WO2015046729A1 - Method for preparing rubber reinforced graft copolymer and rubber reinforced graft copolymer prepared thereby - Google Patents

Abstract

The present disclosure relates to a method for preparing a rubber reinforced graft copolymer and a rubber reinforced graft copolymer prepared thereby and, more specifically, to a method for preparing a rubber reinforced graft copolymer, in which i) 40 to 50 wt% of rubber latex having an average particle size of 0.25 to 0.45 ㎛ and a gel content of 80 to 95 wt%; ii) 10 to 20 wt% of rubber latex having an average particle size of 0.49 to 0.13 ㎛ and a gel content of 85 to 99 wt%; iii) 20 to 35 wt% of α-methyl styrene; and iv) 5 to 20 wt% of a vinyl cyanide monomer are emulsification-polymerized using polymerization water, an emulsifying agent, a molecular weight regulator, an initiator, and an activating agent, wherein the entire quantity of rubber latex of i) and ii) are fed in before polymerization initiation, and the vinyl cyanide monomer of iv) is not or only partially fed in before polymerization initiation, and then the remainder is fed after the polymerization initiation, and to a rubber reinforced graft copolymer prepared thereby. According to the present disclosure, provided are an α-methyl styrene based rubber reinforced graft copolymer capable of improving heat resistance as well as polymerizing productivity and a rubber reinforced graft copolymer prepared thereby.

Description

Method for preparing rubber-reinforced graft copolymer and rubber-reinforced graft copolymer prepared therefrom

The present disclosure relates to a method for preparing a rubber-reinforced graft copolymer and a rubber-reinforced graft copolymer prepared therefrom, and more particularly, to a method for preparing a rubber-reinforced graft copolymer including alpha-methylstyrene, It relates to a rubber reinforced graft copolymer prepared by introducing a rubber latex and improved polymerization productivity and heat resistance characteristics, and rubber reinforced graft copolymer prepared therefrom.

The present invention also relates to a thermoplastic resin composition having excellent heat resistance including the rubber-reinforced graft copolymer and the heat-resistant styrene-acrylonitrile copolymer.

Generally, acrylonitrile-butadiene-styrene copolymer (ABS resin) is a resin having excellent processability and beautiful appearance characteristics such as styrene processability, stiffness and chemical resistance of acrylonitrile, impact resistance of butadiene rubber, etc. It is used in various fields such as home appliances, housings, and toys.

In particular, automotive interior materials, such as high thermal properties (thermal deformation resistance, HDT) is required, ABS resins that can satisfy these high thermal properties are usually produced by emulsion polymerization or solution polymerization, and has a high glass transition temperature (Tg) -Methylstyrene-acrylonitrile copolymer (AMSAN) is prepared by melt mixing a rubber-reinforced graft copolymer (acrylonitrile-butadiene-styrene copolymer) prepared by emulsion polymerization within a range having a predetermined rubber content. do. In this case, alpha-methylstyrene having a higher glass transition temperature may be used in place of styrene when preparing the rubber-reinforced graft copolymer to improve heat resistance. However, when alpha-methylstyrene is used, alpha-methyl styrene is used in the emulsion polymerization step. Due to the low reactivity and the lowering of the polymerization stability, the polymerization rate is greatly lowered and the amount of coagulated product is increased, resulting in a problem of lowering productivity and heat resistance.

In order to solve the problems of the prior art as described above, the present invention provides a rubber latex having an average particle diameter of 0.09 to 0.13 μm and a gel content of 85 to 99 wt% when preparing a rubber-reinforced graft copolymer including alpha-methylstyrene. It is an object of the present invention to provide a method for producing a rubber-reinforced graft copolymer and a rubber-reinforced graft copolymer prepared therefrom, in which not only polymerization productivity but also heat resistance are improved.

