WO2018088677A1 - Thermoplastic resin and thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin and, more specifically, to a thermoplastic resin, which is a graft copolymer having a seed-shell structure and comprises: a bimodal seed comprising a large-diameter rubber polymer having an average diameter greater than 2,000 Å and less than or equal to 3,500 Å and a small-diameter rubber polymer having an average diameter of 500-2,000 Å; and an aromatic vinyl-cyanovinyl shell, wherein a cyanovinyl compound is included in an amount of 5-28 wt% on the basis of the total weight of the shell. The present invention has effects of providing: a thermoplastic resin having a composition capable of improving grafting density; and a thermoplastic resin composition containing the same and having high gloss by increasing dispersity.

Description

Thermoplastic and Thermoplastic Compositions

[Reciprocal citation with application (s)]

This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0149954 dated November 11, 2016 and Korean Patent Application No. 10-2017-0094026 dated July 25, 2017. All content disclosed in the literature is included as part of this specification.

The present invention relates to a thermoplastic resin and a thermoplastic resin composition, and more particularly, to a thermoplastic resin having a composition capable of improving graft density, and a thermoplastic resin composition having high glossiness, including high dispersion.

Acrylonitrile-Butadiene-Styrene (hereinafter referred to as ABS) resins may be used in automotive, electrical, and electronic applications due to the stiffness and chemical resistance of acrylonitrile, the processability of butadiene and styrene, the mechanical strength, and the beautiful appearance. It is widely used in electronic products and office equipment. Surface gloss and dispersion in the various blending resins of these ABS resins are one of the important factors that determine the quality of processed molded articles.

However, the surface gloss and dispersion in various blending resins of ABS resins are affected by various factors, such as unreacted monomer and emulsifier, during processing by high temperature extrusion and injection as well as particle size and distribution. If the additive is low, but additives such as compatibilizers are added separately, in this case, there is a disadvantage such as poor workability or increase the amount of gas generated during the processing, it is a technique of improving the surface gloss and dispersion in various blending resins of ABS resin Development continues to be required in the industry.

[Prior art document]

[Patent Documents] (Patent Document 1) US Patent No. 4,360,618

It is an object of the present invention to provide a thermoplastic resin having a composition capable of improving graft density and a thermoplastic resin composition having high glossiness, including a high dispersion.

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

In order to achieve the above object, the present invention provides a graft copolymer having a seed-shell structure, a large diameter rubber polymer having an average particle diameter of more than 2,000 GPa to 3,500 GPa and a small diameter rubber polymer having an average particle diameter of 500 GPa to 2,000 GPa A bimodal seed comprising an aromatic vinyl-vinylcyan polymer shell surrounding the seed, wherein the vinylcyan compound is included in the range of 5 to 28% by weight relative to the total weight of the shell; Provide resin.

In another aspect, the present invention provides a thermoplastic resin composition comprising the thermoplastic resin and polyarylene ether, wherein the thermoplastic resin is 15 to 50% by weight, the polyarylene ether is contained in 50 to 85% by weight. .

According to the present invention, there is an effect of providing a thermoplastic resin composition having a high glossiness by providing a composition of a thermoplastic resin which can improve graft density, thereby increasing dispersion.

1 is a SEM photograph of the dispersion degree of the specimen prepared from the thermoplastic resin composition according to the Examples and Comparative Examples. Respective examples are (a) Example 1, (b) Comparative Example 1, and (c) Comparative Example 2.

2 is a thermogravimetric analysis (TGA) graph comparing the thermal stability of each emulsifier.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin according to the present invention is a graft copolymer having a seed-shell structure, comprising a large diameter rubber polymer having an average particle diameter of more than 2,000 mm 3 and less than 3,500 mm 3 and a small diameter rubber polymer having an average particle diameter of 500 mm 2 to 2,000 mm 3 A modal seed, comprising an aromatic vinyl-vinylcyan polymer shell surrounding the seed, wherein the vinylcyan compound is included in the range of 5 to 28% by weight relative to the total weight of the shell.

The graft copolymer of the seed-shell structure may include, for example, (a) a seed comprising a bimodal conjugated diene rubber polymer; And (b) a shell surrounding the seed and polymerized with an aromatic vinyl compound and a vinyl cyan compound, and a fatty acid dimer or a metal salt thereof.

The conjugated diene rubber polymer of the seed is, for example, a 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 polymerized including at least one conjugated diene-based compound selected from.

For example, the seed may be emulsion polymerized, and in this case, there is an effect of excellent mechanical properties, and is not particularly limited as long as it is manufactured according to a conventional emulsion polymerization method. In another example, the seed may be in the form of a latex in which the polymerized rubbery polymer is dispersed in water in a colloidal state.

The seed has, for example, an average particle diameter of more than 2,000 kPa to 3,500 kPa or less, 2,500 kPa or more to 3,500 kPa or less, or 3,000 kPa or more and 3,500 kPa or less, and a gel content of 60 to 95 wt%, 65 to 80 wt%, or 65 To 75% by weight large diameter seeds, for example, with an average particle diameter of 500 kPa to 2,000 kPa, 1,000 kPa to 2,000 kPa, or 1,000 kPa to 1,500 kPa, with a gel content of 60 to 95 wt%, 70 to 95 wt%, or 80 It may be bimodal of the small diameter seed to 95% by weight, and within this range there is an excellent impact strength and mechanical properties.

In this description, the average particle diameter is measured by a dynamic laser light skating method using a Nicomp 370HPL device manufactured by Nicomp.

In the present description, the gel content is determined by coagulation of polybutadiene rubber latex with dilute acid or metal salt, washing, drying in a vacuum oven at 60 ° C. for 24 hours, and then crushing the obtained rubber mass with scissors, and then removing 1 g of rubber sections. 100 g of toluene was stored in a dark room at room temperature for 48 hours, separated into sol and gel, dried, and then measured by the following equation.

The large-diameter seed and the small-diameter seed constituting the seed may be 50:50 to 90:10, 60:40 to 75:25, 60:40 to 70:20, or 70:30 to 75:25 by weight, for example. Within this range, the dispersion and the surface properties are excellent.

