KR20210020680A - Method for preparing vinylcyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer and thermoplastic resin composition contatining the same - Google Patents

Abstract

The present invention relates to a method for preparing a graft copolymer and a thermoplastic resin composition including the graft copolymer. Particularly, the method for preparing a graft copolymer includes the steps of: carrying out graft polymerization of 50-70 wt% of conjugated diene rubber latex having a solid content of 30-65 wt% with 20-40 wt% of an aromatic vinyl compound and 1-20 wt% of a vinyl cyanide compound to obtain graft copolymer latex; a first agglomeration step of introducing 0.4-2.5 parts by weight of an acid agglomerating agent to 100 parts by weight (solid content basis) of the resultant graft copolymer latex to perform agglomeration; and a second agglomeration step of introducing 0.03-0.55 parts by weight of a polymer agglomerating agent after the first agglomeration step to perform agglomeration, wherein the total content of the acid agglomerating agent and polymer agglomerating agent is 0.58-2.85 parts by weight. According to the present invention, the graft copolymer obtained by the method shows high agglomeration efficiency and glossiness, and has a low b value and a low b value after retention, as measured by using a Hunter-lab color-meter, to realize a good color.

Description

TECHNICAL FIELD The method for preparing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and a thermoplastic resin composition containing the graft copolymer TECHNICAL FIELD TECHNICAL FIELD CONTATINING THE SAME}

The present invention relates to a method for preparing a graft copolymer and a thermoplastic resin composition comprising the graft copolymer, and more particularly, to a graft copolymer obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound on a conjugated diene rubber latex. A method for producing a graft copolymer having excellent cohesion efficiency and excellent gloss, color, and processing characteristics by coagulating with an acid coagulant and then again coagulating with an acid coagulant for the combined latex, and a thermoplastic containing the graft co-polymer It relates to a resin composition.

Acrylonitrile-butadiene-styrene copolymer represented by vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (hereinafter referred to as "ABS-based copolymer") has impact resistance, mechanical strength, moldability, and gloss It is widely used in various fields such as electric parts, electronic parts, office equipment, and automobile parts due to its good physical properties such as degrees.

In general, when an ABS-based copolymer is prepared by grafting an aromatic vinyl compound and a vinyl cyan compound monomer to a conjugated diene-based rubber latex by emulsion polymerization, it shows a good balance of properties compared to the ABS-based copolymer prepared by bulk polymerization, and has excellent gloss, etc. ABS-based copolymer is mainly produced by emulsion polymerization because it has the advantage of having.

In addition, the ABS-based copolymer latex produced by emulsion polymerization is preferably processed into powder for reduction in volume, various utility, and ease of handling.In general, the ABS-based resin latex is agglomerated, aged, dehydrated and dried. ABS resin powder can be obtained.

The agglomeration of the ABS-based copolymer latex prepared by the emulsion polymerization can chemically agglomerate the latex particles stabilized by the emulsifier used in the emulsion polymerization by using various coagulants, and the coagulant is an acid or metal salt. I can. Aggregation of latex using an acid has a disadvantage in that the thermal stability of the ABS resin is lowered due to residual acid, and the amount of gas generated during the thermoforming process is large and the yellowness of the resin is high. In addition, the aggregation of latex using a metal salt has a problem that the amount of gas generated and the yellowness are relatively low, but the productivity is low.

Accordingly, there is a need to develop a method for producing an ABS-based copolymer having excellent color while efficiently coagulating the ABS-based copolymer latex.

Korean Patent Registration No. 10-0463482

In order to solve the problems of the prior art as described above, the present substrate is an acid coagulant 0.4 to 2.5 based on 100 parts by weight (solid content) of the graft copolymer latex obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound on a conjugated diene rubber latex. A first coagulation step of coagulating by adding a weight part; And a second agglomeration step of adding 0.03 to 0.55 parts by weight of a polymer coagulant after the first coagulation step to agglomerate; including, but adjusting the total weight of the acid coagulant and the polymer coagulant to 0.58 to 2.85 parts by weight, resulting in good cohesion efficiency and glossiness. The method of producing a graft copolymer with excellent color and this graft copolymer is excellent and the b value measured using a Hunter Lab color meter and the b value measured after staying at 250℃ for 15 minutes in an injection machine is low. It is an object of the present invention to provide a thermoplastic resin composition comprising a.

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

In order to achieve the above object, the present substrate is graft polymerization of 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyan compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight. Preparing a graft copolymer latex; A first agglomeration step of coagulating by adding 0.4 to 2.5 parts by weight of an acid coagulant to 100 parts by weight of the prepared graft copolymer latex (based on solid content); And a second agglomeration step of adding 0.03 to 0.55 parts by weight of a polymer coagulant after the first coagulation step to coagulate; including, wherein the total amount of the acid coagulant and the polymer coagulant is 0.58 to 2.85 parts by weight-conjugated diene It provides a method for preparing a compound-aromatic vinyl compound graft copolymer.

In addition, the present disclosure provides a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer prepared by the above production method.

In addition, the present substrate is a thermoplastic comprising 20 to 40% by weight of the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer and 60 to 80% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer Provides a resin composition.

According to the present description, a graft copolymer latex obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound on a conjugated diene rubber latex is agglomerated with 0.4 to 2.5 parts by weight of an acid coagulant, and then again coagulated with 0.03 to 0.55 parts by weight of a polymer coagulant. When the total amount of the acid coagulant and the polymer coagulant is 0.58 to 2.85 parts by weight, the coagulation efficiency is excellent, the b-value measured using a Hunter Lab color meter and the b-value measured after staying at 250°C for 15 minutes in an injection machine are low and glossiness. The color has a beautiful effect as is improved.

