KR20220046849A - A methods for preparing vinylcyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, methods for thermoplastic resin compositin comprising the same, and thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a preparation method of a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, a preparation method of a thermoplastic resin composition comprising the same, and a thermoplastic resin composition. More specifically, during the polymerization of a conjugated diene rubber, a conjugated diene compound and a molecular weight regulator are added in portions and the content of an emulsifier is reduced to lower the content of gel, and the enlarged conjugated diene-based rubber latex, which is enlarged with an organic acid thickening agent has the effect of improving gloss, reflection haze, induction and impact resistance and reducing residues during injection molding as the full width at half maximum of particle diameter is widened.

Description

Vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer manufacturing method, thermoplastic resin composition manufacturing method and thermoplastic resin composition comprising the same METHODS FOR THERMOPLASTIC RESIN COMPOSITIN COMPRISING THE SAME, AND THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a method for preparing a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, a method for preparing a thermoplastic resin composition comprising the same, and a thermoplastic resin composition, and more particularly, to a gel content of the conjugated diene rubber latex By lowering and widening the full width at half maximum particle diameter of the enlarged conjugated diene rubber latex, the gloss, reflection haze and impact resistance of the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer containing it are improved, and residues during injection molding It relates to a method for producing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, a method for producing a thermoplastic resin composition comprising the same, and a thermoplastic resin composition.

The acrylonitrile-butadiene-styrene (hereinafter referred to as 'ABS') copolymer has relatively good physical properties such as formability and gloss as well as mechanical strength such as impact resistance. It is widely used in office equipment or automobile parts.

In general, when an ABS copolymer is prepared by grafting styrene and acrylonitrile to butadiene rubber latex by emulsion polymerization, it exhibits a good balance of properties and excellent gloss compared to the ABS copolymer prepared by the bulk polymerization method. ABS copolymers are mainly produced by emulsion polymerization.

Furthermore, the ABS copolymer prepared as described above is mixed with a styrene-acrylonitrile (hereinafter referred to as 'SAN') copolymer and subjected to a thermoforming process to prepare a final product. It is affected by the gel content and particle size distribution of the dispersed rubber polymer. In addition, in the thermoplastic resin composition, the emulsifier remaining in the butadiene rubber during the high-temperature injection process remains in the injection mold. These residues also affect productivity, as they cause product failures and have to be temporarily stopped during production by cleaning processes to remove them.

Accordingly, there is a need to develop a method for manufacturing an ABS copolymer capable of improving productivity by further improving the impact strength of the ABS copolymer while reducing appearance quality such as glossiness and residues during injection molding.

Korean Patent No. 0527095

In order to solve the problems of the prior art as described above, the present invention has excellent fluidity, reflective haze and gloss, while further improving impact resistance and reducing residues in the mold during injection molding, so that both impact resistance, glossiness and workability are An object of the present invention is to provide a method for producing a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, a method for producing a thermoplastic resin composition comprising the same, and a thermoplastic resin composition, which can be applied in high quality to the required fields.

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

In order to achieve the above object, the present invention comprises the steps of: a) polymerization reaction including 0.1 to 2 parts by weight of an emulsifier, a molecular weight regulator and an electrolyte in 20 to 40 parts by weight of a total of 100 parts by weight of the conjugated diene compound; b) after step a), adding a residual conjugated diene compound and a molecular weight modifier to polymerization to obtain a conjugated diene rubber latex; c) preparing an enlarged conjugated diene rubber latex by adding 0.3 to 1 part by weight of an organic acid thickening agent to 100 parts by weight of the conjugated diene rubber latex (based on solid content); And d) 40 to 70% by weight of the enlarged conjugated diene rubber latex (based on solid content), 15 to 45% by weight of an aromatic vinyl compound, and 5 to 25% by weight of a vinyl cyan compound by graft polymerization reaction to the vinyl cyan compound-conjugated Diene rubber - obtaining an aromatic vinyl compound graft copolymer; including, wherein the enlarged conjugated diene rubber latex obtained in step c) has an average particle diameter of 3100 to 3500 Å and a full width at half maximum particle diameter of 2200 to 3000 Å It provides a method for producing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, characterized in that.

In addition, the present invention comprises the steps of preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer according to the above manufacturing method; And 15 to 35% by weight of the prepared graft copolymer and 65 to 85% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer are added to an extruder, melt-kneaded, and then extruded; Thermoplastic resin comprising a A method for preparing the composition is provided.

In addition, the present invention includes a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer 15 to 35 wt% and an aromatic vinyl compound-vinyl cyan compound copolymer 65 to 85 wt%, wherein the conjugated diene rubber is average A thermoplastic resin composition, characterized in that the particle diameter is 3100 to 3500 Å, the full width at half maximum particle diameter is 2200 to 3000 Å, and the Izod impact strength measured with a specimen thickness of 1/8″ according to ASTM D256 is 38 kgf cm/cm or more to provide.

In addition, the present invention provides a molded article comprising the thermoplastic resin composition.

According to the present invention, it has excellent fluidity, reflective haze and gloss, and has excellent impact resistance compared to conventional ABS resins, and has excellent productivity and quality because residues in the mold are reduced during injection molding, so impact resistance, glossiness and processability are all required. There is an effect of providing a method for producing a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, a method for producing a thermoplastic resin composition including the same, and a thermoplastic resin composition, which can be applied in high quality to the field.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure for demonstrating the full width at half maximum of a particle diameter.

Hereinafter, a method for preparing a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer of the present disclosure, a method for preparing a thermoplastic resin composition including the same, and a thermoplastic resin composition will be described in detail.

When the present inventors change the input method of the conjugated diene compound and the molecular weight regulator during polymerization of the conjugated diene rubber and reduce the content of the emulsifier, the gel content is reduced and the enlarged conjugated diene rubber, which is enlarged with an organic acid thickener, has a full width at half maximum particle size. It was confirmed that the impact strength was greatly improved while the reflective haze and gloss were excellent, and the injection residue was reduced in the mold during injection molding, and based on this, further research was completed and the present invention was completed.