For example, the seed may be included in an amount of 30 to 80 wt%, 40 to 75 wt%, or 50 to 70 wt% based on 100 wt% of the total content of the conjugated diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound. Mechanical properties and surface properties are excellent within.

The shell is emulsified graft polymerized to include the fatty acid having a mean carbon number and molecular weight or a metal salt thereof surrounding the bimodal seed, for example 100% by weight of the total content of the conjugated diene rubber polymer, aromatic vinyl compound and vinyl cyan compound It may be included in 20 to 70% by weight, 25 to 60% by weight, or 30 to 50% by weight on the basis, there is an excellent effect of mechanical and physical properties balance within this range.

The aromatic vinyl compound includes, for example, styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene and derivatives thereof. It may be at least one selected from the group, and the vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof.

In the present description, the derivative may mean a compound in which one or two or more hydrogen atoms of the original compound are substituted with a halogen group, an alkyl group, and a hydroxy group.

The vinylcyan compound is 5 to 28% by weight, 5 to 20% by weight or less, 5 to 20% by weight, 5 to 15% by weight, or 5 to 28% by weight of the total weight of the shell (aromatic vinyl-vinylcyan polymer shell). It may be preferable to be included in 10% by weight, there is an effect that the mechanical properties and physical properties balance within this range. The content of the aromatic vinyl compound and the vinyl cyan compound included in the shell may be included, for example, in the range of 90:10 to 99: 1 based on the weight ratio.

The fatty acid may be, for example, two or more kinds, two to ten kinds, or two to five kinds of fatty acid dimers, metal salts thereof, or mixtures thereof having different carbon numbers in the chain. The average carbon number of the chain of the fatty acid may be, for example, 10 or more, 33 or more, 33 to 44, or 33 to 36, and excellent thermal stability within this range, thereby reducing the amount of gas generated during extrusion and injection processing. have.

The fatty acid may include, for example, an unsaturated fatty acid dimer having an unsaturation of 1 to 20, 1 to 10, 1 to 5, or 2 to 3, and has a low volatile content during extrusion injection molding within this range.

The molecular weight of the fatty acid may be, for example, 500 g / mol or more, 500 to 2000 g / mol, or 500 to 1000 g / mol, and has excellent thermal stability within this range, thereby reducing the amount of gas generated during extrusion and injection processing. It is effective to let.

The molecular weight here refers to the average molecular weight or weight average molecular weight measured by a gel permeation chromatography (GPC) instrument after drying for 15 minutes in a 120 ℃ oven to obtain a solid content, 0.2% by weight solution in THF solvent.

The fatty acid may include, for example, one or more selected from the group consisting of oleic acid, oleic acid-based dimer, myristoleic acid, linoleic acid, and metal salts thereof.

The metal of the metal salt is, for example, an alkali metal, and in particular, may be potassium or sodium.

The fatty acid is, for example, 0.1 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.1 to 1 parts by weight, or 0.1 to 0.3 parts by weight based on 100 parts by weight of the total content of the conjugated diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound. It can be included as a portion, there is an effect to increase the polymerization stability and storage stability of the polymer within this range.

The fatty acid may include, for example, 50% by weight or more, 60 to 100% by weight, or 61 to 100% by weight of an oleic acid-based dimer, and excellent thermal stability within this range, so that the gas during extrusion and injection processing There is an effect of reducing the amount of generation.

The fatty acid is, for example, 0.1 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.1 to 1 parts by weight, or 0.1 to 0.3 parts by weight based on 100 parts by weight of the total content of the conjugated diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound. It can be included as a wealth.

For example, the thermoplastic resin of the present invention may have a graft ratio of 50% or more, 60 to 90%, or 70 to 85%, and excellent surface gloss and dispersion in this range, and excellent mechanical properties.

The thermoplastic resin of the present invention may, for example, have a weight average molecular weight of 20,000 to 200,000 g / mol, 20,000 to 150,000 g / mol, 20,000 to 100,000 g / mol, 30,000 g / mol or more and less than 85,000 g / mol, or 30,000 to 70,000 g It may be / mol, excellent surface gloss and dispersion in this range, and excellent mechanical properties.

In another example, the thermoplastic resin of the present invention may have a weight average molecular weight of 100,000 to 200,000 g / mol, 120,000 to 180,000 g / mol, or 130,000 to 170,000 g / mol, and have excellent surface gloss and dispersibility within this range. In addition, the mechanical properties are excellent.

Here, a weight average molecular weight refers to the molecular weight measured by gel permeation chromatography (GPC).

The thermoplastic resin of the present invention may have a graft density (σ) of more than 0.12 to 0.80 or less, 0.20 to 0.70, or 0.30 to 0.64, and excellent surface gloss and dispersibility within this range, and excellent mechanical properties. have.

Wherein the graft density (σ) is characterized by the following equation:

Where g _d is the graft ratio (%) calculated by Equation 2 below, D is the average particle diameter measured by the light scattering method, and ρ is the density value of butadiene rubber particles measured by the ASTM D792 method, and ρP given in the above formula. Represents large diameter PBL 0.94 g / cm ³ , small diameter PBL 0.97 g / cm ³ , N _A is Avogadro's constant, and Mg is dissolved dry matter of sol separated from supernatant of sol-gel separation in TFT solution. Next molecular weight measured by GPC, in the range of 20,000 to 150,000 g / mol.)

[Equation 2]

(Wherein, the weight of the grafted monomer is (the weight of the precipitate remaining after the sol-gel separation (g))-(rubber weight (g)), the rubber weight is theoretically the solid content basis weight (g) of the rubber polymer injected)

In the sol-gel separation method, for example, 1 g of the thermoplastic resin on the powder obtained is placed in 50 g of acetone, and stirred for 24 hours to dissolve, and the solution is separated by using a centrifuge at 20,000 rpm and -20 ° C. Separating the supernatant may be separated by sol-gel.

The thermoplastic resin on the powder is excellent in thermal decomposition stability obtained by agglomeration using a salt, thereby reducing the amount of gas generated during extrusion and injection processing.