The present inventors coagulate the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer latex with an acid coagulant and then coagulate with a polymer coagulant, but when the acid coagulant and the polymer coagulant are used in a specific amount, the gloss is high. The b value measured using the Hunter Lab color meter and the b value measured after staying at 250°C for 15 minutes in the injection machine (hereinafter referred to as "b value after staying") were low, confirming the excellent effect of color. Further research was devoted to completing the present invention.

A detailed method of preparing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer according to the present disclosure is as follows.

The production method of the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure comprises 20 to 40% by weight of an aromatic vinyl compound and 20 to 40% by weight of an aromatic vinyl compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight. Graft polymerization of 1 to 20% by weight of a cyan compound to prepare a graft copolymer latex; A first agglomeration step of coagulating by adding 0.4 to 2.5 parts by weight of an acid coagulant to 100 parts by weight of the prepared graft copolymer latex (based on solid content); And a second flocculation step of adding 0.03 to 0.55 parts by weight of a polymer flocculant after the first flocculation step to agglomerate; including, wherein the total weight of the acid flocculant and the polymer flocculant is 0.58 to 2.85 parts by weight, in this case The cohesive efficiency is excellent, the b-value measured using a Hunter Lab color meter and the b-value after stay are low, and the color is excellent due to high glossiness. It works.

The manufacturing method of the present disclosure will be described step by step as follows.

Conjugated diene Steps to Prepare Rubber Latex

The method for producing a conjugated diene rubber latex included in the production of the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is, for example, 100 parts by weight of the conjugated diene compound, 30 to 100 parts by weight of ion-exchanged water, 0.5 to the emulsifier. 3 parts by weight of an electrolyte, 0.01 to 0.5 parts by weight of an electrolyte, 0.1 to 0.5 parts by weight of a molecular weight modifier, and 0.1 to 1 parts by weight of an initiator may be added and polymerized to prepare a conjugated diene rubber latex, and in this case, excellent impact resistance It works.

In another example, the method for producing a conjugated diene rubber latex includes 100 parts by weight of a conjugated diene compound, 40 to 70 parts by weight of ion-exchanged water, 1 to 2.5 parts by weight of an emulsifier, 0.05 to 0.3 parts by weight of an electrolyte, 0.2 to 0.4 parts by weight of a molecular weight modifier. And 0.3 to 0.8 parts by weight of the initiator may be added and polymerized to prepare a conjugated diene rubber latex, and in this case, the impact resistance is excellent.

As a specific example, the method for preparing the conjugated diene rubber latex includes 30 to 100 parts by weight of ion-exchanged water, 0.3 to 2 parts by weight of emulsifier, 0.01 to 0.5 parts by weight of electrolyte, and molecular weight modifier in 75 to 90 parts by weight of 100 parts by weight of the conjugated diene compound. Adding 0.1 to 0.5 parts by weight and 0.05 to 0.5 parts by weight of an initiator and performing primary polymerization; 0.05 to 0.5 parts by weight of an initiator and 10 to 25 parts by weight of a conjugated diene compound are continuously added to a polymerization conversion rate of 35 to 45% after the first polymerization step, followed by secondary polymerization; Adding 0.2 to 1 parts by weight of an emulsifier and performing tertiary polymerization at a point in which the polymerization conversion rate is 70 to 80% after the second polymerization step; After the tertiary polymerization step, terminating the polymerization at a polymerization conversion rate of 93 to 99% by weight; may include, and in this case, there is an effect of excellent impact resistance.

In the present description, the polymerization conversion rate may be defined as the weight% of the monomer converted to the polymer until measurement based on 100% of the total weight of the monomers added until the polymerization is completed, and the method of measuring the polymerization conversion rate is determined according to this definition. The method of measuring the polymerization conversion rate is not particularly limited, and as a specific example, 1.5 g of the prepared latex is dried in a hot air dryer at 150° C. for 15 minutes, and then the weight is measured and the total solid content (TSC) is calculated by Equation 1 below. It can be obtained and calculated using Equation 2 below. Equation 2 is based on the total weight of the added monomer is 100 parts by weight.

[Equation 1]

[Equation 2]

Polymerization conversion rate (%) = [Total solid content (TSC) × (total weight of added monomer, ion-exchanged water, and sub-materials) / 100]-(weight of sub-materials added other than monomer and ion-exchanged water)

Sub-materials in Equation 2 refer to initiators, emulsifiers, electrolytes, and molecular weight modifiers.

The added monomer refers to a conjugated diene compound.

The conjugated diene compound is one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and isoprene, for example It can be more than that.

The emulsifier may be, for example, one or more selected from the group consisting of rosin acid metal salts, alkyl aryl sulfonates, alkalimethyl alkyl sulfates, sulfonated alkyl esters, and metal salts of unsaturated fatty acids.

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 , It may be at least one selected from the group consisting of _{Na 3} PO ₄ , K ₂ HPO ₄ and Na ₂ HPO _4.

The initiator may be, for example, a water-soluble persulfate polymerization initiator, a fat-soluble polymerization initiator, or an oxidation-reduction catalyst system, and the water-soluble persulfate polymerization initiator is, for example, a group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate. The oil-soluble polymerization initiator may be one or more selected from, for example, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, t-butyl hydroperoxide, paramethane hydroperoxide and benzoyl It may be one or more selected from the group consisting of peroxide, and examples of the oxidation-reduction catalyst system include sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, and sodium pyrrolate. It may be one or more selected from the group consisting of sodium sulfate.

When preparing the conjugated diene rubber latex, it may be most preferably potassium persulfate.

The molecular weight modifier may be a mercaptans-based molecular weight modifier as an example, and in particular, tertiary dodecyl mercaptan is preferred.

The conjugated diene rubber latex of the present disclosure may be, for example, an average particle diameter of 1,800 to 5,000 Å, preferably 2,000 to 4,000 Å, more preferably 2,500 to 3,500 Å, and has excellent impact resistance within this range.

