the weight to obtain a total solids content (TSC), and using Equation 1 below. This equation is based on the total weight of the injected monomer is 100 parts by weight.

[Equation 1]

Polymerization conversion rate (%) = [Total solid content (TSC) X (weight of injected monomers and auxiliary materials) / 100]-(weight of added auxiliary materials other than monomers)

In the present description, the total solid content (TSC) means a value obtained by evaporating moisture from latex and converting the amount of solid material remaining as a percentage.

The conjugated diene monomer of the present invention may include, for example, one or more compounds selected from the group consisting of 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene and chloroprene, and derivatives thereof may also be used. Yes.

In step iii), for example, 45 to 90 parts by weight, 55 to 90 parts by weight, or 65 to 90 parts by weight, preferably 75 to 90 parts by weight, of 100 parts by weight of the conjugated diene monomer used for preparing the conjugated diene rubber latex is added. If it can be used within this range, the number of base particles formed at the beginning of the reaction is appropriate, and the base particles can be largely cured in a short period of time, but there is an advantage of not causing an overreaction by polymerization heat.

Another example of the present invention may be used by mixing the conjugated diene monomer with an ethylenically unsaturated monomer copolymerizable therewith.

The ethylenically unsaturated monomer may include, but is not limited to, one or more compounds selected from the group consisting of aromatic vinyl compounds, acrylic acid esters, methacrylic acid esters, and vinyl cyan compounds, for example.

When the ethylenically unsaturated monomer is included, it may be preferable to use 20 parts by weight or less or 0.1 to 20 parts by weight based on 100 parts by weight of the monomers used in preparing the conjugated diene rubber latex, and within this range, conjugated diene rubber It is possible to improve the oil resistance and tensile strength of the resin produced from latex.

The emulsifier used in step iv) of the present invention may preferably contain a multimer acid of unsaturated fatty acids or a metal salt thereof, which has a higher molecular weight than conventional emulsifiers for PBL production, such as rosin acid metal salts, so as to It is possible to improve the glossiness and clarity of the injection product by reducing the amount of gas generated.

The unsaturated fatty acid may be, for example, a straight chain, branched or cyclic unsaturated fatty acid having 8 to 22 carbon atoms, which can improve the stability of the conjugated diene rubber latex, as well as reduce the amount of gas generated in the injection process, thereby reducing the amount of resin. It can contribute to the improvement of quality.

The emulsifier of step iv) may use, for example, a dimer acid of unsaturated fatty acids or a metal salt thereof, which improves the stability of the conjugated diene rubber latex and reduces the amount of gas generated in the injection process, thereby contributing to the improvement of the resin quality. Can.

The emulsifier of step iv) may be one or more dimer acids or metal salts thereof selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 6, which is improved in stability of large-diameter conjugated diene rubber latex and prepared from the latex. It can contribute to the improvement of the quality of the ABS graft copolymer injection, that is, the injection molded product, especially surface gloss and clarity.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In a more specific example, the emulsifier is 3-octenic acid, 10-undecenoic acid, oleic acid, linoleic acid, elaidic acid, palmitoleic acid, lenolenic acid, or a mixture of unsaturated carboxylic acids, tall oil fatty acid, soybean oil fatty acid, palm oil fatty acid, It is noted that dimer acids or metal salts thereof derived from compounds selected from the group comprising Uji fatty acids, Donji fatty acids, Abji fatty acids, Rice bran oil fatty acids, and Flaxseed oil fatty acids may be used, but are not limited thereto.

Also, the metal salt may be an alkali metal salt or an alkaline earth metal salt, the alkali metal salt may be, for example, a sodium salt or a potassium salt, and the alkaline earth metal salt may be, for example, a magnesium salt or a calcium salt, but is not limited thereto. do.

The multimer of the unsaturated fatty acid or a metal salt thereof may be, for example, 0.1 to 1.4 parts by weight, 0.2 to 1.2 parts by weight, or 0.3 to 1.0 parts by weight, preferably 0.4 to 0.7 parts by weight based on 100 parts by weight of the conjugated diene monomer. In addition, within the above-described range, while the stability of latex is excellent, the amount of gas generated on the resin surface during the high-temperature injection process is reduced, thereby improving the surface glossiness and clarity of the injection product.

The critical micelle concentration (CMC) of the emulsifier is, for example, preferably in the range of 0.01 to 0.15 mol/L or 0.01 to 0.05 mol/L, which promotes the formation of base particles of the conjugated diene rubber polymer, thereby reducing the amount of emulsifier. It is possible to make a latex excellent in thermal stability while having a desired average particle size even when used.