The method for preparing the vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer of the present invention comprises: a) 0.1 to 2 parts by weight of an emulsifier, a molecular weight regulator, and an electrolyte in 20 to 40 parts by weight of a total of 100 parts by weight of the conjugated diene compound including polymerization; b) after step a), adding a residual conjugated diene compound and a molecular weight modifier to polymerization to obtain a conjugated diene rubber latex; c) preparing an enlarged conjugated diene rubber latex by adding 0.3 to 1 part by weight of an organic acid thickening agent to 100 parts by weight of the conjugated diene rubber latex (based on solid content); And d) 40 to 70% by weight of the enlarged conjugated diene rubber latex (based on solid content), 15 to 45% by weight of an aromatic vinyl compound, and 5 to 25% by weight of a vinyl cyan compound by graft polymerization reaction to the vinyl cyan compound-conjugated Diene rubber - obtaining an aromatic vinyl compound graft copolymer; including, wherein the enlarged conjugated diene rubber latex obtained in step c) has an average particle diameter of 3100 to 3500 Å and a full width at half maximum particle diameter of 2200 to 3000 Å characterized in that In this case, while excellent in fluidity, reflective haze and gloss, impact resistance is greatly improved compared to conventional ABS resins, and residues during injection molding are significantly reduced.

Hereinafter, the method for preparing the vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer of the present invention will be described in detail step by step.

a) polymerization reaction including 0.1 to 2 parts by weight of an emulsifier, a molecular weight regulator and an electrolyte in 20 to 40 parts by weight of a total of 100 parts by weight of the conjugated diene compound

In step a), the emulsifier may be preferably 0.3 to 1.7 parts by weight, more preferably 0.5 to 1.5 parts by weight, and still more preferably 0.7 to 1.3 parts by weight, within this range, the impact resistance is improved and injection molding is performed. Residue is reduced, and thus productivity and appearance quality are excellent.

When polymerizing the conventional conjugated diene rubber latex, 3 parts by weight or more of the emulsifier is added based on 100 parts by weight of the conjugated diene compound for a smooth polymerization reaction. There is a problem in that productivity is lowered and the appearance of the product is defective due to adhesion. In the present invention, the conjugated diene compound and the molecular weight regulator are separately injected after the reaction start time and the polymerization reaction at 50 to 60 ° C. for 50 to 70 minutes, respectively, so that even if the emulsifier content is greatly reduced, impact resistance, fluidity, and reflection It has excellent haze and gloss, and has the effect of significantly reducing injection mold residues during injection molding.

In step a), the emulsifier is, for example, at least 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. and preferably fatty acid soap, in which case impact resistance is improved and residues during injection molding are reduced, so that productivity and appearance quality are excellent.

The molecular weight modifier in step a) may be, for example, 0.05 to 0.3 parts by weight, preferably 0.1 to 0.25 parts by weight, more preferably 0.13 to 0.2 parts by weight, and the gel content is reduced within this range to improve impact resistance. has the effect of being

The molecular weight regulator may be, for example, a mercaptan-based molecular weight regulator, and in particular, tertiary dodecyl mercaptan is preferable.

In step a), the electrolyte is, for example, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , Na ₂ SO ₄ , K ₄ P ₂ O ₇ , Na ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ and at least one selected from the group consisting of Na ₂ HPO ₄ , and may preferably be K ₂ CO ₃ , in which case the gel content is As the full width of the reduced and enlarged conjugated diene rubber at half maximum particle diameter is widened, impact resistance is greatly increased, and fluidity, reflection haze and glossiness are also excellent.

In step a), the electrolyte may be, for example, 0.1 to 0.5 parts by weight, preferably 0.2 to 0.4 parts by weight, within this range, the gel content is reduced and the full width at half maximum particle diameter of the enlarged conjugated diene rubber is widened, so that the impact resistance is improved. As it rises significantly, fluidity, reflection haze, and glossiness all have excellent effects.

In step a), for example, the polymerization reaction may be carried out at 50 to 60 ° C. for 50 to 70 minutes, and preferably, the polymerization reaction may be made at 53 to 57 ° C. for 55 to 65 minutes, in which case the gel content is As the full width of the reduced and enlarged conjugated diene rubber at half maximum particle diameter is widened, impact resistance is greatly increased, and fluidity, reflection haze and glossiness are all excellent.

Step a) may include, for example, 0.1 to 0.5 parts by weight of an oxidation-reduction catalyst, 0.01 to 0.7 parts by weight of a fat-soluble polymerization initiator, and 80 to 120 parts by weight of ion-exchanged water. 0.1 to 0.3 parts by weight of a catalyst, 0.05 to 0.5 parts by weight of a fat-soluble polymerization initiator, and 90 to 110 parts by weight of ion-exchanged water can be included in the polymerization reaction, and by reducing unreacted monomers within this range, the vinyl cyan compound-conjugated diene rubber- There is an effect of increasing the productivity of the aromatic vinyl compound graft copolymer as well as improving the glossiness and reflection haze of the copolymer.

The oxidation-reduction catalyst may include, for example, at least one selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrole phosphate and sodium sulfite, , by reducing unreacted monomers within this range, there is an effect of increasing the productivity of the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, as well as improving the glossiness and reflection haze of the copolymer.

The oil-soluble polymerization initiator may be, for example, at least one selected from the group consisting of alkyl peroxide, aryl peroxide and azonitrile, specifically cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutyl At least one selected from the group consisting of nitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide and benzoyl peroxide may be used, and preferably tertiary butyl hydroperoxide.

b) After step a), the remaining conjugated diene compound, and a molecular weight regulator are added to the polymerization reaction to obtain a conjugated diene rubber latex

In step b), preferably, the residual conjugated diene compound and the molecular weight regulator after step a) may be continuously introduced while raising the temperature to 73 to 83° C. for 8 to 10 hours, preferably up to 75 to 80° C. It can be continuously added while raising the temperature for 8.5 to 9.5 hours. In this case, the gel content and the coagulated material content are reduced and the full width at half maximum particle diameter of the enlarged conjugated diene rubber is widened, so that the impact resistance is greatly increased, and fluidity, reflection haze and It also has an excellent effect of glossiness.

In the present description, 'continuous input' means not 'batch input', for example, 10 minutes or more, 30 minutes or more, 1 hour or more, preferably 2 hours or more drop-by-drop within the polymerization reaction time range. by drop), little by little, step by step, or continuous flow.