The average particle diameter of this description is a sample prepared by diluting the conjugated diene rubber latex to a total solid content (TSC) of 0.1% or less, and then using a Nicomp ^TM 380 device (PSS, Nicomp, USA) by a dynamic laser light scattering method. It can be measured using.

Graft Steps for preparing copolymer latex

The step of preparing the graft copolymer latex is, for example, grafting 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinylcyan compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight. It is possible to perform graft polymerization, preferably 25 to 35% by weight of an aromatic vinyl compound and 5 to 15% by weight of a vinyl cyan compound in 55 to 65% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight. And within this range, there is an effect excellent in impact resistance, mechanical strength and moldability.

In this description, the solid content is defined as the content of the active ingredient remaining when all the moisture in the latex has been evaporated. After measuring 2.5 g of latex in an aluminum dish with a balance, heating at 150°C for 5 minutes to evaporate all the moisture. By measuring the weight, it can be obtained by Equation 3 below.

[Equation 3]

Solid content (% by weight) = 100-[(Weight of latex before moisture drying (g)-Weight of remaining powder after moisture drying (g)) / Weight of latex before moisture drying X 100]

The step of preparing the graft copolymer latex is, for example, a conjugated diene rubber latex, an aromatic vinyl compound, and a vinyl cyan compound in a total of 100 parts by weight, ion exchange water 70 to 200 parts by weight, initiator 0.1 to 2 parts by weight, emulsifier 0.1 to After polymerization by adding 2 parts by weight and 0.05 to 1.5 parts by weight of a molecular weight control agent, the polymerization reaction may be terminated at a polymerization conversion rate of 93 to 99% by weight.

In this step, the polymerization conversion rate follows the definition and measurement method of the polymerization conversion rate described above in the preparation of the conjugated diene rubber latex, but the added monomer refers to a conjugated diene compound, an aromatic vinyl compound, and a vinyl cyan compound contained in the rubber latex.

In another example, the step of preparing the graft copolymer latex includes a total of 100 parts by weight of a conjugated diene rubber latex, an aromatic vinyl compound and a vinyl cyan compound, 100 to 170 parts by weight of ion exchange water, 0.3 to 1 part by weight of an initiator, and an emulsifier. 0.5 to 1.5 parts by weight and 0.1 to 1.0 parts by weight of a molecular weight modifier are added to perform the polymerization reaction, and the polymerization reaction can be terminated at a polymerization conversion ratio of 95 to 98% by weight.

As a specific example, the step of preparing the graft copolymer latex includes 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight based on a total of 100 parts by weight of a conjugated diene rubber, an aromatic vinyl compound, and a vinyl cyan compound, and ions. 60 to 150 parts by weight of exchange water, 20 to 40 parts by weight of an aromatic vinyl compound mixed in a separate mixing device, 1 to 20 parts by weight of a vinyl cyanide compound, 10 to 50 parts by weight of ion-exchanged water, 0.09 to 1.5 parts by weight of an initiator, A mixed solution containing 0.1 to 2 parts by weight of an emulsifier and 0.05 to 1.5 parts by weight of a molecular weight control agent was added at 65 to 75°C for 2 to 4 hours, and then 0.01 to 0.5 parts by weight of an initiator was added, and 75 to 80 over 30 to 90 minutes. After raising the temperature to °C, the graft polymerization can be terminated at a polymerization conversion rate of 93 to 99% by weight, and in this case, there is an effect of excellent impact resistance, mechanical strength and moldability.

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

The emulsifier, initiator, and molecular weight modifier may be used within the range used in the preparation step of the conjugated diene rubber latex, for example.

Other additives, such as electrolytes not specifically mentioned in the present description, may be appropriately selected as needed, and are particularly limited if they are within the range generally applied to the production of vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer latex. It doesn't work.

In addition to the above description, other reaction conditions such as reaction time, reaction temperature, pressure, and addition time of reactants in the method for preparing the graft copolymer are not particularly limited if they are within the range commonly used in the technical field to which the present invention belongs, and is necessary. It can be appropriately selected and implemented according to.

Graft Agglomeration step of copolymer latex

The graft copolymer latex prepared above is agglomerated by a coagulant to form a graft copolymer slurry.

The agglomeration step includes a first agglomeration step of adding 0.4 to 2.5 parts by weight of an acid coagulant to 100 parts by weight (based on solid content) of the prepared graft copolymer latex as an example and coagulating; And a second agglomeration step of adding 0.03 to 0.55 parts by weight of a polymer coagulant after the first coagulation step to agglomerate; but, the total amount of the acid coagulant and the polymer coagulant may be 0.58 to 2.85 parts by weight, and in this case, the coagulation is efficiently It is made with high gloss, and the b-value measured using the Hunter Lab color meter and the b-value after stay are low, so the color is beautiful.

The first coagulation step may be, for example, a step of adding an acid coagulant to the graft copolymer latex at 75 to 85°C, and then raising the temperature by 5 to 10°C over 5 to 35 minutes, and preferably acid After the flocculant is added at 78 to 82° C., it may be a step of raising the temperature by 5 to 8° C. over 10 to 30 minutes. In this case, the agglomeration is uniform and the agglomeration efficiency is excellent.

In the second agglomeration step, for example, a polymer coagulant may be added at 80 to 95°C, preferably at 80 to 90°C, more preferably at 82 to 87°C, and within this range, the aggregation is uniformly performed and the aggregation efficiency This has an excellent effect.

As a specific example, the temperature at which the first coagulation step ends and the temperature at which the second coagulation step starts may be the same.

The second coagulation step may be, for example, a step of coagulating for 5 to 100 minutes, preferably 20 to 40 minutes after the polymer coagulant is added. In this case, the coagulation is uniform and the coagulation efficiency is excellent and the aging There is an effect made.