In the present description, the critical micelle concentration (CMC) of the emulsifier can be determined by preparing a 25mM emulsifier aqueous solution, diluting the concentration at 0.5mM intervals by adding distilled water thereto, and measuring the respective conductivity at 25°C and atmospheric pressure.

In addition, the emulsifier is, for example, one or more selected from the group consisting of metal salts of metal salts of rosin acids, alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, and unsaturated fatty acids. It can be used by mixing in parts by weight, preferably 0.5 to 1.5 parts by weight, more preferably 0.5 to 1.0 parts by weight, and within the above range, the content of latex is reduced, and at the same time, the amount of gas generated in the injection process at high temperature is reduced. It can contribute to the improvement of the quality of the ABS graft copolymer.

The water-soluble polymerization initiator of step iv) may be one or more selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate.

The amount of the water-soluble polymerization initiator used in step iii) may be preferably 0.01 to 3 parts by weight, 0.1 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.1 to 1 part by weight, for example, when used within the above range. It has the advantage of preventing coagulation and producing a large-diameter latex with a uniform size distribution.

In addition, the polymerization reaction of iv) may be preferably performed at 50 to 80°C, 60 to 80°C or 65 to 75°C for 0.5 to 5 hours, 1 to 3 hours or 1 to 2 hours, for example. Within the range, there is an effect of forming base particles for producing a conjugated diene rubber polymer having a large diameter within a short time.

The step iii) may further include an electrolyte or a molecular weight modifier as needed.

The electrolyte may be preferably used in an amount of 0.01 to 3 parts by weight or 0.1 to 1.5 parts by weight based on 100 parts by weight of the conjugated diene monomer as an example, and within this range, large diameter can be cured in a short time by fusion between base particles formed at the beginning of the reaction. It has the advantage of being able to.

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 and K ₂ HPO ₄ , Na ₂ HPO ₄ may be selected from the group consisting of one or more, but is not limited thereto.

For example, the molecular weight modifier may be preferably used in an amount of 0.01 to 3 parts by weight or 0.2 to 0.7 parts by weight based on 100 parts by weight of the conjugated diene monomer. When the molecular weight modifier is further included within the above range, a rubbery latex having a desired average particle size and uniform size may be prepared.

The molecular weight modifier may be a mercaptan compound such as tertiary dodecyl mercaptan, for example, but is not limited thereto.

Step ii) of the present invention is, for example, 10 to 55 parts by weight, 10 to 45 parts by weight, 10 to 35 parts by weight, or 10 to 25 parts by weight of the total 100 parts by weight of the conjugated diene monomer polymerization conversion rate of 25 to 55%, 30 to It may be characterized in that it is introduced at 50% or 35 to 45%, and within the above-described range, it may be possible to manufacture a conjugated diene rubber polymer having a large diameter evenly distributed in a short time.

When the total amount of the conjugated diene monomer is not added in the initial stage of the reaction, and a partial amount is added at a polymerization conversion rate of 25 to 55% after partial injection in the initial stage of the reaction, the productivity of latex is improved.

In addition, the conjugated diene monomer of the step ii) may be preferably continuously added up to a polymerization conversion rate of 60 to 85%, which minimizes the amount of unreacted monomers present in the reactants to prevent side reactions and to achieve a uniform size distribution. It may enable the production of conjugated diene rubber latex.

In the present description, the continuous input is continuously adding or drop-by-drop the compound input to the reaction for a predetermined time, 1 minute to 2 hours, 10 minutes to 1 hour, or 20 to 50 minutes without a pause, or among the compounds. It is assumed that all the cases in which a predetermined amount is added over 2 or more steps, 5 or more steps, or 5 to 20 steps are included.

In one example, the continuous input of step ii) may mean that the conjugated diene monomer used in step ii) is introduced over 2 to 5 steps.

In another example, the continuous injection of step ii) may mean that the conjugated diene monomer is injected at a rate of 0.01 to 0.2 g/min from a polymerization conversion rate of 25 to 55% to a time of 60 to 85%.

The water-soluble polymerization initiator of step ii) may be, for example, one or more selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate, and the amount used is 0.01 to 3 parts by weight, 0.1 to 3 parts by weight, 0.1 It may be preferably from 2 parts by weight or 0.1 to 1 part by weight, and when it is added within this range, it may be possible to produce a large-diameter rubbery polymer having an even average particle diameter in a relatively short time.

In addition, if the water-soluble polymerization initiator is not added at the initial stage of the reaction but is added at the initial stage of the reaction for the first time and then added at a polymerization conversion rate of 25 to 55%, a high degree of polymerization can be achieved and the stability of the latex is improved by easy heat removal. Can be.