The salt may be, for example, a sulfate such as MgSO ₄ , a calcium salt such as CaCl ₂ , a carbonate, or a mixture thereof. In this case, the volatilization temperature of the residual emulsifier increases due to the bonding, so that the gas may be caused by the residue during processing at high temperature. Since the amount of generation is reduced, the formation of deposits on the surface of the injection molding is suppressed and the surface smoothness is improved, which is advantageous in obtaining a beautiful appearance during secondary processing such as plating.

Since the thermoplastic resin of the present invention provides a composition for improving the graft density, the dispersion resin has a high glossiness by increasing the dispersion degree.

The thermoplastic resin of the present invention is not specific to the manufacturing method, for example, the step of polymerizing the seed; And a fatty acid or a metal salt thereof having an average carbon number of 10 or more and a molecular weight of 500 to 2000 g / mol in the shell, and preparing an shell by emulsion graft polymerization.

The seed may include, for example, a large diameter rubbery polymer having an average particle diameter of more than 2,000 mm 3 and up to 3,500 mm 3 and a small diameter rubbery polymer having an average particle diameter of 500 mm 2 to 2,000 mm 3.

The seed polymerization may be carried out, for example, by emulsion polymerization.

The seed polymerization and emulsion graft polymerization method is not particularly limited in the case of seed polymerization and emulsion graft polymerization generally used in the production method of ABS resin.

In one embodiment, the thermoplastic resin manufacturing method of the present invention is selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters and metal salts of unsaturated fatty acids as emulsifiers during seed polymerization and / or emulsion graft polymerization. It may further comprise more than one species, the amount may be, for example, 1.0 to 3.0 parts by weight based on a total of 100 parts by weight of the monomer (including rubbery polymer during emulsion graft polymerization).

In the thermoplastic resin manufacturing method of the present invention, a water-soluble initiator or a fat-soluble initiator may be used as an initiator during seed polymerization and / or emulsion graft polymerization, and the water-soluble initiator may include sodium persulfate, potassium persulfate, ammonium persulfate, or the like. The fat-soluble initiator includes cumene hydro peroxide, diisopropylbenzene hydro peroxide, tertiary butyl hydro peroxide, paramethane hydro peroxide, benzoyl peroxide, and the like, and if necessary, the combination thereof may be used. It is possible.

The initiator may be used in an amount of 0.01 to 0.5 parts by weight or 0.1 to 0.3 parts by weight, for example, based on a total of 100 parts by weight of a monomer (including a rubbery polymer during emulsion graft polymerization), and does not cause an overreaction within the above range, It can be a polymer having a desired particle size and size distribution.

The thermoplastic resin production method of the present invention is, for example, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, pyrrole as an oxidation-reduction catalyst during seed polymerization and / or emulsion graft polymerization. It may include one or more selected from the group consisting of sodium phosphate, sodium sulfite.

The redox-based catalyst may be used in an example of 0.001 to 0.4 parts by weight, 0.005 to 0.2 parts by weight or 0.01 to 0.2 parts by weight based on a total of 100 parts by weight of the monomer (including rubbery polymer during emulsion graft polymerization). Within this range, the polymerization reaction can be promoted to produce the thermoplastic resin in a short time.

In the step of emulsion graft polymerization of the shell, it is preferable to add the reactants, and then graft polymerization by reacting at 60 to 90 ° C. or 60 to 80 ° C. for 3 to 5 hours or 2 to 4 hours. This is because the polymerization reaction is initiated by the activation of the initiator within the above-mentioned range, and the heat removal is easy. In addition, when controlling the temperature and the reaction time in the above-described range, a polymer having a uniform size distribution can be prepared.

Emulsion graft polymerization of the shell may be performed by using a molecular weight modifier, if necessary, based on 100 parts by weight of the total content of the conjugated diene rubbery polymer, aromatic vinyl compound and vinyl cyan compound, 0.1 to 1 part by weight, 0.2 to 0.6 part by weight or It may further comprise 0.3 to 0.5 parts by weight, it may be advantageous to form a polymer having a desired average particle diameter in the case of further comprising a molecular weight regulator in the above-described range, there is an effect that the size of the polymer is uniform.

As said molecular weight modifier, mercaptan compounds, such as tertiary dodecyl mercaptan, can be used as an example.

Another example of the present invention is that the total amount of the initiator and the redox-based catalyst used in the graft polymerization reaction can be added at the beginning of the reaction, but when the initiator and the redox-based catalyst are separately added as described above, It is easy to remove the heat and suppress the side reactions while reducing the content of unreacted monomer can improve the quality and productivity of the polymer.

After the above-mentioned charge, the secondary graft polymerization reaction may be performed by raising the temperature to 60 to 100 ° C., or 70 to 90 ° C. under a temperature increase rate of 5 to 30 / hr, or 10 to 20 / hr. By raising the temperature of the reactants as described above, it is possible to promote the reaction of the unreacted monomer and achieve high conversion in a shorter time.

For example, the polymerization reaction may be preferably terminated at a polymerization conversion rate of 90 to 99%, 95 to 99%, or 97 to 99%. In the above range, a polymer having a low unreacted monomer content and a high degree of polymerization in the product may be used. Can be prepared.

In the present description, the polymerization conversion rate is 1.5 g of the graft copolymer latex in a 150 ° C. hot air dryer, and then weighed to obtain a total solids content (TSC), which is measured by the following equation.

TSC: Total solids content (parts by weight)

M: total monomer content added (parts by weight)

W: input water content (parts by weight)

S: content of the added emulsifier and other auxiliary raw materials (parts by weight)

Other reaction conditions, such as graft rate, reaction pressure, etc., in addition to the above-described substrates, are not particularly limited as long as they are within a range generally practiced in the art to which the present invention pertains, and may be appropriately selected and performed as necessary.

The graft copolymer latex prepared according to the present invention is prepared in the form of a powder through conventional processes such as salt agglomeration, washing, and drying, and the powder is mixed with a nonpolar resin such as a poly (arylene ether) resin. And extruded and injected to produce a molded article.

That is, the thermoplastic resin composition of the present invention is characterized by including the thermoplastic resin and the polyarylene ether resin.

For example, the thermoplastic resin composition may be in a form in which the thermoplastic resin is dispersed in a matrix resin made of a polyarylene ether resin (see FIG. 1), and in this case, an excellent balance of physical properties such as impact strength and gloss is excellent.

