KR20210087171A - Thermoplastic resin composition, method for preparing the same and article prepared therefrom - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, a method for preparing the same and a molded article obtained therefrom. Particularly, the thermoplastic resin composition includes: (A) 10-40 wt% of a first acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer including a seed, an acrylate rubber core surrounding the seed and having an average particle diameter, including the seed, of larger than 140 nm and smaller than 380 nm, and a shell surrounding the rubber core; (B) 5-35 wt% of a second acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer including an acrylate rubber core having an average particle diameter of 400-600 nm, and a shell surrounding the rubber core; and (C) 40-70 wt% of a matrix polymer, and has a flow index (220℃, 10 kg) of 15 g/10min or more, as determined according to ASTM D1238. The thermoplastic resin composition according to the present invention shows excellent impact resistance, colourability and flowability as well as excellent weather resistance.

Description

Thermoplastic resin composition, manufacturing method thereof, and molded article manufactured therefrom {THERMOPLASTIC RESIN COMPOSITION, METHOD FOR PREPARING THE SAME AND ARTICLE PREPARED THEREFROM}

The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article prepared therefrom, and more particularly, by using a mixture of two types of acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymers having a predetermined average particle diameter. The present invention relates to a thermoplastic resin composition having excellent weather resistance and excellent impact resistance, colorability and fluidity, a method for manufacturing the same, and a molded article manufactured therefrom.

Acrylonitrile-butadiene-styrene resin (hereinafter referred to as 'ABS resin') based on conjugated diene rubber has excellent processability, mechanical properties and appearance characteristics, so parts of electrical and electronic products, automobiles, small toys, and furniture It is widely used in building materials, etc. However, since the ABS resin is based on butadiene rubber containing chemically unstable unsaturated bonds, the rubber polymer is easily aged by ultraviolet rays, and the weather resistance is very weak, so it is not suitable as an outdoor material.

In order to overcome the problems of the ABS resin as described above, an acrylic copolymer represented by an acrylate-styrene-acrylonitrile graft copolymer without an ethylenically unsaturated bond (hereinafter referred to as 'ASA resin') is used. .

However, ASA resin has excellent weather resistance compared to ABS resin, but has poor impact and colorability. In order to compensate for this, a large-diameter ASA resin with an average particle diameter of 400 nm or more and a small-diameter ASA resin with an average particle diameter of less than 140 nm are mixed. Although the impact strength was improved by using it, it is not sufficient, and when mixed with polymethyl methacrylate (PMMA) resin, the colorability is improved, but there is a problem that the impact strength is lowered.

Therefore, it is necessary to develop a thermoplastic resin composition that can fully satisfy the needs of consumers by improving all of fluidity, impact resistance and colorability while having weather resistance.

Korean Patent Publication No. 2011-0079011

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a thermoplastic resin composition excellent in both impact resistance, colorability and fluidity while having excellent weather resistance, a manufacturing method thereof, and a molded article manufactured therefrom.

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 is (A) a seed; An acrylate rubber core surrounding the seed and having an average particle diameter of more than 140 nm to less than 380 nm including the seed; and 10 to 40 wt% of a first acrylate-aromatic vinyl compound-vinylcyanide compound graft copolymer containing a shell surrounding the rubber core; (B) an acrylate rubber core having an average particle diameter of 400 to 600 nm; and 5 to 35 wt% of a second acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing a shell surrounding the rubber core; And (C) 40 to 70% by weight of the matrix polymer; includes, but provides a thermoplastic resin composition, characterized in that the flow index (220 ℃, 10 kg) measured according to ASTM D1238 is 15 g / 10 min or more.

In addition, the present invention is a method for producing a thermoplastic resin composition, (A) a seed; An acrylate rubber core surrounding the seed and having an average particle diameter of more than 140 nm to less than 380 nm including the seed; and 10 to 40 wt% of a first acrylate-aromatic vinyl compound-vinylcyanide compound graft copolymer containing a shell surrounding the rubber core; (B) an acrylate rubber core having an average particle diameter of 400 to 600 nm; and 5 to 35 wt% of a second acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing a shell surrounding the rubber core; And (C) 40 to 70% by weight of the matrix polymer; kneading and extruding under 200 to 300 ℃ and 80 to 400 rpm conditions, wherein the thermoplastic resin composition is a flow index (220 ℃ measured according to ASTM D1238) , 10 kg) provides a method for producing a thermoplastic resin composition, characterized in that 15 g / 10 min or more.

In addition, the present invention provides a molded article, characterized in that produced from the thermoplastic resin composition.

According to the present invention, there is an effect of providing a thermoplastic resin composition having excellent weather resistance and excellent impact resistance, colorability and fluidity, a method for manufacturing the same, and a molded article manufactured therefrom.

Hereinafter, the thermoplastic resin composition of the present disclosure, a method for producing the same, and a molded article manufactured therefrom will be described in detail.

In order to improve the impact resistance and colorability of ASA resins, the present inventors have developed two types of acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymers having a predetermined average particle diameter instead of conventionally used resins such as polymethyl methacrylate, etc. In the case of mixed use, the weather resistance and fluidity are greatly improved, so that the processability is improved and both the impact resistance and the colorability are improved, and based on this, further research was completed and the present invention was completed.

The thermoplastic resin composition of the present invention comprises (A) a seed; An acrylate rubber core surrounding the seed and having an average particle diameter of more than 140 nm to less than 380 nm including the seed; and 10 to 40 wt% of a first acrylate-aromatic vinyl compound-vinylcyanide compound graft copolymer containing a shell surrounding the rubber core; (B) an acrylate rubber core having an average particle diameter of 400 to 600 nm; and 5 to 35 wt% of a second acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing a shell surrounding the rubber core; And (C) 40 to 70% by weight of the matrix polymer; but, characterized in that the flow index (220 ℃, 10 kg) measured according to ASTM D1238 is 15 g/10min or more. In this case, the thermoplastic resin composition has excellent weather resistance and excellent impact resistance, colorability and processability.

Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each configuration.

(A) first acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer

The (A) first graft copolymer is, for example, a seed; An acrylate rubber core surrounding the seed and having an average particle diameter of more than 140 nm to less than 380 nm including the seed; and a shell enclosing the rubber core, and in this case, excellent weather resistance, impact resistance, colorability, and fluidity are all excellent.

The seed of the (A) first graft copolymer may have, for example, an average particle diameter of 50 to 300 nm, preferably 70 to 270 nm, and more preferably 100 to 220 nm, within this range, the finally manufactured thermoplastic Excellent weather resistance, impact resistance, fluidity and colorability can be imparted to the resin composition.

The acrylate rubber of the (A) first graft copolymer has, for example, an average particle diameter including seeds of more than 140 nm to less than 380 nm, preferably 150 to 370 nm, more preferably 150 to 350 nm, even more preferably It may be 200 to 300 nm (however, it is larger than the average particle diameter of the seed since it includes the seed), and excellent weather resistance, impact resistance, fluidity and colorability can be imparted to the finally manufactured thermoplastic resin composition within this range.

In the present description, the average particle diameter may be measured using dynamic light scattering, and in detail, may be measured using Nicomp 380 equipment (manufacturer: PSS).

In addition, in the present description, the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, specifically, an average particle diameter of scattering intensity.

The (A) first graft copolymer is, for example, 10 to 40% by weight, preferably 15 to 35% by weight, more preferably 20 to 30% by weight, based on the total weight of the thermoplastic resin composition, and weather resistance within this range, There is an effect excellent in fluidity, impact resistance and colorability.

The refractive index of the seed and the shell of the (A) first graft copolymer is, for example, _{a difference from the refractive index of the matrix polymer (μ D} ²⁵ ) is less than 0.035, preferably 0.03 or less, more preferably 0.02 or less, more More preferably, it may be 0.01 or less, and there is an excellent effect of colorability within this range.

The refractive index of the core of the (A) first graft copolymer is, for example, _{a difference from the refractive index (μ D} ²⁵ ) of the matrix polymer is more than 0.056, preferably 0.08 or more, more preferably 0.06 to 0.15, even more preferably It may be 0.08 to 0.13, and within this range, the effect of improving colorability is clearly seen, and when butadiene or styrene, which has a relatively high refractive index, is used as a core to lower the refractive index difference, weather resistance and impact strength are lowered, respectively. occurs

The (A) first graft copolymer may satisfy the following Equations 1 and 2 at the same time as an example, and in this case, the thickness of the core part having a large refractive index difference from the matrix part is reduced, and the core size is appropriately adjusted to provide transparency It has the effect of remarkably improving colorability.

[Equation 1]

140 < 2*r2 < 380

[Equation 2]

10 ≤ r2 - r1 ≤ 60

(In Equations 1 and 2, r1 is the thickness (nm) from the center of the (A) first graft copolymer to the seed, and r2 is (A) from the center to the core of the first graft copolymer. thickness (nm).

The r1 is, for example, the radius or average radius of the seed, which means 1/2 of the seed diameter or the average particle diameter.

The r2 is, for example, the radius or average radius of the core including the seed, which means 1/2 of the particle diameter or the average particle diameter of the core including the seed.

Equation 1 is, for example, 140 < 2*r2 < 380, preferably 150 ≤ 2*r2 ≤ 370, more preferably 150 ≤ 2*r2 ≤ 350, even more preferably 200 ≤ 2*r2 ≤ 300 , more preferably 250 ≤ 2*r2 ≤ 300, and there is an excellent effect of colorability within this range.

Equation 2 is, for example, 10 ≤ r2 - r1 ≤ 60, preferably 20 ≤ r2 - r1 ≤ 55, more preferably 30 ≤ r2 - r1 ≤ 55, even more preferably 50 ≤ r2 - r1 ≤ 55 may be, and within this range, there is an excellent effect of colorability.

The (A) first graft copolymer may have, for example, a gel content of 65 to 95%, preferably 75 to 90%, more preferably 82 to 88%, within this range, mechanical properties such as impact resistance It has excellent physical properties and excellent weather resistance.

The (A) first graft copolymer may have, for example, a swelling index of 3 to 10, preferably 4 to 7, more preferably 5.5 to 6.5, and has excellent mechanical properties such as impact resistance within this range. It has an excellent weather resistance effect.

The (A) first graft copolymer may have, for example, a graft rate of 25% or more, preferably 25 to 70%, more preferably 25 to 60%, and mechanical properties such as impact resistance within this range It has excellent weather resistance and excellent effects.

The gel content and swelling index of this base material is determined by adding acetone to 1 g of the graft copolymer powder, stirring at room temperature for 24 hours, and then centrifuging to collect only the parts that are not soluble in acetone, and then measure the weight before and after drying. The gel content and swelling index can be measured in this way.

* Gel content (%) = weight after centrifugation and drying / sample weight × 100

* Swelling index = weight before drying after centrifugation / weight after drying after centrifugation

In the present description, the graft rate is obtained by coagulating, washing, and drying the resin latex of the graft polymer to obtain a powder form, put 2 g of this powder in 300 ml of acetone and stirred for 24 hours, and then the solution is separated using an ultracentrifuge After that, the separated acetone solution is dropped into methanol to obtain a non-grafted portion, dried and weighed. From these weights, the graft ratio is calculated according to the following formula.