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

In order to achieve the above object, the present substrate is i) 40-50% by weight rubber latex having an average particle diameter of 0.25 to 0.45 ㎛ and gel content of 80 to 95% by weight; ii) 10 to 20% by weight rubber latex having an average particle diameter of 0.09 to 0.13 mu m and a gel content of 85 to 99% by weight; iii) 20 to 35 weight percent of alpha-methylstyrene; And iv) 5 to 20% by weight of vinyl cyan monomer; emulsion polymerization using a polymerization water, an emulsifier, a molecular weight regulator, an initiator and an activator, wherein the rubber latex of i) and ii) is added to the entire polymerization initiation; The vinyl cyan monomer of iv) provides a method for preparing a rubber-reinforced graft copolymer, characterized in that it is not added before the start of polymerization or a part is added and then the remainder is added after the start of polymerization.

In addition, the present disclosure provides a rubber-reinforced graft copolymer, characterized in that it is prepared according to the method for producing the rubber-reinforced graft copolymer.

In addition, the present invention is a) i) 40-50% by weight rubber latex having an average particle diameter of 0.25 to 0.45 ㎛, gel content of 80 to 95% by weight, ii) 0.09 to 0.13 ㎛ average particle diameter and 85 to 99 gel content 10% to 20% by weight of rubber latex, iii) 20 to 35% by weight of alpha-methylstyrene, and iv) 5 to 20% by weight of vinyl cyan monomer, and a polymerization water, an emulsifier, a molecular weight regulator, a fat-soluble initiator and an activator. Emulsion polymerization using; And b) blending the rubber-reinforced graft copolymer prepared by the emulsion polymerization with a heat-resistant styrene-acrylonitrile-based copolymer; wherein the rubber latex of steps i) and ii) is polymerized. The whole amount is added, and the vinyl cyan monomer of iv) provides a method for producing a thermoplastic resin composition, wherein the remaining amount is added after the start of the polymerization after the start of the polymerization or a part of the vinyl cyan monomer is added.

In addition, the present disclosure provides a thermoplastic resin composition comprising the rubber-reinforced graft copolymer and a heat resistant styrene-acrylonitrile copolymer.

As described above, according to the present disclosure, there is provided a method for preparing a rubber-reinforced graft copolymer including alpha-methylstyrene that can improve not only polymerization productivity but also heat resistance, and a rubber-reinforced graft copolymer prepared therefrom. It works.

In addition, according to the present invention has an effect of providing a thermoplastic resin composition having excellent heat resistance comprising the rubber-reinforced graft copolymer and the heat-resistant styrene-acrylonitrile-based copolymer.

Hereinafter, the present description will be described in detail.

The method for producing a rubber-reinforced graft copolymer of the present disclosure includes: i) 40-50 wt% of rubber latex having an average particle diameter of 0.25-0.45 μm and a gel content of 80-95 wt%; ii) 10 to 20% by weight rubber latex having an average particle diameter of 0.09 to 0.13 mu m and a gel content of 85 to 99% by weight; iii) 20 to 35 weight percent of alpha-methylstyrene; And iv) 5 to 20% by weight of vinyl cyan monomer; emulsion polymerization using a polymerization water, an emulsifier, a molecular weight regulator, an initiator and an activator, wherein the rubber latex of i) and ii) is added to the entire polymerization initiation; The vinyl cyan monomer of iv) is not added before the start of polymerization or after a part is added, and then the remainder is added after the start of polymerization.

If the rubber latex of i) is less than 40% by weight, there is a decrease in impact resistance, and when the rubber latex is more than 50% by weight, there is a problem in that polymerization rate and stability are lowered.

In addition, when the rubber latex of ii) is less than 10% by weight, the effect of improving the polymerization rate and polymerization stability is insignificant, and when the rubber latex exceeds 20% by weight, impact resistance is inferior.

In addition, when the gel content of the rubber latex of i) is less than 80% by weight, the appearance characteristics are poor, and when it exceeds 95% by weight, the impact resistance is poor.

In addition, if the gel content of the rubber latex of ii) is less than 85% by weight has a poor effect on the appearance properties, when it exceeds 99% by weight has a poor impact resistance.

In addition, when the alpha-methylstyrene of iii) is less than 20% by weight, the effect of improving heat resistance is insignificant, and when it exceeds 35% by weight, there is a problem in that the polymerization time is long due to the decrease in reactivity, resulting in inferior economic efficiency.

In addition, when the vinyl cyan monomer of iv) is less than 5% by weight or more than 20% by weight, there is a problem that the heat resistance characteristics are inferior.