The poly (arylene ether) resin may be, for example, a homopolymer of a compound represented by Formula 1 or Formula 2, or a copolymer including a compound of Formula 1 or Formula 2.

R _a , R ₁ , R ₂ , R ₃ and R ₄ are substituents of arylene group (Ar) or phenylene group, each independently or simultaneously hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl , Methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, phenoxy or nitro group, n is an integer of 4 to 20, Ar is an arylene group having 7 to 20 carbon atoms. In an example, R ₁ and R ₂ may be an alkyl group or an alkyl group having 1 to 4 carbon atoms, and R ₃ and R ₄ may be hydrogen.

The poly (arylene ether) resin may be, for example, a poly (phenylene ether) resin.

The poly (phenylene ether) -based resin means a poly (arylene ether) resin that can be represented by the following [Formula 3].

W, X, Y and Z are hydrogen or a substituent, n is a repeating unit.

W, X, Y and Z are each independently or simultaneously hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, memeth Oxy, phenoxy or nitro group, wherein n is an integer from 4 to 20.

The homopolymer of the poly (arylene ether) resin is not particularly limited, but specific examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenyl Ethylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl -1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2, 6-dibromomethyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether and poly (2,5-dimethyl-1,4-phenylene) ether It may be one or more selected from the group consisting of.

In addition, the copolymer of the poly (arylene ether) resin is not particularly limited, but specific examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and o-cresol It may be one or more selected from the group consisting of a copolymer of and a copolymer of 2,3,6-trimethylphenol and o-cresol.

The poly (arylene ether) resin may be 50 to 85% by weight, or 50 to 80% by weight based on the total weight of the resin composition according to the present invention, for example, impact strength, mechanical properties and surface gloss within this range This has an excellent effect.

The poly (arylene ether) resin, for example, may have a weight average molecular weight of 10,000 to 100,000 g / mol, 10,000 to 70,000 g / mol, or 15,000 to 45,000 g / mol, within this range the dimensional stability and physical property balance Excellent effect.

The thermoplastic resin composition may further include additives such as heat stabilizers, light stabilizers, antioxidants, antistatic agents, antibacterial agents, or lubricants, for example, in a range that does not affect the physical properties.

In the case of the melt-extruded specimen of the thermoplastic resin composition of the present invention, when the glossiness of the 45 ° light source is measured, the surface glossiness may have a high glossiness of more than 66, more than 80, 85 to 99, or 88 to 96.

The specimens may have improved mechanical properties of greater than 32%, greater than 40%, or between 42 and 65% tensile elongation measured according to ASTM D 638.

The specimen may be manufactured by injection molding or extruding the thermoplastic resin composition at a processing temperature of 250 to 300 ° C., or by extruding to produce pellets.

The thermoplastic resin composition of the present invention is not only excellent in mechanical strength but also excellent in gloss and is expected to be able to replace the existing blending material.

Hereinafter, preferred examples are provided to aid in understanding the present invention, but the following examples are merely for exemplifying the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

Example 1

Thermoplastics Manufacturing Steps

Seed Polymerization Step-Large Diameter Seed Polymerization:

In a nitrogen-substituted polymerization reactor, 100 parts by weight of ion-exchanged water, 65 parts by weight of 1,3-butadiene as monomer, 2.5 parts by weight of a mixed emulsifier of the oleic acid dimer and rosin soap as shown in Table 1 as an emulsifier, potassium carbonate (K ₂ CO ₃ ) 1.2 parts by weight, 0.4 parts by weight of tertiary dodecyl mercaptan (TDDM) as the molecular weight regulator, 0.3 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as the polymerization initiator and polymerization at a reaction temperature of 70 ℃ After reacting up to 30-40% conversion, 35 parts by weight of 1,3-butadiene was continuously administered, and 0.2 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) was collectively administered after reacting at 75 ° C. to 60% polymerization conversion. It heated up to 82 degreeC and the reaction was complete | finished by 95% of the polymerization conversion ratio, and the polybutadiene rubber latex (large diameter seed) of 3100 micrometers of average particle diameters and 70 weight% of gel contents was obtained.

Seed Polymerization Step—Small Diameter Seed Polymerization:

In a nitrogen-substituted polymerization reactor, 100 parts by weight of ion-exchanged water, 80 parts by weight of 1,3-butadiene as a monomer, 3.0 parts by weight of a mixed emulsifier of the oleic acid dimer and rosin soap shown in Table 1 as emulsifiers, potassium carbonate (K ₂ CO ₃ ) 0.5 parts by weight, 0.4 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, 0.3 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as a polymerization initiator and polymerization at a reaction temperature of 70 ℃ After reacting up to 30-40% conversion, 20 parts by weight of 1,3-butadiene was continuously administered, and 0.2 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) was collectively administered after reaction at 75 ° C. to 60% polymerization conversion. It heated up to 82 degreeC and the reaction was complete | finished by 95% of the polymerization conversion ratio, and the polybutadiene rubber latex (small diameter seed) of 1200 GPa of average particle diameter and 90 weight% of gel content was obtained.

Shell polymerization stage

In a nitrogen-substituted polymerization reactor, 100 parts by weight of ion-exchanged water, 50 parts by weight of polybutadiene rubber latex (large diameter seed) polymerized in the seed polymerization step (based on solids), and polybutadiene rubber latex polymerized in the seed polymerization step (small Caliber seed) 5 parts by weight (based on solids) was added, followed by 5 parts by weight of a mixture of styrene and acrylonitrile monomers (5% by weight of acrylonitrile), and 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator. Then, 0.2 part by weight of t-butyl hydroperoxide was sequentially added as a polymerization initiator, stirred at 50 ° C. for 30 minutes, and then an oxidation-reduction catalyst composed of 0.035 part by weight of dextrose, 0.06 part by weight of sodium pyrolate, and 0.0015 part by weight of ferrous sulfate. The batch was administered and polymerization was performed while raising the temperature at 70 ° C. for 1 hour.