* Graft rate (%) = (weight of grafted monomer (g) / weight of rubber (g)) × 100

The (A) first graft copolymer may include, for example, 5 to 40 wt% of a seed comprising at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth)acrylate compound; 20 to 60% by weight of an acrylate rubber core surrounding the seed and comprising an alkyl acrylate; and a shell surrounding the core and comprising 20 to 60% by weight of at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth)acrylate compound; and within this range It has excellent mechanical properties and excellent colorability.

The (A) first graft copolymer preferably comprises 15 to 30 wt% of seeds comprising at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth)acrylate compound; Surrounding the seed, 30 to 50% by weight of an acrylate rubber core comprising an alkyl acrylate; and a shell surrounding the core and comprising 30 to 50% by weight of at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth)acrylate compound; and within this range It has excellent mechanical properties and excellent colorability.

When the seed content is less than the above range, the colorability is poor, and when the seed content exceeds the above range, the impact resistance is deteriorated.

If the content of the core is less than the above range, the rubber content may decrease and the impact reinforcing effect may be reduced as a graft copolymer. Since it is significantly lowered, it may not be possible to obtain a desired refractive index along with a reduction in the impact reinforcement effect.

The core of the rubber component may be, for example, an acrylic rubber polymerized including an alkyl acrylate and a crosslinking agent, and when the crosslinking agent is included, the gel content may be controlled and the impact resistance is excellent.

On the other hand, the average particle diameter to the core including the seed is, for example, more than 140 nm to less than 380 nm, preferably 150 to 370 nm, more preferably 150 to 350 nm, even more preferably 200 to 300 nm, further Preferably, it is 250-300 nm, and it is preferable for impact resistance and coloring property balance maintenance.

In the present description, the aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-styrene, p-styrene, and styrene monomer derivatives of vinyl toluene.

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.

In the present description, alkyl (meth)acrylate may be defined to include both alkyl acrylates and alkyl methacrylates.

In the present description, the alkyl acrylate may be, for example, an alkyl acrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, and octyl. It may be at least one selected from the group consisting of acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate and lauryl acrylate, and preferably a C1-C4 chain alkyl group It may be an alkyl acrylate containing, more preferably n-butyl acrylate or 2-ethylhexyl acrylate.

In the present description, the alkyl methacrylate may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples thereof include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylbutyl methacrylate. , may be at least one selected from the group consisting of 2-ethylhexyl methacrylate and lauryl methacrylate, preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, more preferably methyl methacrylate.

The seed, the core, or all of them may be formed by further including, for example, at least one compound represented by the following Chemical Formula 1 as a crosslinking agent.

[Formula 1]

(Wherein, A is independently a substituent having a vinyl group or a (meth)acrylate group, and A' is a hydrogen group, a substituent having a vinyl group, an alkyl group having 1 to 30 carbon atoms, an arylalkyl group having 5 to 24 carbon atoms, or 5 carbon atoms. to 24 arylamine group, or an aryl group having 6 to 30 carbon atoms,

R is independently a divalent ethyl group or a propyl group, and n is an integer of 0 to 15, 0 to 5, or 0 to 4.)

In another example, the seed, core, or both may be used as a crosslinking agent for divinylbenzene, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4- Butanediol dimethacrylate, aryl acrylate, aryl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate Late, neopentyl glycol dimethacrylate, triallyl isocyanurate, triarylamine, and may further include one or more from the group consisting of diallylamine.

As an example, the crosslinking agent is used in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total monomer used in preparing the (A) first graft copolymer.

In addition, the shell may be included in an amount of 20 to 60 parts by weight based on 100 parts by weight of the total of the monomers forming the (A) first graft copolymer, for example. When the content of the shell is small, the grafting efficiency is lowered and the rubber is agglomerated, and the impact reinforcing effect is reduced due to a decrease in compatibility with the resin, and when the content of the shell is excessive, the impact efficiency is decreased due to a decrease in the relative rubber content.

The shell is, for example, a copolymer comprising at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate in order to control polymerization reactivity and refractive index to an appropriate level, by graft polymerization. it will be formed

In another example, the shell is formed by graft polymerization with an aromatic vinyl compound and a vinyl cyan compound, or a copolymer comprising an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate.

The (A) method for preparing the first graft copolymer is, for example, i) polymerizing 5 to 40 wt% of at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate compound. preparing a seed; ii) preparing a core by polymerizing 20 to 60% by weight of an alkyl acrylate in the presence of the seed; and iii) graft emulsion polymerization of 20 to 60% by weight of at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth)acrylate compound in the presence of the core to form a seed-core-shell structure It may include the step of preparing a graft copolymer, in this case there is an effect excellent in weather resistance and colorability.

The (A) first graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, chemical resistance, weather resistance, fluidity, tensile strength and impact strength are excellent.

The emulsion polymerization is not particularly limited if the emulsion graft polymerization method commonly carried out in the art to which the present invention belongs.

(B) Second acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer

The (B) second graft copolymer may include, for example, an acrylate rubber core having an average particle diameter of 400 to 600 nm; and a shell enclosing the rubber core, and in this case, it is effective because it has excellent weather resistance and excellent impact resistance, colorability and fluidity.

The acrylate rubber core of the (B) second graft copolymer may have, for example, an average particle diameter of 400 to 600 nm, preferably 400 to 550 nm, more preferably 450 to 530 nm, within this range. It has good weather resistance and excellent mechanical strength such as fluidity and impact resistance.