For example, the polymerization reaction may be terminated at a polymerization conversion rate of 90 to 99%, 93 to 99%, 95 to 99%, or 97 to 99%, and the polymerization degree is high within the above range and the particle distribution is uniform. Conjugated diene rubber polymers can be prepared.

The conjugated diene rubber latex according to the present invention is a large-diameter conjugated diene rubber latex, and for example, it may be preferable to have a value of 2700 to 3300 mm 2 or 2900 to 3200 mm 2, and is prepared from rubber having a particle diameter within the above range. ABS graft copolymer has the advantage of excellent mechanical properties, surface properties and balance of properties.

The average particle diameter of latex in this substrate can be calculated as an intensity value in a Gaussian mode using Nicomp 370HPL as a dynamic laser light scattering method after mixing 1 g of latex with 100 g of distilled water.

The conjugated diene rubber latex according to the present invention may preferably have a coagulant content of 0.1 part by weight or less, 0.08 part by weight or less, or 0.05 part by weight or less based on 100 parts by weight of the latex, and ABS having excellent mechanical properties within the above range There is an advantage that a graft copolymer can be obtained in high yield.

In the present description, the coagulum content (Coagulum, g/100g) of latex can be calculated by measuring the weight of the coagulum produced in the reactor, the total rubber weight, and the monomer weight and using Equation 2 below.

[Equation 2]

Coagulant content = weight of coagulum produced inside the reactor (g) / total rubber weight and monomer weight (100 g)

Other reaction conditions, such as the amount of polymerization water, the reaction pressure, etc., other than the above-mentioned description, are not particularly limited when they are within the range commonly used in the technical field to which the present invention belongs, and indicate that they can be appropriately selected and carried out as necessary.

b) Preparation step of graft copolymer latex

In the production step of the graft copolymer latex according to the present disclosure, 50 to 70% by weight of the conjugated diene rubber latex (based on solid content), 20 to 40% by weight of the aromatic vinyl compound and 1 to 20% by weight of the vinyl cyan compound are grafted. It may include a step of preparing a graft copolymer latex by polymerization, and within this range, there is an effect of excellent impact resistance, mechanical strength, and moldability.

In one example, the manufacturing step of the graft copolymer latex is grafted to the above-mentioned conjugated diene rubber latex 55 to 65% by weight (based on solid content) of 25 to 35% by weight of aromatic vinyl compound and 5 to 15% by weight of vinyl cyan compound; It may include a step of preparing a graft copolymer latex by polymerization, and within this range, there is an effect of excellent impact resistance, mechanical strength, and moldability.

The graft polymerization may be polymerized by including at least one selected from the group consisting of emulsifiers, initiators, and molecular weight modifiers.

As a specific example, the graft polymerization is conjugated diene rubber latex 50 to 70% by weight (based on solid content), 70 to 150 parts by weight of ion-exchanged water, 20 to 40% by weight of aromatic vinyl compound, 1 to 20% by weight of vinyl cyan compound , 10 to 50 parts by weight of ion-exchanged water, 0.5 to 3 parts by weight of the initiator, 0.1 to 2 parts by weight of the emulsifier and 0.05 to 1.5 parts by weight of the molecular weight modifier were added thereto to polymerize for 2 to 4 hours at 65 to 75°C After the preparation, the initiator may be added with 0.05 to 0.5 parts by weight, heated to 75 to 80°C over 30 minutes to 90 minutes, and then terminated graft polymerization at a polymerization conversion rate of 93 to 99% by weight, in this case impact resistance, mechanical It has an effect of excellent strength and formability. Here, the total weight of the conjugated diene rubber latex (based on solid content), the aromatic vinyl compound, and the vinyl cyan compound is 100 parts by weight.

The vinyl cyan compound may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof.

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, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyl toluene, vinyl xylene, fluorostyrene and vinyl naphthalene.

The emulsifier used in the preparation of the ABS graft copolymer is, for example, 0.05 to 1 part by weight or 0.1 to 1 part by weight based on 100 parts by weight of the reaction mixture consisting of conjugated diene rubber latex (solid content), aromatic vinyl compound, and vinyl cyan compound. It may be desirable to deny, which can contribute to improving the physical property balance of the copolymer prepared by ensuring the stability of the graft polymerization reaction.

The emulsifier used in manufacturing the ABS graft copolymer may use a compound that is commonly used in the same technical field, and specifically, a rosin acid metal salt, a C10 to C18 fatty acid metal salt, or the like may be used.

The initiator may be, for example, an oxidation-reduction-based initiator or a fat-soluble peroxide-based initiator, and for example, tertiary butyl hydroperoxide or benzoyl peroxide may be used.