Then, 100 parts by weight of ion-exchanged water, 40 parts by weight of a mixture of styrene and acrylonitrile monomers (5% by weight of acrylonitrile content), 1.0 part by weight of oleic acid dimer (C36) as an emulsifier, and a tertiary dodecyl mercaptan 0.1 as a molecular weight regulator. By weight, an emulsion composed of 0.1 part by weight of cumene hydroperoxide as a polymerization initiator was continuously added for 2 hours at 70 ° C isothermal conditions and maintained at 70 ° C for 2 hours.

At this time, the polymerization conversion rate was 95% level, followed by a batch dose of 0.05 parts by weight of cumene hydroperoxide together with an oxidation-reduction catalyst consisting of 0.035 parts by weight of dextrose, 0.06 parts by weight of sodium pyrolate, and 0.0015 parts by weight of ferrous sulfate and an additional 75 Further polymerization was carried out for 1 hour while the temperature was raised to ° C. The polymerization conversion rate of the final polymer was 98.8%.

Subsequently, the obtained seed-shell structured ABS graft copolymer latex was coagulated with 2 parts by weight of sulfate, followed by washing to obtain powder (a1).

Thermoplastic Resin Composition Manufacturing Step

25 parts by weight of the obtained ABS graft copolymer powder (a1) and 75 parts by weight of polyphenylene ether were mixed in a mixer, melted and kneaded at 250 to 300 ° C. using an extruder, and pelletized. Using the specimen (A1) of Example 1 for the measurement of physical properties.

Example 2

In the shell polymerization step of Example 1, 35 parts by weight instead of 50 parts by weight of the polybutadiene rubber latex (large diameter seed) polymerized in the seed polymerization step and polybutadiene rubber latex (small diameter seed) polymerized in the seed polymerization step ABS graft copolymer powder (a2) was obtained by the same method as Example 1 except 20 parts by weight were added instead of 5 parts by weight.

Furthermore, the present invention was carried out in the same manner as in Example 1 except that the ABS graft copolymer powder (a2) was added instead of the ABS graft copolymer powder (a1) in the thermoplastic resin composition manufacturing step of Example 1. Two specimens A2 were produced.

Example 3

In the thermoplastic resin composition manufacturing step of Example 1, 50 parts by weight of the ABS graft copolymer powder (a1) instead of 25 parts by weight of the ABS graft copolymer powder (a1), 50 parts by weight of polyphenylene ether instead of 75 parts by weight A specimen A3 of Example 3 was prepared in the same manner as in Example 1, except that parts were added.

Example 4

In the shell polymerization step of Example 1, 35 parts by weight instead of 50 parts by weight of polybutadiene rubber latex (large diameter seed) polymerized in the seed polymerization step and polybutadiene rubber latex (small diameter seed) polymerized in the seed polymerization step 20 parts by weight was added instead of 5 parts by weight, and 0.1 parts by weight instead of 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) was used as a molecular weight modifier, and acrylics were added to the styrene and acrylonitrile monomer mixture for initial batch and continuous addition. ABS graft copolymer powder (a3) was obtained in the same manner as in Example 1, except that 10 wt% of acrylonitrile was added instead of 5 wt% of nitrile.

Furthermore, except that the ABS graft copolymer powder (a4) instead of the ABS graft copolymer powder (a1) in the thermoplastic resin composition manufacturing step of Example 1 was carried out in the same manner as in Example 1 Four specimens (A4) were produced.

Example 5

The polymerization was carried out in the same manner as in Example 2 and in a rubber composition, except that a large diameter particle diameter of 3600 mm 3 and a small diameter particle diameter of 900 mm were used to obtain the ABS graft powder (a5) by polymerization in the same manner as in Example 2. The specimen A5 of Example 5 was prepared through the processing of the method.

Example 6

ABS graft powder (a6) was obtained by polymerization in the same manner as in Example 1 except that the same amount of myristic oleic acid dimer was used instead of the oleine phase dimer in the cell polymerization step of Example 1, and the processing of the same method was carried out. Specimen (A6) was produced.

Example 7

In the shell polymerization step of Example 1, 40 parts by weight instead of 50 parts by weight of the polybutadiene rubber latex (large diameter seed) polymerized in the seed polymerization step and polybutadiene rubber latex (small diameter seed) polymerized in the seed polymerization step 15 parts by weight instead of 5 parts by weight, followed by 10 parts by weight of a mixture of styrene and acrylonitrile monomers (5% by weight of acrylonitrile), 0.05 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, and a polymerization initiator 0.2 parts by weight of t-butyl hydroperoxide was added sequentially, followed by stirring at 50 ° C. for 30 minutes, and then a redox catalyst consisting of 0.035 parts by weight of dextrose, 0.06 parts by weight of sodium pyrolate and 0.0015 parts by weight of ferrous sulfate was added in a batch, and 70 The polymerization was carried out while raising the temperature at 1 ° C for 1 hour.

Then, 100 parts by weight of ion-exchanged water, 30 parts by weight of styrene and acrylonitrile monomer mixture (5% by weight of acrylonitrile), 1.0 part by weight of oleic acid dimer (C36) as an emulsifier, and tertiary dodecyl mercaptan 0.05 as a molecular weight regulator By weight, an emulsion composed of 0.1 part by weight of cumene hydroperoxide as a polymerization initiator was continuously added for 2 hours at 70 ° C isothermal conditions and maintained at 70 ° C for 2 hours.

At this time, the polymerization conversion rate was 95% level, followed by a batch dose of 0.05 parts by weight of cumene hydroperoxide together with an oxidation-reduction catalyst consisting of 0.035 parts by weight of dextrose, 0.06 parts by weight of sodium pyrolate, and 0.0015 parts by weight of ferrous sulfate and an additional 75 Further polymerization was carried out for 1 hour while the temperature was raised to ° C. The polymerization conversion rate of the final polymer was 98.8%.

Subsequently, the obtained seed-shell structured ABS graft copolymer latex was solidified with 2 parts by weight of sulfate, followed by washing to obtain a powder (a7).

Furthermore, the present invention was carried out in the same manner as in Example 1, except that the ABS graft copolymer powder (a7) was added instead of the ABS graft copolymer powder (a1) in the thermoplastic resin composition manufacturing step of Example 1. 7 specimen (A7) was produced.