The step b), more preferably, b-1) a polymerization reaction by continuously introducing the residual conjugated diene compound and a molecular weight modifier while raising the temperature to 73 to 83° C. for 8 to 10 hours; b-2) adding 0.05 to 0.2 parts by weight of a water-soluble initiator and 0.05 to 0.3 parts by weight of an emulsifier at a polymerization conversion rate of 30 to 40% by weight, followed by polymerization; and b-3) terminating the polymerization reaction when the polymerization conversion rate is 93 to 99% by weight.

In step b), the molecular weight modifier may be, for example, 0.05 to 0.5 parts by weight, preferably 0.1 to 0.4 parts by weight, more preferably 0.1 to 0.3 parts by weight, and within this range, the coagulated product of the conjugated diene rubber latex As the content is reduced, the full width at half maximum particle diameter is widened, which has excellent impact strength and fluidity.

The molecular weight modifier used in step b) may be within the same range as the type used in step a).

In the present invention, since the conjugated diene compound and the molecular weight regulator are divided into steps a) and b), the polymerization reaction of the conjugated diene rubber latex is smooth even if the content of the emulsifier is reduced, so that the gel content and the coagulated product content are reduced and the hypertrophy resulting from the enlargement Conjugated diene rubber latex has a wider particle diameter and full width at half maximum, resulting in excellent impact resistance.

In the present description, the polymerization conversion rate may be defined as the weight% of the monomers converted to the polymer until measured based on 100% by weight of the total weight of the monomers input until the end of the polymerization, and the method for measuring the polymerization conversion rate is measured according to this definition The method for measuring the polymerization conversion rate is not particularly limited, and after drying 1.5 g of the prepared latex in a hot air dryer at 150° C. for 15 minutes, the weight is measured and the total solid content (Total Solid Content; TSC) , and it can be calculated using Equation 2 below. Equation 2 is based on the total weight of the added monomer being 100 parts by weight.

[Equation 1]

[Equation 2]

Polymerization conversion (%) = [total solid content (TSC) X (total weight of the added monomer, ion-exchanged water, and auxiliary materials) / 100] - (weight of added additives other than monomer and ion-exchanged water)

In Equation 2, the auxiliary material refers to an initiator, an emulsifier, an electrolyte, and a molecular weight regulator.

The input monomer refers to a conjugated diene compound in the case of conjugated diene rubber latex polymerization, and in the case of a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer latex polymerization, a conjugated diene compound, a vinyl cyan compound, and an aromatic vinyl compound refers to

The water-soluble initiator in step b-2) may preferably be 0.07 to 0.15 parts by weight, and the productivity of the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer is increased by reducing unreacted monomers within this range. Of course, there is an effect of improving the glossiness and reflection haze of the copolymer.

In step b-2), the water-soluble initiator may be, for example, at least one selected from the group consisting of hydrogen peroxide, potassium persulfate, sodium persulfate and ammonium persulfate, and preferably potassium persulfate.

The emulsifier in step b-2) may be preferably 0.1 to 0.25 parts by weight, more preferably 0.1 to 0.2 parts by weight, within this range, the gel content is reduced to improve impact resistance and to remove residues during injection molding. has a decreasing effect.

The emulsifier used in step b-2) may be within the same category as the type used in step a).

The conjugated diene rubber latex obtained in step b) may have a gel content of, for example, 80% or less, preferably 78% or less, more preferably 76% or less, within this range, the gel content is reduced and enlarged conjugated. The full width at half maximum particle diameter of diene rubber is widened, and impact resistance is greatly increased, and fluidity, reflective haze and glossiness are also excellent.

In this description, the gel content is determined by coagulating the rubber latex using a dilute acid or metal salt, washing it and drying it in a vacuum oven at 60° C. for 24 hours. After cutting the obtained rubber mass with scissors, 1 g of rubber slices After putting in 100 g of toluene and storing it in a dark room at room temperature for 48 hours, it is separated into a sol and a gel, and the gel content is measured according to Equation 3 below.

[Equation 3]

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

The conjugated diene rubber latex obtained in step b) may have, for example, an average particle diameter of 700 to 1,500 Å, preferably an average particle diameter of 800 to 1,400 Å, more preferably an average particle diameter of 1,000 to 1,200 Å, within this range. The gel content is reduced and the full width at half maximum particle diameter of the enlarged conjugated diene rubber is widened, so the impact resistance is greatly increased, and the fluidity, reflection haze and glossiness are excellent.

In this description, the average particle diameter can be measured using dynamic light scattering, and in detail, using Nicomp 380 equipment (product name, manufacturer: PSS), Gaussian 　 mode 　 intensity 　 value It can be measured with 　.

The conjugated diene rubber latex obtained in step b) may have, for example, a coagulant content of 0.5% by weight or less, preferably 0.4% by weight or less, more preferably 0.35% by weight or less, and the residue during injection molding within this range It has the effect of reducing water.

In this substrate, the coagulated content in the latex is determined by filtering the polymerized latex through a 100 mesh stainless steel mesh, drying the unfiltered coagulated material at 80° C. for 24 hours, measuring the weight, and determining the content of the total solid content. Calculated as a percentage.

c) preparing an enlarged conjugated diene rubber latex by adding 0.3 to 1 part by weight of an organic acid thickening agent to 100 parts by weight of the conjugated diene rubber latex (based on solid content)

The c) step of preparing the enlarged conjugated diene rubber latex is preferably 0.4 to 1 part by weight of the organic acid thickening agent, more preferably 0.5 to 0.9 parts by weight, more preferably based on 100 parts by weight (based on solid content) of the conjugated diene rubber latex Preferably 0.6 to 0.9 parts by weight can be added, and the conjugated diene rubber latex is uniform within this range, but the full width at half maximum particle diameter is enlarged widely and the impact resistance is improved.

The organic acid thickening agent is, for example, at least one selected from the group consisting of citric acid, citric acid monovalent salt, citric acid divalent salt, and a compound represented by the following Chemical Formula 1, preferably citric acid, malonic acid, succinic acid, glutaric acid, It may be at least one member selected from the group consisting of dipic acid, pimelic acid, serveric acid, and azelaic acid, and more preferably at least one member selected from the group consisting of citric acid, malonic acid, succinic acid and azelaic acid, in this case It has the advantage of uniformly enlarged in the particle size, good agglomeration efficiency, and wide full width at half maximum particle size.