The first coagulation step and the second coagulation step may be performed under conditions of, for example, a stirring speed of 5 to 450 rpm, or 10 to 400 rpm, preferably 30 to 300 rpm, more preferably 30 to 100 rpm, , But is not limited thereto. Within the stirring speed range, productivity is excellent, aggregation efficiency is high, and physical property balance is excellent.

The acid flocculant may be, for example, 0.4 to 2.5 parts by weight, or 0.5 to 2.0 parts by weight, preferably 0.5 to 1.5 parts by weight, more preferably 0.5 to 1.0 parts by weight, even more preferably 0.5 to 0.7 parts by weight, In this case, aggregation is efficiently performed, and the gloss is high and the b value measured using a Hunter Lab color meter and the b value after stay are low, so the color is beautiful.

The polymeric coagulant may be, for example, 0.03 to 0.55 parts by weight, or 0.05 to 0.3 parts by weight, preferably 0.05 to 0.2 parts by weight, more preferably 0.05 to 0.1 parts by weight, and agglomeration is efficiently performed within this range. The gloss is high and the b-value measured using a Hunter Lab color meter and the b-value after stay are low, so the color is beautiful.

The total sum of the acid coagulant and the polymer coagulant may be, for example, 0.58 to 2.85 parts by weight, or 0.6 to 2.6 parts by weight, preferably 0.6 to 1.6 parts by weight, more preferably 0.6 to 0.8 parts by weight, and agglomeration within this range. This is done efficiently and has a high glossiness and a low b-value measured using a Hunter Lab color meter and a low b-value after stay, so the color is beautiful.

The acid flocculant may be, for example, one or more selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid and acetic acid, and preferably sulfuric acid, and in this case, the aggregation efficiency is good and the glossiness is excellent.

The polymer flocculant may include, for example, a cationic polymer flocculant including an amino group, an ammonium group, or both at the terminal; An anionic polymer flocculant containing an amide group, a carboxylate group, or both at the terminal; And a nonionic polymer flocculant; may be at least one selected from the group consisting of, preferably a cationic polymer flocculant, in this case, the gloss is high and the b value measured using a Hunter Lab color meter and the b value after stay This low color has a beautiful effect.

The cationic polymer flocculant may be one or more selected from the group consisting of a methacrylate polymer flocculant, an ammonium acrylate polymer flocculant, and an ammonium acrylamide polymer flocculant, and in this case, a high glossiness and a Hunter Lab color meter may be used. The b value measured by using and the b value after stay is low, so the color is beautiful.

The cationic polymer flocculant may be, for example, a molecular weight of 0.01 to 10×10 ⁶ Daltons, preferably 1 to 10×10 ⁶ Daltons, and has excellent aggregation efficiency within this range.

The cationic polymer flocculant may be, for example, a pH of 0 to 5, preferably 1 to 4 in a 0.25 mass% solution, and has excellent flocculation efficiency within this range.

The cationic polymer flocculant may include, for example, a cationic polymer flocculant having a viscosity of 100 to 5000 cps in a 1% by mass stock solution, a molecular weight of 0.01 to 10×10 ⁶ Daltons and a pH of 2 to 4 in a 0.1% by mass solution; A cationic polymer flocculant having a pH of 0-5 in a molecular weight of 0.01-10×10 ^{6 Daltons and 0.25% by mass solution;} Or a mixture thereof; in this case, the gloss is high and the b value measured using a Hunter Lab color meter and the b value after stay are low, so that the color is beautiful.

The anionic polymer flocculant may be, for example, a molecular weight of 0.01 to 15 × 10 ⁶ Daltons, preferably 1 to 15 × 10 ⁶ Daltons, and has excellent aggregation efficiency within this range.

The anionic polymer flocculant may be, for example, a pH of 4 to 11, preferably 5 to 10 in a 0.25 mass% solution, and has excellent flocculation efficiency within this range.

Specific examples of the anionic polymer flocculant may include an anionic polymer flocculant having a viscosity of 1000 to 10000 cps in a 1% by mass stock solution, a molecular weight of 0.05 to 15×10 ⁶ Daltons and a pH of 5 to 9 in a 0.1% by mass solution; Anionic polymer flocculant having a molecular weight of 0.01-15×10 ⁶ Daltons and a pH of 5-10 in a 0.25 mass% solution; Or a mixture thereof; in this case, the gloss is high and the b value measured using a Hunter Lab color meter and the b value after stay are low, so that the color is beautiful.

The nonionic polymer flocculant may be, for example, one or more selected from the group consisting of an acrylamide polymer flocculant, an ethylene oxide polymer flocculant, and a propylene oxide polymer flocculant. In this case, a high glossiness is used and a Hunter Lab color meter is used. The measured b value and the b value after stay are low, so the color has a beautiful effect.

The nonionic polymer flocculant may be, for example, a molecular weight of 0.05 to 10 × 10 ⁶ Daltons, preferably 5 to 10 × 10 ⁶ Daltons, and has excellent aggregation efficiency within this range.

The nonionic polymer flocculant may be, for example, a pH of 4 to 7.5, preferably 5 to 7 in a 0.25 mass% solution, or a pH of 3 to 8, preferably 4 to 7.5 in a 0.1 mass% solution, within this range. It has excellent cohesion efficiency.

The nonionic polymer flocculant is a specific example of a nonionic polymer flocculant having a viscosity of 100 to 4000 cps in a 1% by mass stock solution, a molecular weight of 0.05 to 10×10 ⁶ Daltons and a pH of 4 to 7.5 in a 0.1% by mass solution; A nonionic polymer flocculant having a pH of 5-7 in a molecular weight of 0.05-10 x 10 ^{6 Daltons and 0.25 mass% solution;} Or a mixture thereof; in this case, the gloss is high and the b value measured using a Hunter Lab color meter and the b value after stay are low, so that the color is beautiful.