Example 8

In the shell polymerization step of Example 1, 40 parts by weight instead of 50 parts by weight of the polybutadiene rubber latex (large diameter seed) polymerized in the seed polymerization step and polybutadiene rubber latex (small diameter seed) polymerized in the seed polymerization step 15 parts by weight instead of 5 parts by weight, followed by 10 parts by weight of a mixture of styrene and acrylonitrile monomers (5% by weight of acrylonitrile), 0.02 part by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, and a polymerization initiator 0.2 parts by weight of t-butyl hydroperoxide was added sequentially, followed by stirring at 50 ° C. for 30 minutes, and then a redox catalyst consisting of 0.035 parts by weight of dextrose, 0.06 parts by weight of sodium pyrolate and 0.0015 parts by weight of ferrous sulfate was added in a batch, and 70 The polymerization was carried out while the temperature was raised at 1 ° C. for 1 hour.

Then, 100 parts by weight of ion-exchanged water, 30 parts by weight of styrene and acrylonitrile monomer mixture (5% by weight of acrylonitrile), 1.0 part by weight of oleic acid dimer (C36) as an emulsifier, and tertiary dodecyl mercaptan 0.02 as a molecular weight regulator By weight, an emulsion composed of 0.1 part by weight of cumene hydroperoxide as a polymerization initiator was continuously added for 2 hours at 70 ° C isothermal conditions and maintained at 70 ° C for 2 hours.

At this time, the polymerization conversion rate was 95%, and then 0.05 parts by weight of cumene hydroperoxide was added together with an oxidation-reduction catalyst composed of 0.035 parts by weight of dextrose, 0.06 parts by weight of sodium pyrolate, and 0.0015 parts by weight of ferrous sulfate, and further Further polymerization was carried out for 1 hour while the temperature was raised to 75 ° C. The polymerization conversion rate of the final polymer was 98.8%.

Subsequently, the obtained seed-shell structured ABS graft copolymer latex was solidified with 2 parts by weight of sulfate, followed by washing to obtain powder (a8).

Furthermore, the present invention was carried out in the same manner as in Example 1, except that the ABS graft copolymer powder (a8) was added instead of the ABS graft copolymer powder (a1) in the thermoplastic resin composition manufacturing step of Example 1. 8 specimen (A8) was produced.

Comparative Example 1

In the shell polymerization step of Example 1, 10 parts by weight of the styrene and acrylonitrile monomer mixture (25% by weight of acrylonitrile) was added instead of 5 parts by weight of the styrene and acrylonitrile monomer mixture (5% by weight of acrylonitrile). Instead of 40 parts by weight of the styrene and acrylonitrile monomer mixture (5% by weight of acrylonitrile), 35 parts by weight of the mixture of styrene and acrylonitrile monomers (25% by weight of acrylonitrile) was added as an emulsifier. (C36) ABS graft copolymer powder (b1) was obtained by the same method as Example 1 except that 1.0 part by weight of potassium rosin salt was added instead of 1.0 part by weight.

Further Comparative Example was carried out in the same manner as in Example 1 except that the ABS graft copolymer powder (b1) instead of the ABS graft copolymer powder (a1) in the thermoplastic resin composition manufacturing step of Example 1 was added. 1 specimen (B1) was produced.

Comparative Example 2

Comparative Example 1 was carried out in the same manner as in Example 1, except that 25 parts by weight of the product name SG910 (LG Chem) was added as a high-impact polystyrene (hereinafter referred to as HIPS) without undergoing the thermoplastic resin polymerization step . Specimen B2 of Example 2 was produced.

Comparative Example 3

In Comparative Example 2, 50 parts by weight of polyphenylene ether instead of 75 parts by weight, 50 parts by weight instead of HIPS 25 parts by weight was carried out in the same manner as in Example 1, the specimen of Comparative Example 3 (B3) was produced.

Comparative Example 4

Prepared through the same method as in Comparative Example 1 except that 55 parts by weight of a large diameter rubbery polymer was applied alone in applying the rubbery polymer to prepare a polymer through the same method to prepare a powder (b2) and the same as the comparative example Specimen (B4) was produced by the method and composition.

Comparative Example 5

Prepared by the same method as in Comparative Example 1 except that 55 parts by weight of the small-diameter rubbery polymer is applied alone in applying the rubbery polymer to prepare a polymer through the same method to prepare a powder (b3) and Comparative Example and The specimen (B5) was produced through the same method and composition.

[Test Example]

Physical properties of the ABS graft copolymer powders (a1, a2, a4, a5, a6, a7, a8, b1, b2, b3) obtained in Examples 1 to 2, 4 to 8 and Comparative Examples 1, 4 and 5. Was measured by the following method, and the results are shown in Tables 1 and 2, respectively.

How to measure

* Average particle diameter (Å): Measured by the dynamic laser light skating method using a Nicomp 370HPL instrument of Nicomp.

* Graft rate: A value expressed by the following Equation 6 is an index indicating how many polymers are grafted to the total weight of rubber added during graft polymerization. This shows the value for the weight ratio of the grafted polymer and has a different meaning from the graft density. For example, at the same graft rate, the smaller the molecular weight, the higher the graft density.

[Equation 6]

* Gel content (% by weight): The polybutadiene rubber latex is coagulated with dilute acid or metal salt, washed, dried in a vacuum oven at 60 ° C. for 24 hours, and then chopped into pieces of rubber and then 1 g of rubber Sections were put in 100 g of toluene, stored in a dark room at room temperature for 48 hours, separated into sol and gel, dried, respectively, and the gel content was measured by the following equation (3).

[Equation 3]

* Polymerization Conversion Rate (%): 1.5 g of the graft copolymer latex was dried in a 150 ° C. hot air dryer for 15 minutes, and then weighed to obtain a total solid content (TSC), and the polymerization conversion rate was calculated by Equation 4 below.

[Equation 4]

TSC: Total solids content (parts by weight)

M: total monomer content added (parts by weight)

W: input water content (parts by weight)

S: content of the added emulsifier and other auxiliary raw materials (parts by weight)

Surface gloss (Gloss, 45 °): The specimen was measured at an angle of 45 ° according to standard measurement ASTM D528.

* Coagulum content (Coagulum, weight%): The weight of the coagulum produced in the reaction tank, the total rubber weight and the monomer weight was measured, and the coagulum content was calculated by the following equation (5).