[Formula 1]

HOOC-(CH ₂ )n-COOH

Wherein n is an integer of 1 to 15, for example, preferably an integer of 1 to 8.

The enlarged conjugated diene rubber latex obtained in step c) may have, for example, an average particle diameter of 3100 to 3500 Å, preferably an average particle diameter of 3200 to 3400 Å, more preferably an average particle diameter of 3200 to 3400 Å, Within this range, impact resistance is remarkably improved, and fluidity, reflective haze and gloss are excellent, and injection mold residues are reduced during injection molding.

The enlarged conjugated diene rubber latex obtained in step c) has, for example, a full width at half maximum particle size of 2200 to 3000 Å, preferably 2300 to 2900 Å, more preferably 2300 to 2700 Å, more preferably 2300 to 2500 Å In this range, impact resistance is remarkably improved and fluidity, reflective haze and gloss are excellent, and injection mold residues are reduced during injection molding.

In the present description, the full width at half maximum particle size means a difference between particle sizes corresponding to 1/2 of the maximum particle diameter in the particle size distribution, and the larger the difference, that is, the larger the full width at half maximum particle size, the more uniform the rubber particle size. In FIG. 1, f _max is the maximum particle size, 1/2 of the maximum particle diameter is f _max/2 , and the corresponding particle diameters are X ₁ and X ₂ respectively, and the range of X ₁ to X ₂ , that is, FWHM, is It becomes the full width at half the particle size.

In this description, the full width at half maximum particle size is measured by CHDF (Capillary Hydrodynamic Fractionation) using MATEC CHDF 400.

The enlarged conjugated diene rubber latex obtained in step c) has, for example, a coagulant content of 0.2 wt% or less, preferably 0.15 wt% or less, more preferably 0.1 wt% or less, still more preferably 0.01 to 0.1 wt% In this range, it is uniformly enlarged, impact resistance is improved, and injection mold residue is reduced during injection molding.

d) Graft polymerization including 40 to 70% by weight of the enlarged conjugated diene rubber latex (based on solid content), 15 to 45% by weight of an aromatic vinyl compound, and 5 to 25% by weight of a vinyl cyan compound-conjugated diene obtaining a rubber-aromatic vinyl compound graft copolymer

The step d) obtaining a graft copolymer preferably comprises 45 to 65% by weight of an enlarged conjugated diene rubber latex (based on solid content), 20 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound. It can be subjected to graft polymerization, and more preferably 50 to 60% by weight of the enlarged conjugated diene rubber latex (based on solid content), 25 to 35% by weight of an aromatic vinyl compound, and 12 to 17% by weight of a vinyl cyanide compound. It can be subjected to graft polymerization, and within this range, fluidity, reflective haze, gloss, and impact resistance are all excellent, and there is an effect of reducing residues in the injection mold during injection molding.

In step d), more preferably, based on a total of 100 parts by weight of the conjugated diene rubber latex (based on solid content), the aromatic vinyl compound and the vinyl cyan compound, d-1) 40 to 70 weight of the enlarged conjugated diene rubber latex parts (based on solid content) and 80 to 120 parts by weight of ion-exchanged water, 15 to 45 parts by weight of an aromatic vinyl compound, 5 to 25 parts by weight of a vinyl cyanide compound, 10 to 30 parts by weight of ion-exchanged water, 0.01 to 2 parts by weight of an emulsifier, and A first graft reaction by continuously introducing a mixed solution containing 0.01 to 2 parts by weight of a molecular weight modifier, 0.01 to 2 parts by weight of a fat-soluble polymerization initiator, and 0.001 to 0.4 parts by weight of an oxidation-reduction catalyst at 65 to 75° C. for 2 to 4 hours polymerization step; d-2) after the first graft polymerization step, adding 0.001 to 0.6 parts by weight of an oxidation-reduction catalyst and 0.001 to 0.5 parts by weight of a fat-soluble polymerization initiator; d-3) a second graft polymerization step in which the oxidation-reduction catalyst and the fat-soluble polymerization initiator are added, and the temperature is raised to a temperature of 75 to 85° C. for 50 to 70 minutes to react; and d-4) terminating the polymerization reaction when the conversion rate of the polymerization reaction is 90 to 99%; in this case, fluidity, reflective haze, gloss and impact resistance are all excellent and injection molding is performed It has the effect of reducing the residue on the mold.

In step d-1), the emulsifier may be 0.01 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, more preferably 0.1 to 1 parts by weight, more preferably 0.2 to 0.7 parts by weight, within this range. It has excellent latex stability and has the effect of reducing the coagulant content.

In step d-1), the emulsifier may be, for example, a multimer acid of an unsaturated fatty acid or a metal salt thereof, and in this case, the latex stability is excellent and the coagulant content is reduced.

The unsaturated fatty acid may be, for example, a linear, branched or cyclic unsaturated fatty acid having 8 to 22 carbon atoms, in which case the coagulation of the latex is reduced and the residue in the injection mold is reduced during injection molding.

In step d-1), the molecular weight modifier may be preferably 0.05 to 1.5 parts by weight, more preferably 0.1 to 1 parts by weight, and still more preferably 0.2 to 0.7 parts by weight.

In step d-1), the oxidation-reduction catalyst may be in an amount of preferably 0.01 to 0.3 parts by weight, more preferably 0.05 to 0.2 parts by weight.

The d-1) step, preferably, can be continuously added for 2.5 to 3.5 hours at 67 to 73 ° C., and has excellent grafting efficiency and reduced latex coagulation within this range.

In step d-2), the oxidation-reduction catalyst may be in an amount of preferably 0.001 to 0.6 parts by weight, more preferably 0.01 to 0.3 parts by weight.

In step d-2), the molecular weight modifier may be preferably 0.01 to 0.3 parts by weight, more preferably 0.03 to 0.1 parts by weight.

In step d-3), the reaction may be performed by raising the temperature for 55 to 65 minutes to a temperature of preferably 77 to 82°C, and within this range, the reaction efficiency is excellent and the coagulated content is reduced.

In step d-4), the polymerization reaction may preferably be terminated at a polymerization conversion rate of 93 to 97%.

The latex of the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer obtained in step d-4) may be obtained in powder form, for example, through conventional processes such as agglomeration, washing, and drying.