* The initiator of iv) is, for example, a fat-soluble redox initiator, in which case there is an advantageous effect in terms of polymerization rate.

For example, the rubber latex of i) may have an average particle diameter of 0.25 to 0.35 μm, or 0.3 to 0.4 μm, and has excellent impact resistance within this range.

The rubber latex of i) and ii) may be, for example, a conjugated diene-based rubber latex, in which case the impact strength is excellent.

The conjugated diene rubber latex is, for example, a rubber latex prepared from one or more conjugated diene monomers selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and pyerylene, and preferably 1,3-butadiene Rubber latex, in this case the impact strength is excellent.

For example, the alpha-methylstyrene of iii) may not be added before the start of polymerization or after a part is added, and then the remaining amount may be added after the start of polymerization. In this case, polymerization stability is excellent.

For example, the alpha-methylstyrene of iii) may be added in an amount of 10 to 50% by weight, or 30 to 40% by weight before the start of polymerization, and the remaining amount after the start of polymerization, based on the total amount of alpha-methylstyrene used for polymerization. In this range, the polymerization stability is excellent.

The vinyl cyan monomer of iv) is, for example, 10 to 15% by weight, and has an excellent effect on heat resistance within this range.

For example, the vinyl cyan monomer of iv) may be added in an amount of 0 to 50% by weight, or 30 to 50% by weight before the start of polymerization, and the remaining amount after the start of polymerization, based on the total amount of vinyl cyan monomer used for polymerization. Within the range, there is an excellent effect of excellent heat resistance characteristics.

The vinyl cyan monomer of iv) may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof, preferably acrylonitrile, in which case there is an advantageous effect on the reaction rate and heat resistance characteristics.

The polymerization water, the emulsifier, the initiator and the activator may be dividedly injected before and after the start of polymerization, for example, in this case, the polymerization speed is high and the polymerization stability is excellent.

The molecular weight regulator may be added after the start of polymerization as an example, in this case there is an excellent molecular weight control effect.

As said molecular weight regulator, it is a mercaptan type molecular weight regulator, for example, In this case, it is effective in molecular weight adjustment.

For example, the initiator and the activator may be added after the addition of all monomers is completed, in which case there is an advantageous effect in terms of polymerization rate.

The emulsifier may be at least one selected from the group consisting of, for example, an anionic adsorptive emulsifier, a nonionic emulsifier, a reactive emulsifier and a polymer reactive emulsifier, in which case the polymerization stability and latex storage stability are excellent.

The anionic adsorption-type emulsifier is, for example, potassium rosin acid, fatty acid potassium, sodium lauryl sulfonate, sodium alkyl benzene sulfonate, and the like. In this case, polymerization stability and latex storage stability are excellent.

The fat-soluble redox initiator is, for example, a redox-based polymerization initiator comprising a peroxide as a component, in which case there is an advantageous effect in terms of the polymerization rate.

The peroxide may be at least one selected from the group consisting of hydrogen peroxide, cumene hydroperoxide, diisopropyl benzene hydroperoxide, tertiary butyl hydroperoxide, and paramethane hydroperoxide, in this case, It has a beneficial effect.

The polymerization water or the like is not particularly limited when the amount (parts by weight) that can be conventionally used in the production of rubber-reinforced graft copolymers.

For example, the emulsion polymerization has an polymerization conversion of 97% or more, and has excellent heat resistance within this range.

In the emulsion polymerization, for example, the amount of coagulum produced is less than 0.1 wt% with respect to the total solid content, the balance of physical properties is excellent within this range, and the heat resistance is excellent.

The method of preparing the rubber-reinforced graft copolymer is, for example, at least one selected from the group consisting of sulfuric acid, MgSO ₄ , CaCl ₂ and Al ₂ (SO ₄ ) ₃ in the rubber-reinforced graft copolymer latex prepared by the emulsion polymerization. After the coagulant is added and coagulated, the aggregate may be washed, dehydrated if necessary, and dried to prepare a powder.