In addition, the initiator may be preferably used in an amount of 0.01 to 1 part by weight or 0.05 to 1 part by weight based on 100 parts by weight of the monomer mixture, for example, and the content of the initiator remaining in the resulting ABS graft copolymer is within the above range. It has the effect of promoting the polymerization reaction while minimizing it.

The manufacturing method of the ABS graft copolymer may further include a molecular weight modifier and an oxidation-reduction catalyst as needed, and the molecular weight modifier may use mercaptan compounds such as tertiary dodecyl mercaptan, for example, , The oxidation-reduction-based catalyst may be, for example, ferrous sulfate, dextrose, sodium pyrrophosphate, sodium sulfite, and other compounds, but is not limited thereto.

The manufacturing method of the ABS graft copolymer is not particularly limited when other reaction conditions, such as reaction time, reaction temperature, pressure, reactant input time, etc., are within the range commonly used in the technical field to which the present invention belongs, in addition to the above-described substrates, It can be carried out by appropriately selecting as necessary.

c) agglomeration step

The agglutination step according to the present disclosure may include aggregating the polymer graft copolymer latex by adding 0.1 to 1.0 part by weight of the polymer flocculant and 0.5 to 1.6 part by weight of the acid flocculant, Within the range, the amount of gas generated during injection molding is reduced, thereby preventing the deterioration of the appearance characteristics of the molded article, that is, the effect of improving the appearance characteristics.

The polymer flocculant may be, for example, 0.10 to 0.80 parts by weight, preferably 0.10 to 0.50 parts by weight, and within this range, the amount of gas generated during injection molding is reduced, thereby improving the appearance characteristics of the molded article.

The acid coagulant may be, for example, 0.6 to 1.5 parts by weight or 1.0 to 1.5 parts by weight.

The content of the polymer flocculant in the present description means the solid content or the content of the polymer flocculant component only when the state of the polymer flocculant used is a solution, slurry, or latex.

The sum of the total weight of the polymer flocculant and the acid flocculant may be, for example, 1.0 to 1.7 parts by weight or 1.2 to 1.7, preferably 1.4 to 1.7, and most preferably 1.4 to 1.6, within this range. Agglomeration is achieved efficiently, and the surface clarity is excellent.

The aggregation of step c) may be divided into a polymer coagulant and an acid coagulant at 75 to 85°C in the graft copolymer latex prepared as an example, and in this case, the powder has a uniform effect after the agglomeration.

The splitting input is, for example, the acid coagulant is added within 5 to 10 minutes after the polymer coagulant is added, or as another example, the polymer coagulant and the acid coagulant mixture is roughly evenly divided into 2 to 4 times at intervals of 5 to 10 minutes. It may be introduced, in this case has the effect of reducing the amount of coagulant, thereby reducing impurities and economic benefits.

The agglomeration step may further include, for example, antioxidants, stabilizers, or a mixture thereof, and in this case, there is an excellent effect in physical properties balance after extrusion.

The polymer flocculant is, for example, an unsaturated carboxylic acid, an ester monomer thereof, or a core formed by polymerizing the mixture 10 to 30% by weight; And 65 to 85% by weight of the unsaturated carboxylic acid, an ester monomer thereof, or a mixture thereof, surrounding the core; And 5 to 15% by weight of a comonomer having an amide group, and may be a polymer flocculant comprising a shell formed by graft polymerization, and in this case, flocculation is efficiently performed, and surface clarity is excellent.

The unsaturated carboxylic acid or its ester monomer may be, for example, at least one selected from the group consisting of ethylenically unsaturated carboxylic acid, its ester monomer, and acrylate monomers.

The unsaturated carboxylic acid polymer may further include at least one comonomer selected from the group consisting of C4 to C6 conjugated double bond monomers, monovinyl aromatic hydrocarbon monomers, and vinyl cyan monomers, in this case, mechanical properties. And it has the effect of improving the surface gloss.

The ethylenically unsaturated carboxylic acid may be, for example, one or more selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid.

The unsaturated carboxylic acid ester monomer may be, for example, an alkyl ester of the unsaturated carboxylic acid, that is, an alkyl unsaturated carboxylic acid ester.

The comonomer having the amide group may be, for example, metaacrylamide, acrylamide, or a mixture thereof, and in this case, there is an effect of effectively colliding particles in the latex to increase the particle size.

As another example, the polymer flocculant may be a copolymer having a core-shell structure, in which case latex stability is excellent, solid solidification is reduced, and when it is used in manufacturing an ABS graft copolymer, impact strength, etc. It has the effect of improving the same mechanical properties.