[Equation 5]

* Graft Density (σ), Total Graft Rate (%), Molecular Weight (Mw): 1 g of the thermoplastic resin obtained on the powder was added to 50 g of acetone and stirred for 24 hours to dissolve, and the solution was dissolved at 20,000 rpm at -20 ° C. After separation using a centrifugal separator under the condition, the supernatant was separated, and the precipitate precipitate was dried for 12 hours using a hot air dryer, and then the weight of the dried precipitate was measured. The graft ratio was calculated according to the following Equation 2 according to the measured weight.

[Equation 2]

Graft Rate = Weight of Grafted Monomer (g) / Rubber Weight (g) x 100

Weight of grafted monomer: (weight of sediment remaining after sol-gel separation)-(rubber weight)

Gummy weight: The solids basis weight of theoretically committed rubbery polymer

The dried product of the sol separated from the supernatant was dissolved in a TFT solution and measured by GPC to determine the molecular weight (Mw).

Furthermore, the graft density σ was calculated according to the following equation.

[Equation 1]

g _d is the graft ratio (%) calculated by the above equation (2), D is the average particle diameter measured by the light scattering method.

p is a density value of butadiene rubber particles measured by the ASTM D792 method, where p is represented by a large diameter PBL 0.94 g / cm ³ and a small diameter PBL 0.97 g / cm ³ .

N _A is Avogadro's constant.

Mg is a molecular weight measured by GPC and is in a range of 20,000 to 150,000.

For reference, in the case of Example 1, graft ratio 0.7, NA 6.02x10 ²³ (mol ^-1 ), average particle diameter (P / S) 292.7273 nm, density (g / cm ³ ) 0.943182, molecular weight (Mw / 10 ³ ) 30 g / The graft density calculated in mol is 0.64.

* Gas generation amount (ppm): The gas generation degree for each powder was measured by using a TGA device was measured by weight loss when left for 60 minutes under nitrogen, 250 degree isothermal conditions.

Input classification Kinds Ex1 (a1) Ex2 (a2) Ex4 (a4) Ex5 (a5) Ex6 (a6) Ex7 (a7) Ex8 (a8) 1 ^st batch Large Diameter Seed 50 35 35 35 35 40 40 Small caliber seed 5 20 20 20 20 15 15 Monomer input 5 5 5 5 5 10 10 AN% 5 5 10 5 5 5 5 Molecular weight regulator 0.3 0.1 0.1 0.1 0.1 0.05 0.02 2 ^nd continuous charge Monomer input 40 40 40 40 40 30 30 AN% 5 5 10 5 5 5 5 Molecular weight regulator 0.1 0.1 0.1 0.1 0.1 0.05 0.02 Oleic acid dimer 1.0 1.0 1.0 1.0 1.0 1.0 1.0 % Conversion 98.8 98.9 98.0 98.2 98.4 98.8 98.2 Graft rate 70% 70% 70% 85% 80% 85% 87% Molecular Weight (g / mol) 30,000 45,000 50,000 65,000 62,000 100,000 130,000 Graft density (σ) -Equation 1 0.64 0.35 0.32 0.30 0.31 0.20 0.16 Gas generation amount 1% less than 1% less than 1% less than 1% less than 1% less than 1% less than 1% less than Coagulation content (%) 0.03 0.02 0.03 0.04 0.02 0.03 0.02

Input classification Kinds COM Ex.1 (b1) COM Ex.4 (b2) COM Ex.5 (b3) 1 ^st batch Large Diameter Seed 35 55 - Small caliber seed 20 - 55 Monomer input 10 10 10 AN% 25 25 25 Molecular weight regulator 0.3 0.3 0.3 2 ^nd continuous charge Monomer input 35 35 35 AN% 25 25 25 Molecular weight regulator 0.1 0.1 0.1 Rosin acid potassium salt 1.0 1.0 1.0 % Conversion 97.6 96.6 99.6 Graft rate 37% 36% 36% Molecular Weight (g / mol) 85,000 80,000 90,000 Graft density (σ) -Equation 1 0.10 0.13 0.05 Gas generation amount 2.5% 2.7% 3.0% Coagulation content (%) 0.05 0.07 0.08

Compared to Table 1 and Table 2, in Examples 1 to 2, 4 to 8 prepared according to the present invention, the graft density compared to Comparative Examples 1, 4, 5 is within a specific range, reducing the amount of gas generated and solidification It was confirmed that the latex stability after the polymerization was improved by decreasing the water content.

Additional Test Example

The physical properties of the thermoplastic resin composition specimens (A1, A2, A3, A4, A5, A6, A7, A8, B1, B2, and B3) of Examples 1 to 8 and Comparative Examples 1 to 3 were measured by the following methods, The results are shown in Table 3 below.

How to measure

* Notched Izod Impact Strength (kgf · m / m): Measured according to standard measurement ASTM D256 using a 1/4 "specimen.

* Tensile Strength (TS, kg / cm ² ): Measured according to ASTM D638.

* Tensile Elongation (TE,%): measured according to ASTM D638.

* Surface glossiness (Gloss, 45 °): The specimen was measured at an angle of 45 ° according to standard measurement ASTM D523.

division ( Parts by weight ) Ex1 Ex2 Ex3 Ex4 Ex5 Ex6 Ex7 Ex8 PPO 75 75 50 75 75 75 75 75 ABS a1 (25) a2 (25) a1 (50) a3 (25) a4 (25) a5 (25) a5 (25) a5 (25) HIPS - - - - - - - - Impact strength (1/4 ") 22.5 23.4 27.0 24.2 23.0 22.0 23.7 24.0 The tensile strength (TS) 350 370 320 365 356 375 346 342 Tensile elongation ( TE ) 48 49 65 48 45 42 45 48 Glossiness (45 °) 95 92 88 94 95 96 95 98 division ( Parts by weight ) COM Ex1 COM Ex2 COM Ex3 COM Ex4 COM Ex5 PRO 75 75 50 75 75 ABS b1 (25) - - b2 (25) b3 (25) HIPS - 25 50 - - Impact strength (1/4 ") 10.2 4.8 6.6 12.3 5.0 The tensile strength (TS) 540 710 590 520 700 Tensile elongation ( TE ) 32 22 28 23 20 Glossiness (45 °) 60 50 15 52 55

As shown in Table 3, in Examples 1 to 8 prepared in accordance with the present invention, the average carbon number of the chain of the oleic acid-based dimer emulsifier included in the shell polymerization step is lower than in the content range of the present invention Compared to the molded article blended with the polyphenylene ether, it was confirmed that the impact strength, mechanical properties and gloss were excellent.