For example, a method of preparing the rubber-reinforced graft copolymer may include a) a rubber latex having an average particle diameter of 0.25 to 0.35 μm, a gel content of 80 to 95 wt%, an average particle diameter of 0.09 to 0.13 μm, and a gel content of 85 to Administering 99% by weight of rubber latex, alpha-methylstyrene, vinyl cyan monomer, emulsifier, deionized water, and molecular weight adjusting agent to the reactor, and then initiating polymerization by administering a fat-soluble redox initiator and an activator in a batch; b) reacting the monomer emulsion comprising a residual amount of alpha-methylstyrene, a residual amount of vinyl cyan monomer, an emulsifier, a molecular weight regulator, and deionized water, a fat-soluble redox initiator and an activator after the polymerization in step a) step; And c) it may comprise the step of further reacting by the batch administration of a fat-soluble redox initiator and activator to the reactant of step b).

As another example, the method of manufacturing the rubber-reinforced graft copolymer is a) 40-50 parts by weight of rubber latex having an average particle diameter of 0.25 to 0.45 μm, gel content of 80 to 95 wt%, and average particle diameter of 0.09 to 0.13 μm. 10 to 20 parts by weight of rubber latex having a gel content of 85 to 99% by weight, 0 to 35 parts by weight of alpha-methylstyrene, 0 to 5 parts by weight of acrylonitrile, 0 to 1 parts by weight of an emulsifier, and a fat-soluble redox initiator 0.01 To 1.0 part by weight, activator 0.02 to 0.8 part by weight and deionized water in a batch to start the polymerization reaction; b) 0 to 35 parts by weight of the remaining amount of alpha-methylstyrene after the polymerization reaction of step a), 5 to 15 parts by weight of acrylonitrile, 0 to 1 parts by weight of emulsifier, 0.01 to 2.0 parts by weight of molecular weight regulator, Reacting the monomer emulsion including ionized water with 0.01 to 1.0 parts by weight of a fat-soluble redox initiator and 0.01 to 0.5 parts by weight of an activator to react the same; And c) after the step b), the fat-soluble redox initiator may comprise the step of reacting by adding 0.005 to 1.0 parts by weight and 0.01 to 0.5 parts by weight of the activator in a batch.

The rubber-reinforced graft copolymer of the present disclosure is characterized in that it is prepared according to the preparation method of the rubber-reinforced graft copolymer.

The method for preparing the thermoplastic resin composition of the present invention includes a) i) 40-50 wt% of rubber latex having an average particle diameter of 0.25-0.45 μm and a gel content of 80-95 wt%, ii) a gel having an average particle size of 0.09-0.13 μm 10 to 20% by weight of rubber latex containing 85 to 99% by weight, iii) 20 to 35% by weight of alpha-methylstyrene, and iv) 5 to 20% by weight of vinyl cyan monomer, polymerized water, emulsifier, molecular weight regulator, initiator And emulsion polymerization using an activator; And b) blending the rubber-reinforced graft copolymer prepared by the emulsion polymerization with a heat-resistant styrene-acrylonitrile-based copolymer; wherein the rubber latex of steps i) and ii) is polymerized. The whole amount is added, and the vinyl cyan monomer of iv) is not added before the start of the polymerization, or a part is added, and then the remainder is added after the start of the polymerization.

The initiator of iv) is, for example, a fat-soluble redox initiator, and in this case, there is an advantageous effect in terms of polymerization rate.

The thermoplastic resin composition of the present disclosure is characterized in that it is prepared according to the method for producing the thermoplastic resin composition.

For example, the thermoplastic resin composition may have a total rubber content of 10 to 20% by weight, or 15 to 20% by weight, and have an excellent balance of physical properties and excellent heat resistance within these ranges.

As another example, the thermoplastic resin composition of the present invention is characterized in that it comprises 20 to 50 parts by weight of the rubber-reinforced graft copolymer and 80 to 50 parts by weight of the heat-resistant styrene-acrylonitrile copolymer.

The heat-resistant styrene-acrylonitrile-based copolymer may be a polymerized copolymer including, for example, 70 to 85% by weight of alpha-methylstyrene, 13 to 29% by weight of acrylonitrile, and 1 to 2% by weight of styrene. In this case, the physical property balance is excellent and heat resistance is excellent.