The method for preparing the polymer flocculant having the core-shell structure is, for example, (10) polymerizing the core by introducing 10 to 30 parts by weight of an unsaturated carboxylic acid or its ester monomer relative to 100 parts by weight of the monomers used; (ii) polymerizing the shell by introducing an unsaturated carboxylic acid, an ester monomer thereof, or 65 to 85 parts by weight of a mixture thereof and 5 to 15 parts by weight of a comonomer having an amide group at a polymerization conversion rate of 80 to 95%; And (iii) terminating the polymerization at a polymerization conversion rate of 98% or more; and may be prepared by including, in this range, the effect of increasing the rubber latex is excellent, the stability of the latex is improved, and the solid coagulation effect is reduced. have.

A preferable example of the polymer flocculant may be a butyl acrylate-methacrylic acid-methacrylamide copolymer having a core-shell structure, and in this case, it has an effect of reducing solidified solids while efficiently enlarging the rubber latex.

In step (i), for example, 0.1 to 0.5 parts by weight of an emulsifier, 0.05 to 0.5 parts by weight of a molecular weight modifier, 0.1 to 0.7 parts by weight of an initiator, and 60 to 70 parts by weight of ion-exchanged water may be emulsion-polymerized at 65 to 75°C. .

As another example, the step (i) is 0.1 to 0.3 parts by weight of an emulsifier, 0.1 to 0.3 parts by weight of a molecular weight modifier, 0.2 to 0.5 parts by weight of an initiator, and 60 to 65 parts by weight of ion-exchanged water to perform emulsion polymerization at 65 to 75°C. Can.

In step (i), the emulsifier is, for example, one selected from the group consisting of docusate sodium, allyl aryl sulfonate, alkali methyl alkyl sulfonate, sulfonated alkyl ester, fatty acid soap, and rosin acid alkali salt. It may be abnormal.

In the step (i), the molecular weight modifier and the initiator may include, for example, those used in the preparation of a) conjugated diene rubber latex described above.

In the step (ii), for example, an unsaturated carboxylic acid or an ester monomer thereof, and a mixture of 0.05 to 0.5 parts by weight of a molecular weight modifier in a comonomer having an amide group, 0.5 to 1 parts by weight of an initiator, and 0.01 to 0.5 parts by weight of an emulsifier are continuously added. While it can be emulsion-polymerized at 65 to 75 ℃, in this case is excellent cohesive effect.

As another example, the step (ii) is a mixture of an unsaturated carboxylic acid or an ester monomer thereof, and a 0.1 to 0.3 part by weight of a molecular weight modifier mixed with a comonomer having an amide group, 0.6 to 0.8 parts by weight of an initiator, and 0.03 to 0.1 parts by weight of an emulsifier Emulsion polymerization can be performed at 67 to 73°C while continuously being charged.

The molecular weight modifier, emulsifier and initiator used in step (ii) may include, for example, those used in the preparation of a) conjugated diene rubber latex described above.

In step (ii), an unsaturated carboxylic acid or an ester monomer thereof, and a comonomer having an amide group may be added as an emulsion, for example.

The method for preparing the emulsion is not particularly limited when it is a method generally recognized in the art.

The step (iii) may, for example, terminate the reaction at a polymerization conversion rate of 98% or more, or 99% or more, to obtain a polymer flocculant, and within this range, a polymer flocculant having a high degree of polymerization and an effect of increasing rubber latex is obtained. can do.

ABS graft copolymer

The aggregated ABS graft copolymer may be obtained as an ABS graft copolymer in powder form (Dry Powder; DP) through, for example, aging, dehydration, and drying steps.

The aging, dehydration and drying steps are not particularly limited when the method is generally used in the art.

For example, the aging may be performed at a temperature of 90 to 95°C or 91 to 93°C for 10 to 80 minutes, preferably 40 to 80 minutes, and within this range, there is an effect of increasing the aggregation efficiency in a slurry state.

After the aging, the obtained slurry can be dehydrated using a centrifugal dehydrator, a compression chamber dehydrator, or the like to obtain an ABS graft copolymer in a wet powder state.

The ABS 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% It may be weight%, and in this case, there is an advantage in that productivity is increased by increasing efficiency in a drying step, which is a post-process.

In the present description, the water content (% by weight) was completely dried at 150° C. and then calculated using Equation 3 below.

[Equation 3]

Water content (% by weight) = {(Weight of latex resin powder before drying (g)-weight of latex resin powder after drying (g))/weight of latex resin powder before drying (g)} X 100

The drying is not particularly limited in the case of a known drying process that is commonly practiced in the technical field to which the present invention pertains, but, for example, air using a fluid bed dryer using an ABS graft copolymer in a wet powder state After supplying ), it is possible to obtain an ABS graft copolymer powder after drying.