The (B) second graft copolymer is, for example, 5 to 35% by weight, preferably 10 to 30% by weight, more preferably 15 to 25% by weight, based on the total weight of the thermoplastic resin composition, and weather resistance within this range; There is an effect excellent in fluidity, impact resistance and colorability.

The (B) second graft copolymer may include, for example, 40 to 60% by weight of an acrylate rubber core; and a shell surrounding the rubber core and comprising 25 to 45% by weight of an aromatic vinyl compound, 10 to 20% by weight of a vinyl cyanide compound, and 0 to 20% by weight of an alkyl (meth)acrylate compound, within this range It has excellent effects in weather resistance, fluidity and impact resistance.

Preferably, the (B) second graft copolymer comprises 45 to 55 wt% of an acrylate rubber core; and a shell surrounding the rubber core and comprising 30 to 40 wt% of an aromatic vinyl compound, 10 to 20 wt% of a vinyl cyanide compound, and 0 to 10 wt% of an alkyl (meth)acrylate compound, within this range It has excellent effects in weather resistance, fluidity and impact resistance.

More preferably, the (B) second graft copolymer comprises 45 to 55 wt% of an acrylate rubber core; and a shell surrounding the rubber core and comprising 30 to 40% by weight of an aromatic vinyl compound and 10 to 20% by weight of a vinyl cyan compound, and has excellent weather resistance, fluidity and impact resistance within this range .

The rubber core is, for example, 0 to 20% by weight, preferably 0.1 to 15% by weight of at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl methacrylate, in 100 parts by weight of the core, more preferably may be included in an amount of 1 to 15% by weight, and in this case, weather resistance, fluidity, colorability and impact resistance are excellent, and when it exceeds 20% by weight, impact strength is lowered.

The rubber core may preferably be an acrylate rubber including an alkyl acrylate, and in this case, it has excellent weather resistance, fluidity and impact resistance, and has the effect of further improving colorability.

The rubber core may be prepared by, for example, adding 0.01 to 3 parts by weight, preferably 0.1 to 1 parts by weight of a crosslinking agent, based on 100 parts by weight of (B) the second graft copolymer, and polymerizing the resin within the above range. There is an effect of improving the impact resistance and weather resistance of the

As a specific example, the rubber core may be prepared by adding 0.01 to 3 parts by weight of a crosslinking agent, 0.01 to 3 parts by weight of an initiator, and 0.01 to 5 parts by weight of an emulsifier, based on 100 parts by weight of the second graft copolymer (B), and polymerization. There is an effect of improving the impact resistance and weather resistance of the resin within the above range.

The crosslinking agent may be, for example, used in the polymerization step of the seed, core, or both of the (A) first graft copolymer.

In the present description, 100 parts by weight of the graft copolymer means based on 100 parts by weight of the total weight of the finally obtained graft copolymer, or conveniently, the total weight of the rubber and the shell component, that is, the total weight of the monomer mixture, or rubber manufacturing It may mean based on 100 parts by weight of the total weight of the monomer and the shell component added at the time.

The rubber core may include, for example, a polymer seed, in which case colorability is further improved.

The polymer seed is, for example, (B) 1 to 25% by weight of one or more monomers selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound and an alkyl (meth)acrylate in 100 parts by weight of the second graft copolymer, preferably 3 to 15% by weight, more preferably 3 to 10% by weight may be prepared by polymerization, and within this range, there is an excellent effect in impact resistance, weather resistance, physical property balance, and the like.

As a specific example, the polymer seed is added to at least one monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth)acrylate, based on 100 parts by weight of the graft copolymer, 0.01 to 3 parts by weight of a crosslinking agent, 0.01 to 3 parts by weight of an initiator It can be prepared by polymerization including 3 parts by weight and 0.01 to 5 parts by weight of an emulsifier, and within the above range, a polymer having an even size can be prepared within a short time, and physical properties such as weather resistance and impact resistance can be further improved.

In another specific example, the polymer seed is added to at least one monomer selected from an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth)acrylate, (B) 0.1 to 1 weight of a crosslinking agent based on 100 parts by weight of the second graft copolymer Part, it can be prepared by polymerization including 0.01 to 1 part by weight of an initiator and 0.5 to 1.5 parts by weight of an emulsifier, and a polymer with an even size can be prepared within a short time within the above range, and physical properties such as weather resistance and impact resistance are further improved can be

The polymer seed preferably polymerizes alkyl (meth)acrylate alone, copolymerizes alkyl (meth)acrylate with one of an aromatic vinyl compound or a vinyl cyan compound, or copolymerizes an aromatic vinyl compound and a vinyl cyan compound. and preferably, an aromatic vinyl compound and a vinyl cyan compound may be copolymerized, and in this case, mechanical strength such as weather resistance and impact resistance may be further improved.

The polymer seed may be prepared by optionally further including at least one of an electrolyte and a grafting agent during the polymerization.

The electrolyte may be used, for example, in an amount of 0.0001 to 1 part by weight, preferably 0.001 to 1 part by weight, more preferably 0.05 to 1 part by weight, based on 100 parts by weight of (B) the second graft copolymer, within this range. In the polymerization reaction and the stability of the latex is improved.

In the present substrate, the electrolyte is, for example, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , Na ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ , Na ₂ HPO ₄ , KOH, NaOH and Na ₂ S ₂ O ₇ may be at least one selected from the group consisting of, but not limited thereto.

The grafting agent may be used, for example, in an amount of 0.01 to 3 parts by weight, preferably 0.01 to 1 parts by weight, more preferably 0.01 to 0.1 parts by weight, based on 100 parts by weight of (B) the second graft copolymer. There is an advantage in that the graft rate of the graft polymer can be improved within, and other physical properties are also excellent.