In addition, in the case of Comparative Examples 2 or 3 in which HIPS was blended instead of the ABS thermoplastic resin powder prepared according to the present invention, it was confirmed that the impact strength and glossiness were reduced.

In addition, in the case of the non-modal seed-based ABS thermoplastic resin prepared according to the present invention Comparative Example 4 or 5 rather than the bimodal seed-based ABS thermoplastic resin powder, it was confirmed that the impact strength, gloss is reduced.

FIG. 1 is an SEM result in which a thermoplastic resin composition is dispersed in a domain in each of the polyphenylene ether matrices of Example 1, Comparative Example 1, and Comparative Example 2 of Table 3 described above. Referring to Figure 1, in the case of the thermoplastic resin composition prepared according to the present invention it can be confirmed that the dispersion effect improved than Comparative Example 1 or Comparative Example 2.

2 is a thermogravimetric analysis (TGA) graph of oleic acid dimer, Rosin Soap (potassium rosin) and Fatty Soap (potassium acid salt) including the emulsifiers of Tables 1 and 2 described above. Looking at Figure 2 and Table 4, it can be seen that rosin acid soap is superior to the thermal stability than Fatty soap, oleic acid-based dimer is superior to the thermal stability than rosin acid soap.

Measuring conditions Weight loss (%) Oleic acid dimer 250 degree N2 isothermal condition (60min) 23% Rosin soap 49% Fatty soap 76%

As described above, in the present invention, by blending a thermoplastic resin having a composition capable of improving graft density, the dispersion degree is improved, so that glossiness and mechanical properties equal to or higher than those of conventional blending resins in extrusion and injection molding are improved. It can provide a blending material having a.

Claims (15)

A graft copolymer having a seed-shell structure, comprising: a bimodal seed comprising a large-diameter rubbery polymer having an average particle diameter of greater than 2,000 GPa and less than or equal to 3,500 GPa and a small-diameter rubbery polymer having an average particle diameter of 500 GPa to 2,000 GPa; A thermoplastic resin comprising an encapsulated aromatic vinyl-vinyl cyan shell, wherein the vinyl cyan compound is included in an amount of 5 wt% to 25 wt% based on the total weight of the shell. The method of claim 1, The seed-shell graft copolymer may include: (a) a seed comprising a bimodal conjugated diene rubber polymer; And (b) a shell surrounding the seed and polymerized with an aromatic vinyl compound, a vinyl cyan compound, and a fatty acid or a metal salt thereof. The method of claim 2, The conjugated diene rubber polymer 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 Thermoplastic resin characterized by including the above-mentioned conjugated diene-based compound and polymerized The method of claim 1, The bimodal resin is a thermoplastic resin comprising a large diameter rubber polymer and a small diameter rubber polymer in a weight ratio of 50:50 to 90:10. The method of claim 2, The aromatic vinyl compound is selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene and derivatives thereof. Thermoplastic resin, characterized in that at least one selected. The method of claim 2, The vinyl cyan compound is at least one member selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof. The method of claim 2, The (a) seed may be included in an amount of 30 to 80 wt%, and the (b) shell may be included in an amount of 20 to 70 wt% based on 100 wt% of the total content of the conjugated diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound. , (B) The content of the aromatic vinyl compound and the vinyl cyan compound contained in the shell is a thermoplastic resin, characterized in that contained in a weight ratio of 90:10 to 99: 1. The method of claim 2, The fatty acid or a metal salt thereof is a thermoplastic resin, characterized in that a mixture of fatty acids having a carbon number of 10 or more or a metal salt thereof. The method of claim 2, The fatty acid or its metal salt is a thermoplastic resin, characterized in that it comprises an unsaturated fatty acid having a degree of unsaturation of 1 to 20 or a metal salt thereof. The method of claim 2, The fatty acid or a metal salt thereof is a thermoplastic resin, characterized in that contained in 0.1 to 3 parts by weight based on 100 parts by weight of the total content of the conjugated diene rubber polymer, aromatic vinyl compound and vinyl cyan compound. The method of claim 1, The thermoplastic resin is a thermoplastic resin, characterized in that the graft density (σ) represented by the following formula (1) is more than 0.12 to 0.80 or less: [Equation 1]

Where g _d is the graft ratio (%) calculated by Equation 2 below, D is the average particle diameter measured by the light scattering method, and ρ is the density value of butadiene rubber particles measured by the ASTM D792 method, and ρP given in the above formula. Represents large diameter PBL 0.94 g / cm ³ , small diameter PBL 0.97 g / cm ³ , N _A is Avogadro's constant, and Mg is dissolved dry matter of sol separated from supernatant of sol-gel separation in TFT solution. Next molecular weight measured by GPC, in the range of 20,000 to 150,000 g / mol.)  [Equation 2]

(Wherein, the weight of the grafted monomer is (the weight of the precipitate remaining after the sol-gel separation (g))-(rubber weight (g)), the rubber weight is theoretically the solid content basis weight (g) of the rubber polymer injected) The method of claim 1, The thermoplastic resin is a thermoplastic resin, characterized in that the salt agglomerated powder having a weight average molecular weight of 20,000 to 200,000 g / mol. 13. The method of claim 1, wherein the thermoplastic resin of any one of claims 1 to 12 and polyarylene ether are included, wherein the thermoplastic resin contains 15 to 50% by weight, and the polyarylene ether contains 50 to 85% by weight. Thermoplastic resin composition. The method of claim 13, The thermoplastic resin composition characterized in that the surface gloss (Gloss) measured by using a 45 ° light source for the specimen made by extruding the thermoplastic resin composition is more than 66. The method of claim 13, The thermoplastic resin composition characterized in that the tensile elongation measured in accordance with ASTM D 638 of the specimen made by extruding the thermoplastic resin composition is more than 32%.

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