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

The powder form of the ABS graft copolymer may be prepared, for example, by melt-kneading and extruding to pellets.

The melt kneading and extrusion steps are, for example, 200 to 280°C and 200 to 500 rpm, 220 to 260°C and 200 to 400 rpm, or 220 to 240°C and 250 to 400 rpm, preferably 225 to 235°C. And 300 to 400 rpm, but is not limited thereto.

The melt kneading and extrusion may be performed using, for example, a half-bar mixer, a single-screw extruder, a twin-screw extruder, a kneader rebound, etc., and are not particularly limited.

When the melt-kneading, for example, the ABS graft copolymer and the aromatic vinyl compound-vinyl cyan compound copolymer relative to the total weight of the aromatic vinyl compound-vinyl cyan compound copolymer is 50 to 90% by weight or 70 to 80% by weight of ABS It can be added together with the graft copolymer, and in this case, it has an excellent effect in physical properties balance.

The aromatic vinyl compound and vinyl cyan compound of the aromatic vinyl compound-vinyl cyan compound copolymer may include, for example, those used in the preparation of the above-described b) graft copolymer latex.

When melt-kneading, for example, one or more additives selected from the group consisting of colorants, heat stabilizers, light stabilizers, reinforcing agents, fillers, flame retardants, lubricants, plasticizers, antistatic agents and processing aids, 0.1 to 10 parts by weight or 0.1 to 5 parts by weight It can be additionally added within the range of parts by weight.

The ABS graft copolymer according to the present invention, for example, the gas generation amount at the time of injection may be 1,900 ppm or less, 1,850 ppm or less, or 1,800 ppm or less, preferably 1,650 ppm or less, and an effect of excellent surface quality and appearance characteristics within this range There is.

The ABS graft copolymer may have, for example, a residual metal content of 765 ppm or less or 755 ppm or less, preferably 745 ppm or less, and a reflection haze of 1.1 or less or 1.0 or less, and preferably 0.9 or less. There is an effect excellent in surface clarity within this range.

Hereinafter, a preferred embodiment is provided to help the understanding of the present invention, but the following examples are merely 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]

<Preparation of polymer flocculant>

After filling the inside of the reactor with nitrogen or argon gas, 62 parts by weight of ion-exchanged water, 0.1 parts by weight of docusate sodium as emulsifier, 25 parts by weight of butyl acrylate, 2 parts by weight of methacrylic acid, and 3rd grade dodecane with molecular weight regulator 0.1 parts by weight of mercaptan (TDDM) and 0.3 parts by weight of potassium persulfate as an initiator were added in batch, followed by emulsion polymerization at 70°C. During the emulsion polymerization, 90 parts by weight of polymerization conversion ratio (based on batch monomer conversion rate) was mixed with 63 parts by weight of butyl acrylate, 10 parts by weight of methacrylamide, and 0.1 parts by weight of a molecular weight modifier, and added for 4 hours, and 0.7 parts by weight of potassium persulfate as an initiator. And 0.05 parts by weight of docusate sodium was emulsion-polymerized at 70° C. for 5 hours. During the emulsion polymerization, polymerization was terminated at a polymerization conversion rate of 95% or higher, and the obtained polymer flocculant had a core-shell structure and an average particle diameter of 2708 mm 2.

Example 1

Preparation of conjugated diene rubber latex

In a nitrogen-substituted polymerization reactor (autoclave), 60 parts by weight of ion-exchanged water, 75 parts by weight of 1,3-butadiene, 1.0 part by weight of dimer acid saponified as an emulsifier and 0.8 part by weight of fatty acid soap, 1.5 parts by weight of potassium carbonate as an electrolyte, As a molecular weight modifier, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) and 0.3 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as an initiator were collectively administered and polymerized at a reaction temperature of 70°C. After the polymerization reaction, at a time when the polymerization conversion rate was 30 to 40%, 25 parts by weight of 1,3-butadiene and 0.15 parts by weight of potassium persulfate were added at once, followed by polymerization at 70°C. Subsequently, at a time when the polymerization conversion rate is 60%, 0.03 parts by weight of t-butyl hydroperoxide, 0.054 parts by weight of dextrose, 0.04 parts by weight of sodium pyrrolate, and 0.002 parts by weight of ferrous sulfate are added, and the temperature is raised to 80° C. to polymerize the reaction. To prepare a conjugated diene rubber latex. The prepared conjugated diene rubber latex had an average particle diameter of 3,000 Å.