As the grafting agent in the present description, a compound containing an unsaturated vinyl group having two or more different reactivity may be used, for example, at least one selected from allyl methacrylate, triallyl isocyanurate, triallyl amine and diallyl amine. may, but is not limited thereto.

The (B) method for preparing the second graft copolymer is, for example, i) 40 to 60 wt% of an acrylate rubber having an average particle diameter of 400 to 600 nm, 25 to 45 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyanide compound and graft emulsion polymerization of 100 parts by weight of a monomer mixture containing 0 to 20% by weight of an alkyl (meth)acrylate compound to prepare a core-shell structure graft copolymer, in this case There is an effect excellent in weather resistance and colorability.

As another example, the (B) method for preparing the second graft copolymer comprises i) 1 to 25% by weight of at least one monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth)acrylate compound. polymerizing to prepare a seed; ii) preparing a core by polymerizing 40 to 60% by weight of an alkyl acrylate in the presence of the seed; and iii) graft emulsion polymerization of 25 to 45% by weight of an aromatic vinyl compound, 10 to 20% by weight of a vinylcyan compound, and 0 to 20% by weight of an alkyl (meth)acrylate compound in the presence of the core to form a seed-core-shell structure It may include the step of preparing a graft copolymer of, in this case, there is an effect more excellent in weather resistance and colorability.

The (B) second graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, chemical resistance, weather resistance, fluidity, tensile strength and impact strength are excellent.

The emulsion polymerization is not particularly limited in the case of the emulsion graft polymerization method commonly carried out in the technical sale to which the present invention belongs.

The (B) second graft copolymer may have, for example, a graft rate of 20 to 100%, preferably 30 to 80%, more preferably 45 to 60%, and has excellent weather resistance and colorability within this range. has an improving effect.

The (B) second graft copolymer may have, for example, a gel content of less than 92% by weight, preferably 40 to 90% by weight, more preferably 60 to 90% by weight, and has excellent weather resistance within this range. and has the effect of improving colorability.

The (B) second graft copolymer may have, for example, a swelling index of 4 to 13, preferably 5 to 11, more preferably 5 to 9, and has excellent weather resistance and colorability within this range. It works.

In the present description, the initiator is not particularly limited if it is an initiator generally used in the art to which the present invention belongs, and for example, a water-soluble initiator, a fat-soluble initiator, or a mixture of these initiators may be used.

As the water-soluble initiator, for example, at least one selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide, and the like may be used, but it is not limited thereto.

Examples of the fat-soluble initiator include t-butyl peroxide, cumene hydroperoxide, p-methane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octane Noyl peroxide, dibenzoyl peroxide, diisopropylbenzene hydroperoxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutylate, azobis isobutyronitrile, azobis-2, At least one selected from the group consisting of 4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyrate (butyric acid) methyl may be used, but is not limited thereto.

The (B) second graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, it has excellent effects in weather resistance, fluidity, tensile strength and impact resistance.

The emulsion polymerization is not particularly limited if the emulsion graft polymerization method commonly carried out in the art to which the present invention belongs.

The weight ratio (A:B) of the (A) first graft copolymer and the (B) second graft copolymer is, for example, 1:0.3 to 1:1.5, preferably 1:0.4 to 1:1.35, More preferably 1:0.5 to 1:1.25, even more preferably 1:0.5 to 1:1, there is an effect excellent in weather resistance, fluidity and impact resistance within this range.

(C) matrix polymer

The (C) matrix polymer may be, for example, 40 to 70% by weight based on the total weight of the thermoplastic resin composition, preferably 45 to 65% by weight, more preferably 50 to 60% by weight, within this range It has excellent weather resistance and excellent fluidity.

The matrix polymer may be, for example, at least one selected from a hard matrix polymer including at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth)acrylate compound.

In the present description, the hard matrix resin refers to a resin composed of a hard polymer-forming monomer having a glass transition temperature of at least 80°C and preferably 80 to 200°C.

As another example, the matrix polymer may be an aromatic vinyl compound-vinyl cyan compound copolymer, for example, a SAN (styrene-acrylonitrile) resin.

The aromatic vinyl compound-vinyl cyan compound copolymer may include, for example, 65 to 80 wt% of an aromatic vinyl compound and 20 to 35 wt% of a vinyl cyanide compound, and has excellent processability and impact resistance within this range. .

The aromatic vinyl compound-vinyl cyan compound copolymer may have, for example, a weight average molecular weight of 60,000 to 120,000 g/mol, preferably 70,000 to 110,000 g/mol, more preferably 80,0000 to 100,000 g/mol, and There is an effect of excellent fluidity within the range.

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 for a standard PS (standard polystyrene) sample.

At this time, in the (A) first graft copolymer, the difference between the refractive index of the seed and the refractive index of the shell is _{less than the refractive index of the matrix polymer (μ D} ²⁵ ), for example, less than 0.035, preferably less than 0.03, more preferably less than 0.02 , more preferably 0.01 or less is preferable in consideration of colorability by imparting transparency to the graft copolymer.

In addition, in the (A) first graft copolymer, the refractive index of the core has _{a difference from the refractive index of the matrix polymer (μ D} ²⁵ ), for example, more than 0.056, preferably 0.08 or more, more preferably 0.06 to 0.15, and more More preferably, if the value is 0.08 to 0.13, the effect of improving the colorability is clearly displayed, and when butadiene or styrene having a relatively high refractive index is used for the core in order to reduce the refractive index difference, weather resistance and impact resistance are deteriorated, respectively.

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.