As another example, the heat-resistant styrene-acrylonitrile-based copolymer may be a polymerized copolymer including 60 to 80% by weight of alpha-methylstyrene, 15 to 35% by weight of acrylonitrile and 0.1 to 5% by weight of styrene. In this case, there is an excellent balance of physical properties and excellent heat resistance.

Hereinafter, preferred examples are provided to help the understanding of the present disclosure, but the following examples are merely exemplified by the present disclosure, and it is obvious to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present disclosure. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

Example 1

<Production of Rubber-Reinforced Graft Copolymer>

Polymerization Initiation Step

45 parts by weight of a rubber latex (hereinafter referred to as rubber latex A) having an average particle diameter of 0.32 μm and a gel content of 85 wt% (based on solids), a rubber latex having an average particle diameter of 0.12 μm and a gel content of 95 wt% (based on a solids) Rubber latex B) 15 parts by weight, 120 parts by weight of deionized water, 0.6 parts by weight of alkenyl potassium succinate emulsifier, and maintained the temperature in the reactor at 50 ℃, 10 parts by weight of alpha-methylstyrene, 5 parts by weight of acrylonitrile , 0.087 parts by weight of sodium pyrophosphate, 0.11 parts by weight of dextrose, 0.002 parts by weight of ferrous sulfide, and 0.2 parts by weight of cumyl peroxide, and then the reaction temperature was raised to 70 ° C. for 60 minutes.

Polymerization step

Monomer emulsion and sodium pyrophosphate 0.019 consisting of 10 parts by weight of ion-exchanged water, 20 parts by weight of alpha-methylstyrene, 5 parts by weight of acrylonitrile, 0.6 parts by weight of alkenyl potassium succinate emulsifier, and 0.1 parts by weight of tertiary dodecylmercaptan. By weight, 0.025 part by weight of dextrose, 0.001 part by weight of ferrous sulfide and 0.1 part by weight of cumyl peroxide were continuously administered for 120 minutes.

Polymerization complete step

After the continuous administration, 0.019 parts by weight of sodium pyrophosphate, 0.025 parts by weight of dextrose, 0.001 parts by weight of ferrous sulfide and 0.05 parts by weight of cumyl peroxide were collectively administered, and the temperature was raised to 80 ° C and aged for 60 minutes. Next, it cooled to 60 degreeC and complete | finished reaction. And the rubber-reinforced graft copolymer latex obtained is shown in Table 1 below.

<Production of the thermoplastic resin composition>

2 parts by weight of sulfuric acid was added to the obtained rubber-reinforced graft copolymer latex to coagulate, washed with water, and then dried by hot air drying in a fluidized bed dryer to prepare a powder. The prepared powder was mixed with a heat-resistant styrene-acrylonitrile copolymer (polymerized copolymer including 70 wt% alpha-methylstyrene, 28 wt% acrylonitrile and 2 wt% styrene) prepared by solution polymerization and extruder After the preparation using the pellets, it was injected again to prepare a specimen for measuring the physical properties. At this time, the rubber content of the prepared specimen is 15% by weight, the physical properties thereof are shown in Table 2 below.

Example 2

A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 40 parts by weight of latex A and 20 parts by weight of latex B were used in Example 1.

Example 3

50 parts by weight of latex A, 20 parts by weight of latex B, 5 parts by weight of alpha-methylstyrene, 2 parts by weight of acrylonitrile and 16 parts by weight of alpha-methylstyrene in the polymerization step A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 7 parts by weight of acrylonitrile was used.

Example 4

Example 1 except that 6.5 parts by weight of alpha-methylstyrene and 3.5 parts by weight of acrylonitrile were used in the polymerization initiation step, and 19.5 parts by weight of alpha-methylstyrene and 10.5 parts by weight of acrylonitrile were used in the polymerization step. In the same manner as the rubber-reinforced graft copolymer latex and thermoplastic resin composition was prepared.

Comparative Example 1

A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 60 parts by weight of latex A was used without using latex B in the polymerization initiation step of Example 1.

Comparative Example 2

50 parts by weight of latex A, 5 parts by weight of latex B, 11.5 parts by weight of alpha-methylstyrene, 5.5 parts by weight of acrylonitrile and 20 parts by weight of alpha-methylstyrene in the polymerization step A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 8 parts by weight of acrylonitrile was used.