Preparation of ABS graft copolymer

60 parts by weight of conjugated diene rubber latex (based on solid content) and 100 parts by weight of ion-exchanged water prepared in the nitrogen-substituted polymerization reactor, 10 parts by weight of acrylonitrile, 30 parts by weight of styrene, and ions mixed in a separate mixing device 25 parts by weight of exchanged water, 0.12 parts by weight of t-butyl hydroperoxide, 0.9 parts by weight of potassium rosin and 0.35 parts by weight of tertiary dodecyl mercaptan, 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrrophosphate, and 0.002 part by weight of ferrous sulfate was added together at 70° C. for 3 hours. After the addition, 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 were collectively added to the polymerization reactor, and the temperature was raised to 80°C. After heating over 1 hour, the reaction was terminated to prepare an ABS graft copolymer latex. At this time, the polymerization conversion rate was 97%.

100 parts by weight of the prepared ABS graft copolymer latex (based on solid content), 0.2 parts by weight of the prepared polymer flocculant (based on solid content), and 1.5 parts by weight of sulfuric acid at a concentration of 98% by weight at 76°C, and then 91 to 92 The temperature was raised to ℃ to aggregate. The aggregated ABS graft copolymer was aged for 60-80 minutes at 91-92° C., followed by dehydration and drying to prepare an ABS graft copolymer powder. It was made into pellets under the conditions of 220°C and 400 rpm using a twin screw extruder, and then injected under the conditions of an injection temperature of 210°C and a mold temperature of 220°C using an injection machine to prepare specimens for physical property measurement.

Example 2

It was carried out in the same manner as in Example 1, except that 0.5 part by weight of dimer acid saponified instead of 1.0 part by weight of dimer acid saponified in Example 1.

Example 3

In Example 1, 0.5 parts by weight of dimer acid saponification was added instead of 1.0 parts by weight, 0.5 part by weight of polymer flocculant was added instead of 0.2 parts by weight, and 1.0 part by weight of sulfuric acid was added instead of 1.5 parts by weight. It was carried out in the same manner as in 1.

Example 4

In Example 1, 0.7 parts by weight of dimer acid saponification was added instead of 1.0 parts by weight, 0.5 parts by weight of polymer flocculant was added instead of 0.2 parts by weight, and 1.0 part by weight of sulfuric acid was added instead of 1.5 parts by weight. It was carried out in the same manner as in 1.

Comparative Example 1

In Example 1, it was carried out in the same manner as in Example 1, except that only 1.7 parts by weight of sulfuric acid was added instead of 1.5 parts by weight of sulfuric acid and 0.2 parts by weight of polymer flocculant.

Comparative Example 2

In Example 1, except that 1.0 part by weight of dimer acid saponide was added instead of 1.0 part by weight of dimer acid saponification, and 1.5 parts by weight of sulfuric acid and 0.2 part by weight of polymer flocculant were added, and only 1.7 parts by weight of sulfuric acid was added. It was carried out in the same way.

Comparative Example 3

In Example 1, 0.05 parts by weight of dimer acid saponification was added instead of 1.0 parts by weight, 1.5 parts by weight of polymer flocculant was added instead of 0.2 parts by weight, and 1.0 part by weight of sulfuric acid was added instead of 1.5 parts by weight. It was carried out in the same manner as in 1.

Comparative Example 4

In Example 1, 0.05 parts by weight of dimer acid saponification was added instead of 1.0 parts by weight, 0.05 parts by weight of polymer flocculant was added instead of 0.2 parts by weight, and 1.0 part by weight of sulfuric acid was added instead of 1.5 parts by weight. It was carried out in the same manner as in 1.

[Test Example]

The properties of the ABS graft copolymers prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were measured by the following method, and the results are shown in Table 1 below.

* Gas generation during injection (ppm): Total amount of volatile organic compounds (VOC) generated at 250° C. for 1 hour was analyzed for 1 g of ABS graft copolymer powder prepared using HS-GC/MSD. At this time, the smaller the amount of gas generated during injection, the better the ease of injection work and has less influence on the appearance characteristics of the injection.

* Reflection Haze: It was measured by adding gloss values between 17 and 19° and 21 and 23° according to standard measurement ASTM E430 with RhopointQ equipment from Rhopointinstruments.