Thermoplastic resin composition

The thermoplastic resin composition of the present invention has a flow index (220° C., 10 kg) measured according to ASTM D1238 of 15 g/10 min or more, preferably 15-30 g/10 min, more preferably 18-25 g/10 min. characterized by being. In this case, there is an effect excellent in the balance of weather resistance, impact resistance, and colorability.

The thermoplastic resin composition of the present disclosure preferably has an Izod impact strength (1/8", 23° C.) measured according to ASTM D256 of 30 kgf cm/cm or more, preferably 30 to 45 kgf cm/cm, more Preferably, it may be 30 to 40 kgf·cm/cm, and within this range, the balance of weather resistance, fluidity and colorability is excellent.

The thermoplastic resin composition of the present disclosure preferably has a color L value (colorability) of 95 or more, preferably 95 to 100 days, measured using a color meter (model name Color Eye 7000A) based on the CIE1976 L*a*b* color system. There is an excellent effect in the balance of weather resistance, impact resistance and fluidity within this range.

The thermoplastic resin composition of the present disclosure preferably has a weather resistance (ΔE) calculated by the following Equation 3 after 2000 hours measurement by the SAE J1960 method is less than 2.5, preferably 2.5 or less, and within this range, impact resistance, colorability and There is an effect excellent in the balance of fluidity.

[Equation 3]

The thermoplastic resin composition is an example of an antioxidant, a UV stabilizer, a UV stabilizer, an optical brightener, a lubricant, a chain extender, a release agent, a pigment, a dye, an antibacterial agent, a processing aid, a metal deactivator, a smoke suppressant, an inorganic filler, glass fiber, It may further include one or more additives selected from the group consisting of an anti-friction agent and an anti-wear agent, and the additive is, for example, (A) the first graft copolymer, (B) the second graft copolymer, and (C) the matrix. It may be 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight, and more preferably 0.1 to 1 parts by weight based on 100 parts by weight of the total polymer, and in this case, the effect is excellent in improving physical properties and economical due to low manufacturing cost. have.

Hereinafter, a method for producing the thermoplastic resin composition of the present invention and a molded article including the composition will be described. In describing the method for producing the thermoplastic resin composition of the present invention and a molded article including the composition, all of the above-described thermoplastic resin composition is included.

Method for producing a thermoplastic resin composition

The method for producing the thermoplastic resin composition of the present invention preferably comprises (A) a seed; An acrylate rubber core surrounding the seed and having an average particle diameter of more than 140 nm to less than 380 nm; and 10 to 40 wt% of a first acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing a shell surrounding the rubber core; (B) an acrylate rubber core having an average particle diameter of 400 to 600 nm; and 5 to 35 wt% of a second acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing a shell surrounding the rubber core; and (C) 40 to 70 wt% of the matrix polymer; kneading and extruding at 200 to 300 °C and 80 to 400 rpm conditions, wherein the thermoplastic resin composition has a flow index (220 °C) measured according to ASTM D1238 , 10 kg) is characterized in that 15 g/10 min or more. In this case, the thermoplastic resin composition has excellent weather resistance and excellent impact resistance, colorability and fluidity.

The kneading and extrusion may be performed by, for example, a single-screw extruder, a twin-screw extruder, or a Banbury mixer, in which case the composition is uniformly dispersed to have excellent compatibility.

The kneading and extrusion may be carried out, for example, at a barrel temperature of 200 to 300 ° C, preferably 200 to 250 ° C. 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.

The kneading and extrusion may be performed under the condition that the screw rotation speed is 80 to 400 rpm, preferably 100 to 200 rpm, for example, and in this case, the throughput per unit time is appropriate and the process efficiency is excellent, and the effect of suppressing excessive cutting there is

molded product

The molded article of the present substrate may be made of, for example, the thermoplastic resin composition of the present substrate, and in this case, it has excellent mechanical properties such as impact strength, and excellent chemical resistance, processability and colorability expressed by melt index.

The molded article may be, for example, a large-sized injection molding product or a control panel having a complex molding structure, specifically, a washing machine front panel, a detergent inlet panel, an automobile power window bezel, or a bidet control panel, and in this case, the thermoplastic resin composition of the present disclosure It has the advantage of being able to provide a higher quality than the quality for weather resistance, impact resistance, fluidity and colorability required by the market, as well as providing a beautiful effect without painting.

Hereinafter, preferred examples are presented to aid 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]

(A-1) Copolymer: the first graft copolymer (16.5 wt% of styrene and 5.5 wt% of acrylonitrile as a core, 45 wt% of a butylacrylate polymer as a core, and 24.5 wt% of styrene as a shell and 8.5 wt% of acrylnitrile %, the average particle diameter of the core including the seed 250 nm, the core thickness (r2-r1) 50 nm, the gel content 84.8%, the swelling index 5.8, the graft rate 26.5%, (A-1) the seed of the copolymer ( C) It is characterized in that the difference in refractive index with the matrix resin is 0.0023, and the difference in refractive index between the core of the copolymer (A-1) and (C) the matrix resin is 0.1240.)

(A-2) copolymer: the first graft copolymer (16.5 wt% of styrene and 5.5 wt% of acrylonitrile as a core, 41 wt% of a butylacrylate polymer as a core, and 27 wt% of styrene as a shell, 10 wt% of acrylnitrile %, the average particle diameter of the core including the seed 260 nm, the core thickness (r2-r1) 40 nm, the gel content 82.7%, the swelling index 5.7, the graft rate 31.2%, (A-2) the seed of the copolymer ( C) The difference in refractive index with the matrix resin and the difference in refractive index between the core of the copolymer (A-2) and the (C) matrix resin are the same as those of the copolymer (A-1).)