Comparative Example 3

A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 35 parts by weight of latex A and 25 parts by weight of latex B were used in the polymerization initiation step of Example 1.

Comparative Example 4

A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that latex B having a gel content of 95 wt% and an average particle diameter of 0.05 μm was used in the polymerization initiation step of Example 1. It was.

Comparative Example 5

A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that latex B having a gel content of 95 wt% and an average particle diameter of 0.20 μm was used in the polymerization initiation step of Example 1. It was.

Comparative Example 6

A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were manufactured in the same manner as in Example 1, except that latex A having a gel content of 85 wt% and an average particle diameter of 0.2 μm was used in the polymerization initiation step of Example 1. It was.

Comparative Example 7

A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that latex A having a gel content of 83 wt% and an average particle diameter of 0.5 μm was used in the polymerization initiation step of Example 1. It was.

Comparative Example 8

A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were manufactured in the same manner as in Example 1, except that latex B having a gel content of 70 wt% and an average particle size of 0.12 μm was used in the polymerization initiation step of Example 1. It was.

Comparative Example 9

A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were manufactured in the same manner as in Example 1, except that latex A having a gel content of 70 wt% and an average particle diameter of 0.32 μm was used in the polymerization initiation step of Example 1. It was.

Comparative Example 10

A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that latex B having a gel content of 97 wt% and an average particle size of 0.32 μm was used in the polymerization initiation step of Example 1. It was.

Comparative Example 11

In the polymerization initiation step of Example 1, 5 parts by weight of alpha-methylstyrene, 5 parts by weight of styrene, 5 parts by weight of acrylonitrile and 10 parts by weight of alpha-methylstyrene, 10 parts by weight of styrene and acrylonitrile in the polymerization step A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1 except that 5 parts by weight was used.

Comparative Example 12

Except that 20 parts by weight of alpha-methylstyrene, 4 parts by weight of acrylonitrile in the polymerization start step of Example 1 and 16 parts by weight of alpha-methylstyrene, 0 parts by weight of acrylonitrile in the polymerization step A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1.

 [Test Example]

The properties of the rubber-reinforced graft copolymer latex and the thermoplastic resin composition prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Tables 1 to 6 below.

* Average particle diameter: measured using an intensity Gaussian distribution (Nicomp 380) by dynamic laser light scattering method.

Gel content: The gel content was measured by centrifugation after stirring for 24 hours in acetone.

* Polymerization conversion rate: The total solid content (TSC) was calculated by weighing 2 g of each prepared latex in a 150 ° C. hot air dryer for 15 minutes and then calculating the polymerization conversion rate according to the following equation.

Polymerization Conversion Rate = TSC * (Weighed Monomer and Subsidiary Parts) / 100

               -(Parts by weight of additional raw materials added in vitro)

* Polymerized Coagulant: The rubber-reinforced graft copolymer stability was recorded as% of the total solid weight obtained by theoretically obtaining the coagulum from the latex obtained after polymerization in a 100 mesh network.

Proportion of product aggregate = weight of aggregate produced in the reactor / weight of total monomers administered * 100

* Izod impact strength: Measured according to ASTM D256 method with 1/4 "thickness of specimen, the unit is Kg.cm/cm.

* Heat resistance (HDT): The heat distortion temperature was measured by the ASTM D648 method.

* Surface gloss: measured according to the ASTM D528 method at a 45 ° angle.

Table 1

		Example 1	Example 2	Example 3	Example 4
Composition of Rubber Reinforced Graft Copolymer	Rubber Latex A	45	40	50	45
	Rubber Latex B	15	20	20	15
	AMS	30	30	21	26
	AN	10	10	9	14
	Sum	100	100	100	100
% Polymerization conversion		97.2	97.5	97.2	98.2
Polymerized coagulum (%)		0.05	0.02	0.01	0.04