The aggregation may be carried out by adding 0.1 to 2 parts by weight, preferably 0.5 to 1.5 parts by weight of the acid coagulant, based on 100 parts by weight (based on solid content) of the graft copolymer latex, for example.

The acid coagulant may be, for example, at least one selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid and acetic acid, preferably sulfuric acid, and in this case, the coagulation efficiency is good and the gloss is excellent.

The vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer obtained in step d) has, for example, a coagulant content of 0.2 wt% or less, preferably 0.15 wt% or less, more preferably 0.1 wt% or less Within this range, impact resistance is improved and residues on the injection mold are reduced during injection molding.

In the present description, when the electrolyte, the acid thickening agent, and the coagulant include a solvent such as water, their weight means the weight excluding the solvent.

Method for producing a thermoplastic resin composition

The manufacturing method of the thermoplastic resin composition of the present invention comprises the steps of preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer according to the above manufacturing method; And 15 to 35% by weight of the prepared graft copolymer and 65 to 85% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer are added to an extruder, melt-kneaded and then extruded; may include, in this case It has excellent fluidity, reflective haze, and gloss, and, in particular, has excellent impact resistance and has the effect of reducing residues in the injection mold during injection molding.

Preferably, the method for preparing the thermoplastic resin composition comprises: preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer according to the manufacturing method; And 20 to 30% by weight of the prepared graft copolymer and 70 to 80% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer are added to an extruder, melt-kneaded, and then extruded; may include, in this case It has excellent fluidity, reflective haze, and gloss, and, in particular, has excellent impact resistance and has the effect of reducing residues in the injection mold during injection molding.

The melt-kneading and extrusion step is, for example, the barrel temperature is 200 to 330 ℃ for example, preferably 210 to 300 ℃, more preferably 210 to 280 ℃, even more preferably 220 to 250 ℃ It is carried out within the range In this case, the throughput per unit time may be adequate and sufficient melt-kneading may be possible, and there is an effect that does not cause problems such as thermal decomposition of the resin component.

In the melt-kneading and extrusion step, for example, the screw rotation speed is 100 to 500 rpm, preferably 150 to 400 rpm, more preferably 100 to 350 rpm, still more preferably 200 to 310 rpm, most preferably 250 to 350 It may be carried out under the condition of rpm, and in this case, the throughput per unit time is appropriate, so that the process efficiency is excellent, and there is an effect of suppressing excessive cutting.

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

In the melt-kneading, for example, 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, 0.1 to 100 parts by weight of the thermoplastic resin composition 10 parts by weight, preferably, may be added within the range of 0.1 to 5 parts by weight.

The aromatic vinyl compound-vinyl cyan compound copolymer is, for example, 65 to 85 wt % of an aromatic vinyl compound and 15 to 35 wt % of a vinyl cyan compound, preferably 70 to 80 wt % of an aromatic vinyl compound and 20 to 30 wt % of a vinyl cyan compound %, and within this range, fluidity is adequate, so that processability is excellent and impact resistance is excellent.

The aromatic vinyl compound-vinyl cyan compound copolymer may have, for example, a weight average molecular weight of 120,000 to 200,000 g/mol, preferably 140,000 to 180,000 g/mol, and has adequate fluidity within this range to provide excellent processability and resistance It has an excellent impact resistance effect.

In the present description, unless otherwise defined, the weight average molecular weight may be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as the eluent ) can be measured as a relative value with respect to a standard PS (standard polystyrene) sample.

In the present description, a polymer including a certain compound means a polymer polymerized including the compound, and a unit in the polymerized polymer is derived from the compound.

The aromatic vinyl compound-vinyl cyan compound copolymer may be prepared by, for example, solution polymerization or bulk polymerization, preferably bulk polymerization, and in this case, heat resistance and fluidity are excellent.

The solution polymerization and bulk polymerization are not particularly limited in the case of solution polymerization and bulk polymerization methods commonly carried out in the technical sale to which the present invention belongs, respectively.

In the present description, the conjugated diene compound is, for example, 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. It may be one or more types, and may preferably be 1,3-butadiene.

In the present description, the aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-tert-butylstyrene, and is preferably styrene.

In the present description, the vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methnitrolonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, and is preferably acrylonitrile.

Thermoplastic resin composition

The thermoplastic resin composition of the present disclosure includes 15 to 35 wt% of a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer and 65 to 85 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer, wherein the conjugated diene rubber has an average particle diameter of 3100 to 3500 Å, a full width at half maximum particle diameter of 2200 to 3000 Å, and an Izod impact strength of 38 kgf cm/cm or more, measured with a specimen thickness of 1/8″ according to ASTM D256. In this case, while the impact resistance is greatly increased, fluidity, reflective haze, and gloss are all excellent, and there is an effect of reducing residues in the injection mold during injection molding.

The conjugated diene rubber latex may have an average particle diameter of preferably 3200 to 3400 Å, more preferably 3200 to 3400 Å, within this range, impact resistance is remarkably improved and fluidity, reflective haze and glossiness are excellent, and injection There is an effect of reducing the injection mold residue during molding.

The conjugated diene rubber latex may have a full width at half maximum particle size of preferably 2300 to 2900 Å, more preferably 2300 to 2700 Å, more preferably 2300 to 2500 Å, within this range, impact resistance is significantly improved while fluidity , It has excellent reflective haze and gloss, and has the effect of reducing injection mold residues during injection molding.

The thermoplastic resin composition preferably has an Izod impact strength of 40 kgf·cm/cm or more, more preferably 41 kgf·cm/cm or more, even more preferably, measured with a specimen thickness of 1/8″ according to ASTM D256. may be 43 to 47 kgf·cm/cm, and within this range, the physical property balance has an excellent effect.

The thermoplastic resin composition has an Izod impact strength of 24 kgf·cm/cm or more, preferably 25 kgf·cm/cm or more, more preferably 25 to It may be 30 kgf·cm/cm, and within this range, the physical property balance has an excellent effect.

The thermoplastic resin composition has a flow index of 21 g/10min or more, preferably 22 g/10min or more, more preferably 23 to 27 g/10min, measured for 10 minutes at 220°C under a 10Kg load, according to ASTM D1238, for example. may be, and it has excellent fluidity within this range and has the advantage of easy molding into various shapes.