(A-3) copolymer: the first graft copolymer (18.5 wt% of styrene and 6.5 wt% of acrylonitrile as a seed, 42 wt% of a butylacrylate polymer as a core, and 25.5 wt% of styrene as a shell and 7.5 wt% of acrylnitrile %, the average particle diameter of the core including the seed 270 nm, the core thickness (r2-r1) 40 nm, the gel content 86.5%, the swelling index 6.1, the graft rate 29.1%, (A-3) the seed of the copolymer ( C) The difference in refractive index with the matrix resin and the difference in refractive index between the core of the copolymer (A-3) and the (C) matrix resin are the same as those of the copolymer (A-1).)

(A-4) Copolymer: the first graft copolymer (16.5 wt% of styrene and 5.5 wt% of acrylonitrile as a core, 45 wt% of a butylacrylate polymer as a core, and 24.5 wt% of styrene as a shell and 8.5 wt% of acrylnitrile %, the average particle diameter of the core including the seed 240 nm, the core thickness (r2-r1) 50 nm, the gel content 87.6%, the swelling index 6.5, the graft rate 30.8%, (A-4) the seed of the copolymer ( C) The difference in refractive index with the matrix resin and the difference in refractive index between the core of the copolymer (A-4) and the (C) matrix resin are the same as those of the copolymer (A-1).)

(A-5) copolymer: the first graft copolymer (13.5 wt% of styrene and 4.5 wt% of acrylonitrile as a seed, 45 wt% of a butylacrylate polymer as a core, and 25.5 wt% of styrene as a shell and 8.5 wt% of acrylnitrile %, the average particle diameter of the core including the seed 250 nm, the core thickness (r2-r1) 70 nm, the gel content 80.9%, the swelling index 5.6, the graft rate 28.5%, (A-5) the seed of the copolymer ( C) The difference in refractive index with the matrix resin and the difference in refractive index between the core of the copolymer (A-5) and the (C) matrix resin are the same as those of the copolymer (A-1).)

(D) copolymer: small diameter graft copolymer (7.5 wt% of styrene and 2.5 wt% of acrylonitrile as a core, 50 wt% of a butylacrylate polymer as a core, and 30 wt% of styrene as a shell and 10 wt% of acrylnitrile The average particle diameter of the core including the seed is 100 nm, (D) the difference in refractive index between the seed of the copolymer and (C) the matrix resin is 0.0033, (D) the difference in the refractive index between the core of the copolymer and (C) the matrix resin is 0.1240 It is characterized by being.)

(B) copolymer: the second graft copolymer (3.5 wt% of styrene as seed and 1.5 wt% of acrylonitrile as a core, 55 wt% of a butyl acrylate polymer having an average particle diameter of 500 nm including seeds as a core, and 30 wt% of shello styrene % and 10% by weight of acrylnitrile, characterized in that it is a graft copolymer.)

(C) Matrix polymer: styrene-acrylonitrile copolymer (weight average molecular weight 80,000 g/mol)

Examples 1 to 7, Comparative Examples 1 to 5 and Reference Examples 1 to 3

To the components and contents described in Tables 1 and 2, respectively, _{6 parts by weight of TiO 2} , kneaded and extruded at 230° C. to prepare pellets. The 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.

[Test Example]

The properties of the pellets and specimens prepared in Examples 1 to 7, Comparative Examples 1 to 5 and Reference Examples 1 to 3 were measured by the following method, and the results are shown in Tables 1 to 3 below.

* Refractive index: The powder was compressed and measured with a refractometer (Metricon 2010).

* Average particle diameter of seed / core / shell: Each latex was measured as an intensity value in Gaussian mode using the NICOMP 380 Particle Size Analyzer by dynamic laser light scattering method, and also prepared with acrylic The nitrile-acrylate-styrene graft copolymer was prepared by TEM (Jeol. JEM-1400) to Acc. Measure at the ratio of SPOT Size: 1 (× 10K, × 25K, × 50K) under the condition of Volt: 120KV to obtain all the longest particle diameters of the seed/core/shell of the particles corresponding to the top 10% of particle size, then average these values Confirmed.

For reference, r1 was measured as a value obtained by dividing the average particle diameter of the seed in half, and r2 was measured as a value obtained by dividing the average particle diameter of the seed-containing core in half.

* Flow index (g/10min; melt index): The prepared pellets were measured by ASTM D1238 under the conditions of 220°C/10kg.

* Izod impact strength (kgf·cm/cm; IMP): The thickness of the specimen was 1/8″ and was measured by ASTM 256 method.

* L value (colorability): Based on the CIE1976 L*a*b* color system, the color L value was measured using a color meter (model name: Color Eye 7000A). At this time, if L=100, it means pure white, and if L=0, it means pure black. The higher the L value, the higher the colorability because the color of the white plate on the back plate of the specimen is projected.

* Weather resistance: After 2000 hours of measurement by the SAE J1960 method, it was evaluated as ΔE calculated by Equation 3 below. When the ΔE value is low, the weather resistance is excellent.