* Residual metal content (ppm): 0.1 g of the sample was taken in a vial and was wet decomposed with sulfuric acid, nitric acid and hydrogen peroxide, and then diluted to 20 g with ultrapure water. Residual metal content was measured by ICP for this sample. For reference, the smaller the residual metal content in the prepared ABS graft copolymer powder (DP), the better the thermal stability of the resin.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Dimer acid saponification (parts by weight) 1.0 0.5 0.5 1.0 2.0 Sulfuric acid (parts by weight) 1.5 1.5 1.0 1.7 1.7 Polymer flocculant (parts by weight) 0.2 0.2 0.5 - - Gas generation during injection (ppm) 1,800 1,600 1,400 2,100 2,500 Reflection haze 1.0 0.9 0.8 1.2 1.5 Residual metal content (ppm) 750 740 600 790 1,090

division Example 4 Comparative Example 3 Comparative Example 4 Dimer acid saponification (parts by weight) 0.7 0.05 0.05 Sulfuric acid (parts by weight) 1.0 1.0 1.0 Polymer flocculant (parts by weight) 0.5 1.5 0.05 Gas generation during injection (ppm) 1600 2500 1300 Reflection haze 0.9 1.4 1.0 Residual metal content (ppm) 730 900 800

As shown in Table 1, according to the method for preparing the ABS graft copolymer of the present invention, dimer acid saponide is used as an emulsifier in the production of butadiene rubber latex within a predetermined content range, and the polymer is aggregated when the ABS graft copolymer latex is aggregated. When a flocculant and a sulfuric acid flocculant are used within a predetermined content range (see Examples 1 to 3), a polymer flocculant is not used (see Comparative Example 1), or an excess of dimer acid saponification is used (see Comparative Example 2), and Compared to the case where the polymer flocculant was used in an excessive amount or in a very small amount (refer to Comparative Examples 3 and 4), it was confirmed that the gas generation amount and the residual metal content during injection molding were greatly reduced and the surface quality was excellent.

Claims (13)

a) comprising 100 parts by weight of a conjugated diene monomer, 0.1 to 1.4 parts by weight of an unsaturated fatty acid multimer acid or a metal salt thereof and 0.02 to 6 parts by weight of a water-soluble polymerization initiator as an emulsifier to prepare a conjugated diene rubber latex ,
b) 50 to 70% by weight of the prepared conjugated diene rubber latex (based on solid content), 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyan compound are graft polymerized to prepare a graft copolymer latex. , And
c) characterized in that it comprises the step of agglomeration by adding 0.1 to 1.0 parts by weight of polymer flocculant and 0.5 to 1.6 parts by weight of acid flocculant to 100 parts by weight of the prepared graft copolymer latex (based on solid content).
Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer. According to claim 1,
The sum of the total weight of the polymer flocculant and the acid flocculant in step c) is 1.0 to 1.7 parts by weight.
Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer. According to claim 1,
The unsaturated fatty acid in step a) is characterized in that it is a straight chain or branched or cyclic unsaturated fatty acid having 8 to 22 carbon atoms.
Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer. According to claim 1,
The step a) is characterized in that it comprises 0.1 to 1.5 parts by weight of at least one selected from the group consisting of metal salts of rosin acid metal salts, alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters and unsaturated fatty acids as emulsifiers. To do
Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer. According to claim 1,
The conjugated diene monomer of step a) is characterized in that at least one member selected from the group consisting of 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene and chloroprene.
Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer. According to claim 1,
The water-soluble polymerization initiator of step a) is characterized in that at least one member selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate.
Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer. According to claim 1,
The conjugated diene rubber latex of step a) is characterized in that the average particle diameter is 2700 to 3300 mm 2
Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer. According to claim 1,
The graft polymerization of step b) is 100 parts by weight of the reaction mixture containing the prepared conjugated diene rubber latex (based on solid content), an aromatic vinyl monomer, and a vinyl cyan monomer, 0.05 to 1 part by weight of an emulsifier, and 0.01 to 1 part by weight of an initiator Characterized by being carried out
Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer. According to claim 1,
The polymer flocculant in step c) comprises 10 to 30% by weight of a polymerized core including an unsaturated carboxylic acid, an ester monomer thereof or a mixture thereof; And 65 to 85% by weight of the unsaturated carboxylic acid, an ester monomer thereof, or a mixture thereof, surrounding the core; And 5 to 15% by weight of a comonomer having an amide group.
Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer. According to claim 1,
The acid coagulant of step c) is characterized in that at least one member selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid, nitric acid, phosphoric acid and acetic acid
Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer. According to claim 1,
The c) step of aggregation is characterized in that a polymer coagulant and an acid coagulant are separately added at 75 to 85°C to the prepared graft copolymer latex.
Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer. According to claim 1,
The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is characterized in that the gas generation during injection is 1,900 ppm or less
Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer. According to claim 1,
The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer has a residual metal content of 765 ppm or less, and a reflection haze of 1.1 or less.
Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.