In the present description, the viscosity can be measured using a Brookfield viscometer at room temperature (20-25°C) unless otherwise stated.

In the present description, the molecular weight can be measured using gel permeation chromatography (GPC) unless otherwise stated.

In this description, the pH can be measured using a general pH measuring device at room temperature (20 to 25°C) unless otherwise stated, and specifically, it can be measured using the Thermo Scientific Orion Star A Series.

The polymer coagulant may be in the form of an emulsion, for example, a solid content of 0.1 to 10% by weight, emulsifier 1 to 20% by weight, dispersion stabilizer 0.1 to 10% by weight, and water may include 75 to 95% by weight, In this case, there is an effect of easy dispersion.

The solid content of the polymer coagulant may be, for example, 0.1 to 10% by weight, preferably 1 to 8% by weight, more preferably 3 to 7% by weight, and in this case, there is an effect of easy dispersion.

In the present description, an emulsion refers to a state in which two liquids that are not mixed with each other have a constant ratio and are dispersed in another liquid in the form of small droplets.

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

After the agglomeration step, the agglomerated graft copolymer latex can be obtained as a graft copolymer powder by dehydrating and drying, for example.

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

In the present description, the average particle diameter of the powder can be measured by the DP caking test. For DP caking test, 10 g of powder was compressed with a weight of 20 kg for 10 minutes, and then layered from #8 mesh (2380㎛) to #625 mesh (20㎛) on a sieve vibrator (Analysette 3) of Fritsch, Germany, and #625 mesh. After installing a stainless steel container that can collect the powder passing through the #625 mesh, vibrating the sieve vibrator for 20 minutes, and then check the particle size distribution of the powder remaining in the mesh. The diameter of the particles passing through 50% by weight is taken as the average particle diameter of the powder.

The dehydration and drying step is not particularly limited if it is a method generally used in the art.

The slurry obtained after the agglomeration may be dehydrated using a centrifugal dehydrator, a compression dehydrator, or the like, to obtain a graft copolymer in a wet powder state.

The dehydration may be preferably performed one or more times, preferably 1 to 3 times, more preferably 2 to 3 times, in this case, and in this case, the residual emulsifier content is reduced to improve surface properties such as glossiness. Has the effect of being.

The graft copolymer in a wet powder state obtained after the dehydration has a moisture content of, for example, 40% by weight or less, preferably 10 to 40% by weight, more preferably 10 to 35% by weight or 10 to 30% by weight. %, and in this case, there is an advantage of excellent productivity by increasing the efficiency in the drying step, which is a post process.

The drying is not particularly limited in the case of a known drying process commonly practiced in the technical field to which the present invention belongs, but as an example, the graft copolymer in a wet powder state is aired using a fluidized bed dryer. After supplying and drying, the graft copolymer powder can be obtained.

In addition, the graft copolymer powder obtained by drying the graft copolymer in the wet powder state may have a moisture content of 2% by weight or less, preferably 0.1 to 2% by weight, more preferably 0.1 to 1% by weight. And, within this range, there are advantages of excellent productivity of the copolymer and excellent physical properties such as mechanical strength, heat resistance, and surface gloss.

In the present description, the moisture content can be measured using a moisture analyzer, and specifically, a moisture analyzer of METTLER TOLEDO, Switzerland.

The graft copolymer powder can be extruded after melt-kneading with an aromatic vinyl compound-vinyl cyan compound copolymer as an example, and in this case, it has excellent impact resistance, chemical resistance, molding processability and gloss, and a Hunter Lab color meter is used. The measured b value and the b value after staying at 250° C. for 15 minutes are low, so that a thermoplastic resin composition having a beautiful color can be prepared.

The melt-kneading and extrusion steps may be performed under 220 to 240°C and 250 to 400 rpm, preferably at 225 to 235°C and 300 to 400 rpm, but are not limited thereto.

The melt-kneading may be performed using, for example, a Banbari mixer, a single screw extruder, a twin screw extruder, a kneader, etc., and is not particularly limited.

During the melt-kneading, for example, 0.1 to 10 parts by weight or 0.1 to 5 parts by weight of at least one additive selected from the group consisting of a colorant, a heat stabilizer, a light stabilizer, a reinforcing agent, a filler, a flame retardant, a lubricant, a plasticizer, an antistatic agent, and a processing aid It can be input within the sub-range.

In addition, the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure is characterized in that it is prepared by the above production method, and in this case, the b value and 250 measured using a Hunter Lab color meter After staying at ℃ for 15 minutes, the b value is low and the gloss is high, so the color is excellent. It works.

In addition, the thermoplastic resin composition of the present invention is the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 20 to 40% by weight, preferably 25 to 35% by weight and aromatic vinyl compound-vinyl cyan compound copolymer 60 To 80% by weight, preferably 65 to 75% by weight, and in this case, the agglomeration efficiency is excellent, the b value measured using a Hunter Lab color meter and the b value after staying at 250°C for 15 minutes This low color has a beautiful effect.

The thermoplastic resin composition has a glossiness of 84 or more, or 84 to 100, preferably 84 to 95, more preferably 85, measured at a 45° angle with a gloss meter according to ASTM D258, for example. To 91, and more preferably 87 to 90, and within this range, there is an excellent effect of physical property balance and color.

The thermoplastic resin composition has a b value of 5.5 or less, or 3.5 to 5.5, preferably 4.7 to 5.5, more preferably 4.8 to 5.2, even more preferably 4.8 to 5.0, measured using a Hunter Lab calimeter as an example. It may be, and within this range, there is an excellent effect of physical property balance and color.

The thermoplastic resin composition has a b value of 8.6 or less, preferably 7.5 to 8.6, more preferably 8.1 to 8.6, and even more preferably 8.2 to 8.4 after staying at 250° C. for 15 minutes using a Hunter Lab color meter as an example. It may be, and within this range, there is an excellent effect of physical property balance and color.