The thermoplastic resin composition has, for example, a reflection haze measured in accordance with ASTM E430 with a RhopointQ device of Rhopoint instruments Co., Ltd. is 1.6 or less, preferably 1.5 or less, more preferably It may be 1.2 or less, and most preferably 0.7 to 1.2, and within this range, the physical property balance is excellent and the surface sharpness is excellent.

The thermoplastic resin composition may have a gloss of 93 or more, preferably 97 or more, more preferably 100 to 110, as measured at a 45° angle with a gloss meter according to ASTM D258, for example, Within this range, the physical property balance is excellent and the surface appearance is excellent.

The thermoplastic resin composition is, for example, using an injection machine (ENGEL, 150 tons) to inject 100 kg of resin at a cylinder temperature of 230°C and a mold temperature of 25°C in a cycle of 30 seconds, and the injection mold residue remaining on the plate It may be 94 mg or less, preferably 92 mg or less, more preferably 85 to 92 mg, and within this range, the physical property balance is excellent, the productivity is excellent, and the appearance quality is excellent.

The time it takes for pellets to melt in the injection machine cylinder at 220°C and to be ejected into the mold at 30°C to harden is 30 seconds, which is one cycle.

The thermoplastic resin composition may optionally contain at least one selected from the group consisting of antioxidants, UV stabilizers, dyes, pigments, flame retardants and inorganic fillers, based on 100 parts by weight of the thermoplastic resin composition, in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, even more preferably 0.5 to 1 parts by weight may further include, within this range, without reducing the original properties of the thermoplastic resin composition of the present base material There is an effect that the necessary physical properties are well realized.

The thermoplastic resin composition shares all the technical features of the method for producing the above-described thermoplastic resin composition. Therefore, a description of the overlapping portion will be omitted.

molded product

The molded article of the present base material is characterized in that it contains the thermoplastic resin composition, and in this case, it has excellent fluidity, reflective haze and gloss, and has significantly improved impact resistance compared to conventional ABS resins, and significantly reduces residues during injection molding, resulting in productivity and excellent product appearance.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such variations and modifications fall within the scope of the appended claims.

[Example]

Example 1

< Conjugated diene rubber latex manufacturing >

90 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor (autoclave), 30 parts by weight out of 100 parts by weight of 1,3-butadiene as a conjugated diene compound, 1 part by weight of fatty acid saponification as an emulsifier, Na ₂ SO ₄ as an electrolyte 0.3 parts by weight, 0.15 parts by weight of tertiary dodecylmercaptan (TDDM) as a molecular weight modifier, 0.15 parts by weight of tertiary butyl hydroperoxide as a fat-soluble initiator, 0.06 parts by weight of dextrose as an oxidation-reduction catalyst, 0.005 sodium pyrophosphate Parts by weight and 0.0025 parts by weight of ferrous sulfate were administered in batches, and the reaction temperature was maintained at 55° C. for 1 hour. Thereafter, the temperature was raised to 78° C. over 9 hours while continuously introducing 70 parts by weight of the remaining 1,3-butadiene and 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator. After reacting to a polymerization conversion of 30 to 40%, 0.1 parts by weight of potassium persulfate as a water-soluble initiator and 0.15 parts by weight of a rosin acid emulsifier were additionally added. The reaction was terminated at a polymerization conversion rate of 95%, and the average particle diameter of the conjugated diene rubber latex was 1180 Å.

< Conjugated diene rubber latex hypertrophy >

To 100 parts by weight of the conjugated diene rubber latex prepared above (based on solid content), an aqueous solution containing 0.6 parts by weight of citric acid as an organic acid thickening agent was added to enlarge it, and the average particle diameter of the enlarged conjugated diene rubber latex was 3420 Å.

< Polymerization of vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer >

In a nitrogen-substituted polymerization reactor, 55 parts by weight (based on solid content) of the enlarged conjugated diene rubber latex prepared above and 100 parts by weight of ion-exchanged water, 15 parts by weight of acrylonitrile, 30 parts by weight of styrene mixed in a separate mixing device, 20 parts by weight of ion-exchanged water, 0.4 parts by weight of saponified dimer acid, and 0.35 parts by weight of tertiary dodecyl mercaptan, 0.12 parts by weight of t-butyl hydroperoxide, 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrrolate Parts and 0.002 parts by weight of ferrous sulfate were continuously added together at 70° C. for 3 hours. After the addition was completed, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrophosphate, 0.001 parts by weight of ferrous sulfate and 0.05 parts by weight of t-butyl hydroperoxide were put into the polymerization reactor at once, and the temperature was increased to 80° C. for 1 hour. After raising the temperature over to terminating the reaction, acrylonitrile-butadiene-styrene (hereinafter referred to as 'ABS') latex was prepared.

Based on 100 parts by weight of the prepared ABS latex (based on solid content), 1 part by weight of MgSO ₄ was added and agglomerated, followed by washing and drying to obtain ABS powder.

<Preparation of thermoplastic resin composition>

25 parts by weight of the ABS powder obtained above and 75 parts by weight of a SAN resin (LG Chem, weight average molecular weight 120,000 g/mol, acrylonitrile content 27% by weight) were kneaded and extruded under 210 to prepare pellets. Melt index was measured with the prepared pellets. In addition, the prepared pellets were injected at a molding temperature of 220° C. to prepare a specimen for measuring physical properties.

Example 2

Example 1 was carried out in the same manner as in Example 1, except that 0.85 parts by weight of citric acid monovalent salt was added instead of 0.6 parts by weight of citric acid as an organic acid thickening agent in <Conjugated diene rubber latex enlargement>.

Example 3

Example 1 was carried out in the same manner as in Example 1, except that 0.5 parts by weight of malonic acid was added as an organic acid thickening agent in <Conjugated diene rubber latex enlargement>.

Example 4

Example 1 was carried out in the same manner as in Example 1, except that 0.86 parts by weight of succinic acid was added as an organic acid thickening agent in <Conjugated diene rubber latex enlargement>.

Example 5

Example 1 was carried out in the same manner as in Example 1, except that 0.86 parts by weight of azelaic acid was added as an organic acid thickening agent in <Conjugated diene rubber latex enlargement>.