[Equation 3]

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 (A-1) copolymer 30 25 20 (A-2) copolymer 30 23 (A-3) copolymer 30 (A-4) copolymer 30 (B) copolymer 15 20 25 15 23 15 15 (C) matrix resin 55 55 55 55 54 55 55 Core diameter including seed in the first graft copolymer (nm) 250 250 250 260 260 270 240 Core thickness (nm) in the first graft copolymer 50 50 50 40 40 40 50 flow index 18.7 18.6 18.7 19.1 17.2 18.8 17.1 impact strength 31.5 33.2 35.9 30.3 30.5 31.0 32.4 L value (colorability) 96.540 96.299 95.511 96.727 96.412 96.428 96.621

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Reference Example 1 Reference Example 2 Reference Example 3 (A-1) copolymer 30 5 45 30 15 (A-5) copolymer 30 (D) copolymer 15 15 10 (B) copolymer 30 35 30 10 15 6 25.5 (C) matrix resin 55 55 55 65 45 55 64 59.5 Core diameter including seed in the first graft copolymer (nm) 250 500 ^* 500 ^* 250 250 250 250 250 Core thickness (nm) in the first graft copolymer 50 250 ^** 250 ^** 50 50 70 50 50 flow index 13.3 13.5 13.7 25.8 8.6 17.2 23.2 19.8 impact strength 18.9 24.4 31.1 20.5 38.7 31.1 15.7 28.2 L value (colorability) 96.918 94.672 94.135 95.322 95.131 93.926 96.703 95.127

^* : (B) Average particle diameter of the core of the copolymer (including seeds)

^** : (B) the core thickness of the copolymer

division Example comparative example Reference example One 2 3 One 2 3 4 5 One 2 3 △E
(weather resistance) 2.4 2.6 2.7 2.5 2.8 2.8 2.9 2.6 2.7 2.6 2.7

As shown in Tables 1 to 3, the thermoplastic resin compositions (Examples 1 to 7) according to the present invention are excellent in both impact strength and L value (colorability) while weather resistance is equal to or higher than Comparative Examples 1 to 5 In particular, it was confirmed that the fluidity improvement effect was excellent when the fluidity index was 15 g/10min or more.

In addition, in Reference Example 1 in which the core thickness of the first graft copolymer was 70 nm, the impact strength was similar, but the flow index, L value, and weather resistance were lowered, and the weight ratio of the first graft copolymer and the second graft copolymer In Reference Examples 2 and 3, where is 1:02 and 1:1.7, respectively, the impact strength was lowered.

Claims (11)

(A) seed; An acrylate rubber core surrounding the seed and having an average particle diameter of more than 140 nm to less than 380 nm including the seed; and 10 to 40 wt% of a first acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing a shell surrounding the rubber core;
(B) an acrylate rubber core having an average particle diameter of 400 to 600 nm; and 5 to 35 wt% of a second acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing a shell surrounding the rubber core; and
(C) 40 to 70% by weight of the matrix polymer;
Characterized in that the flow index (220 ℃, 10 kg) measured according to ASTM D1238 is 15 g/10 min or more
Thermoplastic resin composition.
According to claim 1,
(A) the difference between the refractive index of the seed and the shell of the first graft copolymer and the refractive index of the matrix polymer (μ _D ²⁵ ) is less than 0.035, respectively,
(A) the difference between the refractive index of the core of the first graft copolymer and the refractive index of the matrix polymer (μ _D ²⁵ ) is greater than 0.056,
The (A) first graft copolymer is characterized in that it simultaneously satisfies the following Equations 1 and 2
Thermoplastic resin composition.
[Equation 1]
140 < 2*r2 < 380
[Equation 2]
10 ≤ r2 - r1 ≤ 60
(In Equations 1 and 2, r1 is the thickness (nm) from the center of the (A) first graft copolymer to the seed, and r2 is (A) from the center to the core of the first graft copolymer. thickness (nm).
According to claim 1,
The (A) first graft copolymer has a gel content of 65 to 95%, a swelling index of 3 to 10, and a graft rate of 25% or more
Thermoplastic resin composition.
According to claim 1,
The weight ratio of the (A) first graft copolymer to the (B) second graft copolymer is 1:0.3 to 1:1.5, characterized in that
Thermoplastic resin composition.
According to claim 1,
The (A) first graft copolymer is 5 to 40 wt% of a seed comprising at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth)acrylate compound; 20 to 60% by weight of an acrylate rubber core surrounding the seed and comprising an alkyl acrylate; and a shell surrounding the core and comprising 20 to 60% by weight of at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth)acrylate compound.
Thermoplastic resin composition.
According to claim 1,
The (B) second graft copolymer comprises 40 to 60 wt% of an acrylate rubber core; and a shell surrounding the rubber core and comprising 25 to 45% by weight of an aromatic vinyl compound, 10 to 20% by weight of a vinyl cyan compound, and 0 to 20% by weight of an alkyl (meth)acrylate compound.
Thermoplastic resin composition.
According to claim 1,
The matrix polymer is characterized in that at least one selected from a hard matrix polymer comprising at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth)acrylate compound.
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition is characterized in that the Izod impact strength measured according to ASTM D256 using a specimen thickness of 1/8" is 30 kgf·cm/cm or more
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition is characterized in that the L value (colorability) measured using a color meter (model name Color Eye 7000A) based on the CIE1976 L*a*b* color system is 95.5 or more
Thermoplastic resin composition.
A method for producing a thermoplastic resin composition comprising: (A) a seed; An acrylate rubber core surrounding the seed and having an average particle diameter of more than 140 nm to less than 380 nm including the seed; and 10 to 40 wt% of a first acrylate-aromatic vinyl compound-vinylcyanide compound graft copolymer containing a shell surrounding the rubber core; (B) an acrylate rubber core having an average particle diameter of 400 to 600 nm; and 5 to 35 wt% of a second acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing a shell surrounding the rubber core; And (C) 40 to 70% by weight of the matrix polymer; comprising the step of kneading and extruding under the conditions of 200 to 300 ℃ and 80 to 400 rpm,
The thermoplastic resin composition is characterized in that the flow index (220 ℃, 10 kg) measured according to ASTM D1238 is 15 g/10 min or more
A method for producing a thermoplastic resin composition.
Claims 1 to 9, characterized in that prepared from the thermoplastic resin composition of any one of claims
molded product.