The thermoplastic resin composition is, for example, dissolved 0.3 g of the thermoplastic resin composition in chloroform, precipitated the polymer using methanol, filtered the supernatant, and then used the polymer flocculant into LC/DAD Agilent 1290 LC-2 detectors (DAD and FLD as stand). -alone instrument) The content of the polymer flocculant measured using the equipment is 5,000 ppm or less, or 100 to 5,000 ppm, preferably 400 to 2,000 ppm, more preferably 440 to 1,500 ppm, even more preferably 490 to 1,000 ppm It may be, and there is an effect of excellent glossiness within this range.

In addition, the molded article of the present disclosure is characterized in that it is manufactured from the thermoplastic resin composition, and in this case, it has excellent impact resistance, chemical resistance, molding processability and gloss, and at b-value measured using a Hunter Lab color meter and 250°C. After staying for 15 minutes, the b value is low, so the color is beautiful.

In addition, the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure Vinylcyan compound-conjugated diene compound-aromatic vinyl obtained by graft polymerization of 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyanide compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight As a compound graft copolymer, 0.3 g of the graft copolymer is dissolved in chloroform, the polymer is precipitated using methanol, the supernatant is filtered, and the polymer coagulant is used in LC/DAD Agilent 1290 LC-2 detectors (DAD and FLD stand-alone instrument), the content of the polymer coagulant measured using the equipment is 10 to 19,000 ppm, and in this case, the b value measured using the Hunter Lab color meter is low and the gloss is high, so the color is excellent. It works.

The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer has, for example, a polymer coagulant content of 10 to 19,000 ppm, or 300 to 19,000 ppm, preferably 1,500 to 8,000 ppm, more preferably 1,600 to 5,500 ppm , More preferably, it may be 1,800 to 3,800 ppm, and within this range, the b-value measured using a Hunter Lab color meter and the b-value after stay are low, and the color is excellent due to high gloss It works.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present description, but the following examples are only illustrative of the present description, and that various changes and modifications are possible within the scope of the present description and the scope of the technical idea will be apparent to those skilled in the art, It is natural that such modifications and modifications fall within the appended claims.

[Example]

* Acid flocculant: sulfuric acid

* Cationic polymer flocculant: HCP-800 from HANSOL CHEMICAL with a molecular weight of 1 to 10 × 10 ⁶ Daltons, pH 0 to 5 in a 0.25 mass% solution

* Anionic polymer flocculant: HAP-606 from HANSOL CHEMICAL, having a molecular weight of 1 to 15 × 10 ⁶ Daltons, pH 5 to 10 in a 0.25 mass% solution

* Nonionic polymer flocculant: HNP-910 from HANSOL CHEMICAL with a molecular weight of 5 to 10 × 10 ⁶ Daltons and a pH of 5 to 7 in a 0.25 mass% solution

<Manufacture of conjugated diene rubber latex>

55 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 85 parts by weight of 100 parts by weight of 1,3-butadiene as a monomer, 1.5 parts by weight of a fatty acid metal salt of C16 to C18 as an emulsifier, potassium carbonate as an electrolyte (K ₂ CO ₃ ) 0.15 parts by weight, 0.3 parts by weight of tertiary dodecylmercaptan (TDDM) as a molecular weight control agent, and 0.3 parts by weight of potassium persulfate as an initiator were put together, and polymerization was carried out at a reaction temperature of 70°C. At a polymerization conversion rate of 35 to 45%, 0.3 parts by weight of potassium persulfate was added at once, and the remaining amount of 1,3-butadiene was continuously added to react. After reacting to a polymerization conversion rate of 70 to 80%, 0.3 parts by weight of a saponified rosin acid was added and reacted, and the reaction was terminated at a polymerization conversion rate of 93% to prepare a conjugated diene rubber latex.

The prepared conjugated diene rubber latex had an average particle diameter of 3,000 Å and a solid content of 55 to 60% by weight.

<Preparation of vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (hereinafter referred to as “ABS graft copolymer”)>

In the nitrogen-substituted polymerization reactor, the solid content prepared above is 55 to 60% by weight of conjugated diene rubber latex, 60 parts by weight and 100 parts by weight of ion-exchanged water, 10 parts by weight of acrylonitrile and styrene mixed in a separate mixing device. A mixed solution consisting of 30 parts by weight, 25 parts by weight of ion-exchanged water, 0.12 parts by weight of t-butyl hydroperoxide, 0.9 parts by weight of potassium rosinate, and 0.35 parts by weight of tertiary dodecyl mercaptan, and 0.054 parts by weight of dextrose, pyrroleic acid 0.004 parts by weight of sodium and 0.002 parts by weight of ferrous sulfate were added together at 70° C. for 3 hours. After the above 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, and the temperature was raised to 80° C. over 1 hour. Then, the polymerization reaction was terminated to prepare an ABS graft copolymer latex. At this time, the polymerization conversion rate was 97%.

Example One

After adding 1.5 parts by weight of sulfuric acid to 100 parts by weight of the ABS graft copolymer latex (based on solid content) prepared above at 80° C., the temperature was raised to 5° C. over 15 minutes, and 0.05 parts by weight of a cationic polymer coagulant was added for 30 minutes. Agglomerated. The aggregated ABS graft copolymer was dehydrated and dried to prepare an ABS graft copolymer powder. 27 parts by weight of the prepared ABS graft copolymer powder and 73 parts by weight of an acrylonitrile-styrene copolymer (LG Chemical, 92HR) were mixed into a mixer, and then melt-kneaded at 210°C using an extruder and pelletized, A specimen for measuring physical properties was prepared using an injection machine.