Comparative Example 1

< Conjugated diene rubber latex manufacturing >

75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor (autoclave), 90 parts by weight out of 100 parts by weight of 1,3-butadiene as a monomer, 3 parts by weight of saponified dimer as an emulsifier, potassium carbonate (K ₂ CO ₃ ) 0.1 parts by weight, 0.1 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, 0.15 parts by weight of tertiary butyl hydroperoxide as an initiator, 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrophosphate and sulfuric acid 0.0025 parts by weight of ferrous iron was batch-administered and reacted at a reaction temperature of 55°C to a polymerization conversion rate of 30 to 40%, and then 0.3 mass% of potassium persulfate was batch-injected, the temperature was raised to 72°C, and the residual at a polymerization conversion rate of 60 to 70% 10 parts by weight of 1,3-butadiene was batch-injected, and the reaction was terminated at a polymerization conversion rate of 95%, and the average particle diameter of the obtained conjugated diene rubber latex was 1155 Å.

< Conjugated diene rubber latex hypertrophy >

An aqueous solution containing 1.5 parts by weight of acetic acid as a thickening agent was added to 100 parts by weight of the conjugated diene rubber latex (based on solid content) prepared above to enlarge, and the average particle diameter of the enlarged conjugated diene rubber latex was 3272 Å.

< Polymerization of vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer >

It was carried out in the same manner as <Vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer polymerization> of Example 1.

<Preparation of thermoplastic resin composition>

It was carried out in the same manner as <Preparation of the thermoplastic resin composition> of Example 1.

Comparative Example 2

In <Conjugated diene rubber latex enlargement> of Comparative Example 1, it was carried out in the same manner as in Comparative Example 1, except that 1.45 parts by weight of citric acid monovalent salt was added instead of 1.5 parts by weight of acetic acid as a thickening agent.

Comparative Example 3

Example 1 was carried out in the same manner as in Example 1, except that 0.9 parts by weight of acetic acid was added instead of 0.6 parts by weight of citric acid as a thickening agent in <Conjugated diene rubber latex enlargement>.

Comparative Example 4

Example 1 was carried out in the same manner as in Example 1, except that 1.2 parts by weight of citric acid was added as an organic acid in <Conjugated diene rubber latex enlargement>.

[Test Example]

The properties of the pellets and specimens prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were measured by the following method, and the results are shown in Tables 1 and 2 below.

* Average particle diameter (Å): It can be measured using dynamic light scattering, and in detail, Gaussian 　 modro 　 intensity using Nicomp 380 equipment (product name, manufacturer: PSS) It was measured as a value.

* Particle size full width at half maximum (Å): Capillary hydrodynamic fractionation (CHDF) was measured using MATEC CHDF 400.

* Gel content (%): After the rubber latex is coagulated using dilute acid or metal salt, washed and dried in a vacuum oven at 60° C. for 24 hours, then the obtained rubber mass is chopped with scissors, and 1 g of rubber section was put into 100 g of toluene and stored in a dark room at room temperature for 48 hours, separated into a sol and a gel, and the gel content was calculated according to Equation 3 below.

[Equation 3]

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

* Coagulant content (wt%): After filtering the polymerized latex through a 100 mesh stainless steel mesh, the unfiltered coagulated material is dried at 80 ° C. for 24 hours, and then the weight is measured and the content is calculated based on the total solid content Calculated as a percentage.

* Melt index (g/10min): The prepared pellets were measured according to ASTM D1238 method under the conditions of 220 °C and 10 kg.

* Izod impact strength (IMP; kgf·cm/cm): It was measured according to ASTM D256 at 1/4" and 1/8" thickness of the specimen, respectively.

* Glossiness: measured at 45° according to ASTM D528.

* Reflection Haze: It was measured by adding gloss values between 17 to 19 ° and 21 to 23 ° in accordance with ASTM E430 with a RhopointQ instrument of Rhopoint instruments. The lower the reflection haze, the better the surface quality.

* Mold deposit (mg): 100 kg of resin is injected using an injection machine (ENGEL, 150 tons) at a cylinder temperature of 230°C and a mold temperature of 25°C for 30 seconds The injection residue was weighed.

division Example 1 Example 2 Example 3 Example 4 Example 5 conjugated diene
Rubber
latex Emulsifier (parts by weight) 1.0 1.0 1.0 1.0 1.0 average particle diameter 1180 1180 1180 1180 1180 coagulum content 0.32 0.32 0.32 0.32 0.32 Gel content (%) 75 75 75 75 75 hypertrophic
conjugated diene
Rubber
latex organic acid
hypertrophic
(parts by weight) citric acid
0.6 citric acid monovalent salt
0.85 malonic acid
0.5 succinic acid
0.86 azelaic acid
0.86 coagulum content 0.14 0.05 0.2 0.04 0.05 average particle diameter 3240 3285 3310 3330 3290 full width of particle size 2720 2360 2820 2420 2380 ABS resin coagulum content 0.14 0.03 0.17 0.025 0.03 thermoplastic
profit
composition 1/4" impact strength 25.4 28.2 24.5 27.9 28.4 1/8" impact strength 41.4 45.9 39.7 45.2 46.2 flow index 22.7 24.8 21.9 24.4 24.2 reflex haze 1.6 1.1 1.5 1.0 1.1 glossiness 93 105 93 107 105 Injection mold residue 94 92 91 92 92

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 conjugated diene
Rubber
latex Emulsifier (parts by weight) 3 3 1.0 1.0 average particle diameter 1155 1155 1180 1180 coagulum content 0.31 0.31 0.32 0.32 Gel content (%) 90 90 75 75 hypertrophic
conjugated diene
Rubber
latex Hypertrophic agent (parts by weight) acetic acid
1.5 citric acid monovalent salt
1.45 acetic acid
0.9 citric acid
1.2 coagulum content 0.06 0.05 0.04 1.0 average particle diameter 3272 3240 3200 3680 full width of particle size 620 1312 582 2890 ABS resin coagulum content 0.04 0.05 0.03 1.1 thermoplastic
profit
composition 1/4" impact strength 23 23.7 25.3 10.2 1/8" impact strength 34.2 35.1 35.8 10.3 flow index 23.2 22.9 25.1 19.5 reflex haze 1.5 1.4 1.0 2.3 glossiness 98 96 96 92 injection mold residue 148 145 96 93

As shown in Tables 1 and 2, the thermoplastic resin compositions (Examples 1 to 5) according to the present invention are excellent in fluidity, reflection haze and gloss compared to Comparative Examples 1 to 4, and have a specimen thickness of 1/4" and 1 At /8", the impact strength was significantly increased, and it was confirmed that the injection mold residue was reduced.