TABLE 2

			Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4	Comparative Example 5	Comparative Example 6
Composition of Rubber Reinforced Graft Copolymer	Rubber Latex A	Rubber Latex	60	50	35	45	45	45
		Gel content	85	85	85	85	85	85
		Particle diameter	0.32	0.32	0.32	0.32	0.32	0.2
	Rubber Latex B	Rubber Latex	0	5	25	15	15	15
		Gel content	95	95	95	95	95	95
		Particle size (㎛)	0.12	0.12	0.12	0.05	0.2	0.12
	Monomer	AMS	30	31.5	30	30	30	30
		SM
		AN	10	13.5	10	10	10	10
	Sum		100	100	100	100	100	100
% Polymerization conversion			96.3	94.4	94.1	97.3	95.3	97.7
Polymerized coagulum (%)			1.50	1.91	0.02	0.73	0.55	0.88

TABLE 3

			Comparative Example 7	Comparative Example 8	Comparative Example 9	Comparative Example 10	Comparative Example 11	Comparative Example 12
Composition of Rubber Reinforced Graft Copolymer	Rubber Latex A	Rubber Latex	45	45	45	45	45	45
		Gel content	85	85	70	90	85	85
		Particle diameter	0.5	0.32	0.32	0.32	0.32	0.32
	Rubber Latex B	Rubber Latex	15	15	15	15	15	15
		Gel content	95	70	95	95	95	95
		Particle size (㎛)	0.12	0.12	0.12	0.12	0.12	0.12
	Monomer	AMS	30	30	30	30	10	30
		SM					20
		AN	10	10	10	10	10	4
	Sum		100	100	100	100	100	100
% Polymerization conversion			92.1	97.1	96.9	97.1	98.1	88.1
Polymerized coagulum (%)			0.01	0.01	0.03	0.09	0.01	1.29

As shown in Tables 1 to 3, the rubber-reinforced graft copolymers (Examples 1 to 4) of the present substrate were compared with the rubber-reinforced graft copolymers (Comparative Examples 1 to 12) not containing rubber latex B. It was confirmed that the polymerization conversion rate was high and the polymerization coagulation product was largely small.

Table 4

	Example 1	Example 2	Example 3	Example 4
Impact Strength 1/4 (Kg.cm/cm)	18.8	18.1	18.5	19.0
HDT (℃)	107.5	107.7	104.1	106.9
Polish	100.9	100.9	101.3	101.2

Table 5

	Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4	Comparative Example 5	Comparative Example 6
Impact Strength 1/4 (Kg.cm/cm)	19.8	19.3	12.3	13.4	15.2	11.1
HDT (℃)	104.5	103.8	105.7	106.1	106.0	103.5
Polish	98.6	98.8	102.1	102.7	100.0	100.8

Table 6

	Comparative Example 7	Comparative Example 8	Comparative Example 9	Comparative Example 10	Comparative Example 11	Comparative Example 12
Impact Strength 1/4 (Kg.cm/cm)	22.9	18.9	20.3	14.1	18.9	16.3
HDT (℃)	103.5	103.2	105.8	107.8	100.1	101.1
Polish	98.6	97.1	95.2	100.1	100.7	88.9

As shown in Tables 4 to 6, the thermoplastic resin compositions (Examples 1 to 4) of the present substrate were compared with the thermoplastic resin compositions (Comparative Examples 1 to 12) not containing the rubber-reinforced graft copolymer of the present substrate. It was confirmed that the impact strength, heat resistance and appearance characteristics were all excellent, and in particular, the physical property balance was excellent.

Claims (19)

1. i) 40-50% by weight rubber latex with an average particle diameter of 0.25-0.45 μm and a gel content of 80-95% by weight; ii) 10 to 20% by weight rubber latex having an average particle diameter of 0.09 to 0.13 mu m and a gel content of 85 to 99% by weight; iii) 20 to 35 weight percent of alpha-methylstyrene; And iv) 5 to 20% by weight of vinyl cyan monomer; emulsion polymerization using polymerization water, emulsifier, molecular weight regulator, initiator and activator,

   The rubber latex of i) and ii) is charged before the start of polymerization, and the vinyl cyan monomer of iv) is not added before the start of polymerization or a part of the rubber cyan is added after the start of polymerization.