Example 2 to 20

Example 1 was carried out in the same manner as in Example 1, except that the types and contents of the acid coagulant and the polymer coagulant were changed as shown in Tables 1 to 3.

Comparative example One

After adding 2.0 parts by weight of a cationic polymer coagulant to 100 parts by weight of the ABS graft copolymer latex prepared above (based on solid content) at 80°C, heating up to 93°C over 30 minutes to agglomerate the aggregated ABS graft copolymer Dehydration and drying were performed to prepare ABS graft copolymer powder. 27 parts by weight of the prepared ABS graft copolymer powder and 73 parts by weight of an acrylonitrile-styrene copolymer (LG Chemical, 92HR) were mixed into a mixer, and then melt-kneaded at 210°C using an extruder and pelletized, A specimen for measuring physical properties was prepared using an injection machine.

Comparative example 2

It was carried out in the same manner as in Comparative Example 1, except that 2 parts by weight of sulfuric acid was added instead of 2 parts by weight of the polymer coagulant in Comparative Example 1.

Comparative example 3 to 9

In Example 1, except that the contents of the acid coagulant and the cationic polymer coagulant were changed as shown in Tables 4 and 5 below, it was carried out in the same manner as in Example 1.

Reference example One

Example 1 was carried out in the same manner as in Example 1, except that the polymer coagulant was added at 85° C. and then aged for 120 minutes.

[Test Example]

The properties of the specimens prepared in Examples 1 to 20, Comparative Examples 1 to 9, and Reference Example 1 were measured by the following method, and the results are shown in Tables 1 to 5 below.

How to measure

* Aggregation: After flocculation, the slurry is washed and dehydrated, and the resulting washed mother liquor is visually evaluated, and when the graft copolymer latex is completely agglomerated, it is marked as “○”, and non-aggregated graft copolymer latex is present. The bottom is indicated by "X".

* Glossiness: It was measured at a 45° angle with a gloss meter according to ASTM D258.

* b value: The b value was measured using a Hunter Lab color meter.

* B value after stay: After staying for 15 minutes at 250°C in an injection machine, the b value was measured using a Hunter Lab color meter.

* Polymer coagulant content (ppm): After dissolving 0.3 g of a sample in chloroform, precipitating the polymer with methanol, filtering the supernatant, and then adding the polymer coagulant to LC/DAD Agilent 1290 LC-2 detectors (DAD and FLD as stand- alone instrument) equipment was used to measure the content.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 First flocculant
Content (parts by weight) Sulfuric acid
1.5 Sulfuric acid
1.0 Sulfuric acid
0.7 Sulfuric acid
0.5 Sulfuric acid
0.5 Sulfuric acid
2.5 Sulfuric acid
1.5 Second flocculant
Content (parts by weight) Cation
0.05 Cation
0.05 Cation
0.05 Cation
0.1 Cation
0.2 Cation
0.1 Cation
0.4 Total flocculant
(Part by weight) 1.55 1.05 0.75 0.6 0.7 2.6 1.9 Agglomeration ○ ○ ○ ○ ○ ○ ○ b value 5.4 5.2 4.8 4.8 4.8 5.5 5.5 B value after stay 8.4 8.3 8.3 8.2 8.2 8.5 8.6 Gloss 90 89 90 89 85 85 84 Polymer flocculant
Content (ppm) 440 480 490 900 1800 1000 3950

division Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 First flocculant
Content (parts by weight) Sulfuric acid
2.4 Sulfuric acid
2.3 Sulfuric acid
1.5 Sulfuric acid
1.0 Sulfuric acid
0.7 Sulfuric acid
0.5 Sulfuric acid
0.5 Second flocculant
Content (parts by weight) Cation
0.05 Cation
0.5 Negative ions
0.05 Negative ions
0.05 Negative ions
0.05 Negative ions
0.1 Negative ions
0.2 Total flocculant
(Part by weight) 2.45 2.8 1.55 1.05 0.75 0.6 0.7 Agglomeration ○ ○ ○ ○ ○ ○ ○ b value 5.4 5.4 5.5 5.2 4.9 4.8 4.7 B value after stay 8.6 8.5 8.4 8.3 8.3 8.1 8.2 Gloss 88 84 91 90 90 89 84 Polymer flocculant
Content (ppm) 500 4950 445 483 490 910 1790

division Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 First flocculant
Content (parts by weight) Sulfuric acid
1.5 Sulfuric acid
1.0 Sulfuric acid
0.7 Sulfuric acid
0.5 Sulfuric acid
0.5 Hydrochloric acid
1.5 Second flocculant
Content (parts by weight) Nonionic
0.05 Nonionic
0.05 Nonionic
0.05 Nonionic
0.1 Nonionic
0.2 Cation
0.05 Total flocculant
(Part by weight) 1.55 1.05 0.75 0.6 0.7 1.55 Agglomeration ○ ○ ○ ○ ○ ○ b value 5.4 5.2 4.9 4.8 4.8 5.3 B value after stay 8.5 8.3 8.2 8.2 8.2 8.4 Gloss 91 90 90 89 85 90 Polymer flocculant
Content (ppm) 441 490 490 905 1810 440

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 First flocculant
Content (parts by weight) Cation
2.0 Sulfuric acid
2.0 Sulfuric acid
0.5 Sulfuric acid
2.6 Sulfuric acid
1.5 Second flocculant
Content (parts by weight) - - Cation
0.05 Cation
0.05 Cation
0.01 Total flocculant
(Part by weight) 2.0 2.0 0.55 2.65 1.51 Agglomeration ○ ○ X ○ X b value 4.6 5.5 - 6.8 - B value after stay 8.1 8.8 - 8.9 - Gloss 80 90 - 90 - Polymer flocculant
Content (ppm) 18000 - - 440 -

division Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Reference Example 1 First flocculant
Content (parts by weight) Sulfuric acid
2.8 Sulfuric acid
2.0 Sulfuric acid
0.25 Sulfuric acid
2.5 Sulfuric acid
1.5 Second flocculant
Content (parts by weight) Cation
0.3 Cation
1.1 Cation
0.5 Cation
0.5 Cation
0.05 Total flocculant
(Part by weight) 3.1 3.1 0.75 3.0 1.55 Agglomeration ○ ○ X ○ ○ b value 7.2 5.5 - 6.3 7.5 B value after stay 8.9 8.7 - 8.6 8.4 Gloss 84 81 - 83 90 Polymer flocculant
Content (ppm) 2600 9100 - 5000 440

As shown in Tables 1 to 5, Examples 1 to 17 according to the present invention have excellent cohesive efficiency, high glossiness, and low b-value measured using a Hunter Lab color meter and low b-value after staying. This was excellent.