In addition, Comparative Examples 1 and 2 prepared according to the prior art had a narrow full width at half maximum particle diameter, low impact strength and reflection haze, and a sharp increase in injection mold residues.

In addition, in Comparative Example 3, in which the conjugated diene rubber latex prepared according to the present invention was enlarged with acetic acid, the full width at half maximum particle diameter was very narrow, the impact strength was reduced, and the injection mold residue was increased.

In addition, in Comparative Example 4, in which the organic acid thickening agent exceeded the scope of the present invention, the impact strength, flow index, reflection haze and gloss were all inferior.

Claims (15)

a) a polymerization reaction including 0.1 to 2 parts by weight of an emulsifier, a molecular weight regulator and an electrolyte in 20 to 40 parts by weight of a total of 100 parts by weight of the conjugated diene compound;
b) after step a), adding a residual conjugated diene compound and a molecular weight modifier to polymerization to obtain a conjugated diene rubber latex;
c) preparing an enlarged conjugated diene rubber latex by adding 0.3 to 1 parts by weight of an organic acid thickening agent to 100 parts by weight of the conjugated diene rubber latex (based on solid content); and
d) Graft polymerization including 40 to 70% by weight of the enlarged conjugated diene rubber latex (based on solid content), 15 to 45% by weight of an aromatic vinyl compound, and 5 to 25% by weight of a vinyl cyan compound-conjugated diene Including; obtaining a rubber-aromatic vinyl compound graft copolymer;
The enlarged conjugated diene rubber latex obtained in step c) has an average particle diameter of 3100 to 3500 Å and a full width at half maximum particle diameter of 2200 to 3000 Å
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
The molecular weight regulator in step a) and step b), characterized in that 0.05 to 0.3 parts by weight, 0.1 to 0.5 parts by weight, respectively
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
In step a), the polymerization reaction is carried out at 50 to 60° C. for 50 to 70 minutes.
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
The step a) comprises 0.1 to 0.5 parts by weight of an oxidation-reduction catalyst, 0.01 to 0.7 parts by weight of a fat-soluble polymerization initiator, and 80 to 120 parts by weight of ion-exchanged water, characterized in that the polymerization reaction is carried out.
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
The step b) is characterized in that the residual conjugated diene compound, and the molecular weight regulator are continuously added while raising the temperature to 73 to 83° C. for 8 to 10 hours.
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
In step b), b-1) polymerizing the remaining conjugated diene compound and the molecular weight regulator by continuously adding the temperature to 73 to 83° C. for 8 to 10 hours; b-2) adding 0.05 to 0.2 parts by weight of an initiator and 0.05 to 0.3 parts by weight of an emulsifier at a polymerization conversion rate of 30 to 40% by weight, followed by polymerization; and b-3) terminating the polymerization reaction at a polymerization conversion rate of 93 to 99% by weight.
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
The conjugated diene rubber latex obtained in step b) has a gel content of 80% or less
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to claim 1,
The organic acid thickening agent in step c), characterized in that at least one selected from the group consisting of citric acid, citric acid monovalent salt, citric acid divalent salt, and a compound represented by the following formula (1)
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
[Formula 1]
HOOC-(CH ₂ )n-COOH
Wherein n is an integer of 1 to 10.
According to claim 1,
In step d), based on a total of 100 parts by weight of the conjugated diene rubber latex (based on solid content), the aromatic vinyl compound and the vinyl cyan compound, d-1) 40 to 70 parts by weight of the enlarged conjugated diene rubber latex (based on the solid content) ) and 80 to 120 parts by weight of ion-exchanged water, 15 to 45 parts by weight of an aromatic vinyl compound, 5 to 25 parts by weight of a vinyl cyanide compound, 10 to 30 parts by weight of ion-exchanged water, 0.01 to 2 parts by weight of an emulsifier, and 0.01 to 2 parts by weight of an emulsifier. A first graft polymerization step of continuously introducing and reacting a mixed solution containing 2 parts by weight, 0.01 to 2 parts by weight of a fat-soluble polymerization initiator, and 0.001 to 0.4 parts by weight of an oxidation-reduction catalyst at 65 to 75° C. for 2 to 4 hours; d-2) after the first graft polymerization step, adding 0.001 to 0.6 parts by weight of an oxidation-reduction catalyst and 0.001 to 0.5 parts by weight of a fat-soluble polymerization initiator; d-3) a second graft polymerization step in which the oxidation-reduction catalyst and the fat-soluble polymerization initiator are added, and the temperature is raised to a temperature of 75 to 85° C. for 50 to 70 minutes to react; and d-4) terminating the polymerization reaction when the conversion rate of the polymerization reaction is 90 to 99%.
A method for preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
10. A method for preparing a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound according to any one of claims 1 to 9; and
15 to 35 wt% of the prepared graft copolymer and 65 to 85 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer are added to an extruder, melt-kneaded, and then extruded;
A method for producing a thermoplastic resin composition.
15 to 35 wt% of a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer and 65 to 85 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer,
The conjugated diene rubber has an average particle diameter of 3100 to 3500 Å and a full width at half maximum particle diameter of 2200 to 3000 Å,
Characterized in that the Izod impact strength measured with a specimen thickness of 1/8″ according to ASTM D256 is 38 kgf·cm/cm or more
Thermoplastic resin composition.
12. The method of claim 11,
The thermoplastic resin composition is characterized in that the reflection haze (Reflection Haze) measured according to ASTM E430 with a RhopointQ device of Rhopoint instruments is 1.6 or less.
Thermoplastic resin composition.
12. The method of claim 11,
The thermoplastic resin composition is characterized in that the glossiness measured at 45 ° in accordance with ASTM D528 is 93 or more
Thermoplastic resin composition.
12. The method of claim 11,
The thermoplastic resin composition was obtained by injecting 100 kg of resin in a cycle of 30 seconds at a cylinder temperature of 230°C and a mold temperature of 25°C using an injection machine (ENGEL, 150 tons), and then 94 mg of the injection mold residue remaining on the plate. characterized by the following
Thermoplastic resin composition.
Claims 11 to 14, characterized in that it comprises the thermoplastic resin composition of any one of claims
molded article.

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