   Method for preparing rubber-reinforced graft copolymers.
2. The method of claim 1,

   Rubber latex of i) is characterized in that the average particle diameter of 0.25 to 0.35 ㎛

   Method for preparing rubber-reinforced graft copolymers.
3. The method of claim 1,

   The rubber latex of i) and ii) is a conjugated diene rubber latex, characterized in that

   Method for preparing rubber-reinforced graft copolymers.
4. The method of claim 3, wherein

   The conjugated diene rubber latex is a rubber latex prepared from one or more conjugated diene monomers selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and pyerylene (piperylene).

   Method for preparing rubber-reinforced graft copolymers.
5. The method of claim 1,

   The alpha-methylstyrene of iii) is not added before the start of polymerization or a part is added, and then the remaining amount is added after the start of polymerization.

   Method for preparing rubber-reinforced graft copolymers.
6. The method of claim 1,

   In the alpha-methylstyrene of iii), 10 to 50% of the alpha-methylstyrene used for the polymerization is added before the start of polymerization, and the remaining amount is added after the start of the polymerization.

   Method for preparing rubber-reinforced graft copolymers.
7. The method of claim 1,

   The vinyl cyan monomer of iv) is characterized in that 10 to 15% by weight

   Method for preparing rubber-reinforced graft copolymers.
8. The method of claim 1,

   In the vinyl cyan monomer of iv), 0 to 50% of the vinyl cyan monomer used in the polymerization is added before the start of polymerization, and the remaining amount is added after the start of the polymerization.

   Method for preparing rubber-reinforced graft copolymers.
9. The method of claim 1,

   The vinyl cyan monomer of iv) is acrylonitrile, methacrylonitrile or a mixture thereof

   Method for preparing rubber-reinforced graft copolymers.
10. The method of claim 1,

    The polymerization water, the emulsifier, the initiator and the activator is characterized in that the divided input before and after the polymerization start

    Method for preparing rubber-reinforced graft copolymers.
11. The method of claim 1,

    The molecular weight modifier is characterized in that it is added after the start of the polymerization

    Method for preparing rubber-reinforced graft copolymers.
12. The method of claim 1,

    The initiator and the activator is characterized in that the addition is further added after the addition of all monomers

    Method for preparing rubber-reinforced graft copolymers.
13. The method of claim 1,

    The emulsion polymerization is characterized in that the polymerization conversion is more than 97%

    Method for preparing rubber-reinforced graft copolymers.
14. The method of claim 1,

    The emulsion polymerization is characterized in that the amount of coagulated product is less than 0.1% by weight relative to the total solid content

    Method for preparing rubber-reinforced graft copolymers.
15. The method of claim 1,

    The method of preparing the rubber-reinforced graft copolymer comprises at least one flocculant selected from the group consisting of sulfuric acid, MgSO ₄ , CaCl ₂ and Al ₂ (SO ₄ ) ₃ in the rubber-reinforced graft copolymer latex prepared by the emulsion polymerization. After input and flocculation, further comprising the step of washing and drying the aggregates

    Method for preparing rubber-reinforced graft copolymers.
16. Claim 1 to 15 characterized in that it is prepared according to the method for producing a rubber-reinforced graft copolymer of any one of claims

    Rubber-reinforced graft copolymers.
17. i) 40-50% by weight rubber latex with an average particle diameter of 0.25-0.45 μm and a gel content of 80-95% by weight, ii) a rubber latex with an average particle diameter of 0.09-0.13 μm and a gel content of 85-99% by weight 10 to 20% by weight, iii) 20 to 35% by weight of alpha-methylstyrene, and iv) 5 to 20% by weight of vinyl cyan monomer, using polymerization water, emulsifier, molecular weight regulator, initiator and activator ; And

    b) blending the rubber-reinforced graft copolymer and the heat-resistant styrene-acrylonitrile-based copolymer prepared by the emulsion polymerization;

    In the step a), the rubber latex of i) and ii) is charged before the start of polymerization, and the vinyl cyan monomer of iv) is not added before the start of polymerization or a part of the rubber cyan is added after the start of polymerization. By

    Method for producing a thermoplastic resin composition.
18. It is manufactured according to the manufacturing method of claim 17

    Thermoplastic resin composition.
19. The method of claim 18,

    The thermoplastic resin composition is characterized in that the total rubber content of 10 to 30% by weight

    Thermoplastic resin composition.