On the other hand, Comparative Example 1 coagulated with the polymer coagulant alone had poor gloss, and Comparative Example 2 coagulated with the acid coagulant alone had a poor b value after stay.

In addition, in Comparative Examples 3, 5, and 8 in which the total amount of the acid coagulant and the polymer coagulant, the content of the polymer coagulant, and the content of the acid coagulant were small, the physical properties could not be measured.

In addition, in Comparative Examples 4, 6, 7 and 9 in which the content of the acid coagulant, the content of the polymer coagulant, or their total was out of the scope of the present invention, the b-value, the b-value, or glossiness after the stay was lowered.

In addition, in Reference Example 1, in which the polymer coagulant was added in the second aggregation step and then agglomerated for 120 minutes, the glossiness and the b value after residence were good, but the b value was decreased.

Claims (16)

Graft polymerization of 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyan compound to 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight to prepare a graft copolymer latex;
A first agglomeration step of coagulating by adding 0.4 to 2.5 parts by weight of an acid coagulant to 100 parts by weight of the prepared graft copolymer latex (based on solid content); And
Including; a second agglomeration step of agglomeration by adding 0.03 to 0.55 parts by weight of a polymer flocculant after the first flocculation step
The total amount of the acid coagulant and the polymer coagulant is 0.58 to 2.85 parts by weight, characterized in that
A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
The method of claim 1,
The acid coagulant is characterized in that at least one selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid and acetic acid.
A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
The method of claim 1,
The polymer flocculant may include a cationic polymer flocculant including an amino group, an ammonium group, or both at the terminal; An anionic polymer flocculant containing an amide group, a carboxylate group, or both at the terminal; And nonionic polymer flocculant; characterized in that at least one selected from the group consisting of
A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
The method of claim 1,
The polymeric coagulant is characterized in that the emulsion form
A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
The method of claim 1,
In the first coagulation step, the acid coagulant is added at 75 to 85° C., and the temperature is increased by 5 to 10° C. over 5 to 35 minutes.
A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
The method of claim 1,
The second aggregation step is characterized in that the polymer flocculant is added at 80 to 95°C.
A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
The method of claim 1,
The second coagulation step is characterized in that the polymer coagulant is added and coagulated for 5 to 100 minutes.
A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
The method of claim 1,
The step of preparing the graft copolymer latex includes a total of 100 parts by weight of a conjugated diene rubber latex, an aromatic vinyl compound and a vinyl cyan compound, 70 to 200 parts by weight of ion exchange water, 0.1 to 2 parts by weight of an initiator, 0.1 to 2 parts by weight of an emulsifier It characterized in that the polymerization reaction is terminated at a polymerization conversion rate of 93 to 99% by weight by adding 0.05 to 1.5 parts by weight of a part and a molecular weight modifier.
A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
The method of claim 1,
The step of preparing the graft copolymer latex includes 100 parts by weight of a conjugated diene compound, 30 to 100 parts by weight of ion-exchanged water, 0.5 to 3 parts by weight of an emulsifier, 0.01 to 0.5 parts by weight of an electrolyte, 0.1 to 0.5 parts by weight of a molecular weight modifier, and Including the step of preparing a conjugated diene rubber latex by adding and polymerizing 0.1 to 1 part by weight of an initiator.
A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
The method of claim 1,
The method for preparing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer comprises a dehydration and drying step after the agglomeration step.
A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
It is characterized in that produced by the manufacturing method according to any one of claims 1 to 10
Vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
A vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of claim 11, comprising 20 to 40% by weight and an aromatic vinyl compound-vinyl cyan compound copolymer 60 to 80% by weight
Thermoplastic resin composition.
The method of claim 12,
The thermoplastic resin composition was prepared by dissolving 0.3 g of the thermoplastic resin composition in chloroform, sedimenting the polymer using methanol, filtering the supernatant, and then using the polymer coagulant in LC/DAD Agilent 1290 LC-2 detectors (DAD and FLD as stand-alone). instrument), characterized in that the content of the polymer flocculant measured using the equipment is 5,000 ppm or less.
Thermoplastic resin composition.
The method of claim 12,
The thermoplastic resin composition is characterized in that the gloss measured at a 45° angle with a gloss meter according to ASTM D258 is 84 or more.
Thermoplastic resin composition.
The method of claim 12,
The thermoplastic resin composition is characterized in that the b value measured using a Hunter Lab color meter is 5.5 or less, and the b value measured after staying at 250°C for 15 minutes is 8.6 or less.
Thermoplastic resin composition.
Vinylcyan compound-conjugated diene compound-aromatic vinyl obtained by graft polymerization of 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyanide compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight As a compound graft copolymer, 0.3 g of the graft copolymer is dissolved in chloroform, the polymer is precipitated using methanol, the supernatant is filtered, and the polymer coagulant is used in LC/DAD Agilent 1290 LC-2 detectors (DAD and FLD as stand-alone instrument), characterized in that the content of the polymer flocculant measured using the equipment is 10 to 19,000 ppm
Vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.