KR101178708B1 - A rubber reinforced thermoplastic resin composition having high impact strength and good colorability - Google Patents

Abstract

The present invention relates to a rubber-reinforced thermoplastic resin composition excellent in impact resistance and colorability, wherein the rubber-reinforced graft copolymer used in the production of rubber-reinforced thermoplastic resins is prepared by an emulsion polymerization method. By selectively introducing the seed particles composed of the copolymer on the surface of the diene-based polymer, it is characterized in that a rubber-reinforced thermoplastic resin that significantly improved the coloring, impact resistance, and transparency.

Emulsion polymerization, rubber latex, impact resistant thermoplastics, ABS, polybutadiene

Description

A rubber reinforced thermoplastic resin composition having high impact strength and good colorability}

In the present invention, in preparing the rubber polymer used as the material of the impact resistant resin by emulsion polymerization, by selectively applying a polymer using two or more monomers having different chemical compositions and structures into the rubber polymer, The present invention relates to a rubber-reinforced thermoplastic resin composition comprising a graft copolymer having improved colorability, weather resistance, transparency, and the like.

Generally, impact resistant resins such as ABS (acrylonitrile-butadiene-styrene), MBS (methyl methacrylate-butadiene-styrene), ASA (acrylonitrile-styrene-acrylate), etc., have impact resistance, mechanical strength, and moldability. It is a resin that has excellent gloss, etc., and it is generally applied to parts that need to secure a beautiful appearance and impact resistance from the outside, such as housings of electrical and electronic products, interior and exterior materials of automobiles, and building materials. .

The rubber graft copolymers used in such impact-resistant resins can be broadly classified into bulk polymerization methods and emulsion polymerization methods, depending on the polymerization method. In general, emulsion polymerization methods are advantageously used to satisfy the required physical properties of various applications. The emulsion polymerization method, unlike the bulk polymerization method of making rubber graft particles through phase transition, first polymerizes a rubbery polymer having a low glass transition temperature (Tg) and then has a relatively high glass transition temperature (Tg). It is a two-step polymerization method that uses two or more kinds of monomers, and various control of rubber particle size and type and variety of monomer selection in graft copolymerization are relatively superior to bulk polymerization method. It can be said to be a very advantageous way to secure the characteristics effectively.

In particular, appearance characteristics such as colorability and gloss, as mentioned above, are very important factors in the selection criteria of resins when used in housings of electrical and electronic products, and many researchers have effectively secured them. This is one of the important concerns.

To this end, many companies offer a number of methods to improve physical properties such as colorability and gloss. Typically, when the cell layer having a relatively high glass transition temperature (Tg) is formed on rubber particles, the coloration is optimized by optimizing the graft efficiency. Method of eliminating the variation of the overall color of the resin through the even distribution of the vulnerable rubber particles or to reduce the contrast ratio of the resin by inducing the size of the rubber particles small, or the selection of monomers favorable to the coloring in the production of rubber particles and copolymers using the same Method to improve the colorability of rubber particles, which are relatively vulnerable to colorability, and finally to prepare rubber particles / graft copolymers by emulsion polymerization method and appropriate selection of additives such as lubricants and heat stabilizers in the process of pressure / injection using the same. By reducing the factor of inhibition Capable of the method have been presented and the like.

However, these methods, in particular, the dispersion of rubber particles through the improvement of graft ratio, are focused on improving impact resistance and improving colorability, but they are difficult to differentiate in the method and do not differ significantly in colorability. . In addition, it can be said that it is somewhat effective in the coloring property in the production of rubber particles of small particle size and the production of rubber particles using monomers that are advantageous in colorability, but the increase of rubber content during polymerization is limited in the manufacture of graft copolymers using small particle size rubber particles. At the same time, there is a lot of difficulty in selecting the method because it can cause a serious loss in the impact resistance, which is the most basic physical property of the impact material.

In order to solve the problems of the prior art as described above, the inventors of the present invention to prepare a rubber-reinforced graft copolymer used in the production of rubber-reinforced thermoplastic resin through an emulsion polymerization method to two or more polymer copolymers different in chemical structure from each other By selectively introducing the composed seed particles on the diene-based polymer surface, it has been found to provide a rubber-reinforced thermoplastic resin that significantly improves colorability, impact resistance, and transparency, and has completed the present invention.

That is, an object of the present invention is to provide a rubber-reinforced thermoplastic resin composition that can satisfy the impact resistance and colorability, weather resistance, transparency, etc. when the product is later produced by providing a rubbery polymer and graft copolymer different from the prior art.

In order to achieve the above object, according to the present invention,

(A) 10 to 40% by weight of the graft copolymer; And (B) 60 to 90 weight percent of the thermoplastic copolymer; As a rubber-reinforced thermoplastic resin composition comprising a,

The (A) graft copolymer is

(i) 40 to 80 wt% of a diene rubbery polymer;

(ii) 5 to 50 weight percent of an aromatic vinyl monomer; And

(iii) 5 to 40 weight percent of a vinyl cyan monomer, a (meth) acrylic acid ester monomer or a mixture thereof;

The diene rubber polymer (i)

(a) 5 to 30 weight percent of the thermoplastic seed copolymer; And

(b) 70 to 95 wt% of a diene monomer; And,

The (a) thermoplastic seed copolymer

(a1) 20 to 80 wt% of an aromatic vinyl monomer;

(a2) 10 to 70% by weight of a vinyl cyan monomer, a (meth) acrylic acid ester monomer or a mixture thereof; And

(a3) 10 to 60 wt% of a diene monomer; It provides a rubber-reinforced thermoplastic resin composition comprising a.

The present invention also provides a rubber reinforced thermoplastic resin excellent in impact resistance and colorability prepared from the rubber reinforced thermoplastic resin composition.

Hereinafter, the present invention will be described in detail.

The present invention comprises 10 to 40% by weight of the graft copolymer (A), 60 to 90% by weight of the thermoplastic copolymer (B) relative to 100% by weight of the rubber-reinforced thermoplastic resin composition, wherein the graft copolymer The technical feature is to selectively introduce seed particles composed of two or more polymer copolymers having different chemical structures from each other on the diene polymer surface. More preferably, the graft copolymer (A) is 20 to 40% by weight and the thermoplastic copolymer (B) is 60 to 80% by weight relative to 100% by weight of the rubber-reinforced thermoplastic resin composition.

Specifically, in the case of the graft copolymer, the glass transition temperature (Tg) measured by the DSC method is -10 ° C. or lower, and the diene rubber polymer (A) (i), aromatic vinyl monomer (A) (ii), and It is preferably composed of vinyl cyan monomer (A) (iii), 40 to 80% by weight of the diene rubber polymer (A) (i) to 100% by weight of the total rubber-reinforced graft copolymer (A) is preferred. Preferably, the remaining content is applied to the aromatic vinyl monomer (A) (ii) and the vinyl cyan monomer (A) (iii), wherein the content of each monomer is 5 to 50% by weight of the aromatic vinyl monomer (A) (ii). And the vinyl cyan monomer (A) (iii) are preferably used within the range of 5 to 40% by weight. 40 to 80 wt% of the diene rubber polymer (A) (i) is applied to 100 wt% of the total rubber-reinforced graft copolymer (A), and 15 to 44 wt% of the aromatic vinyl monomer (A) (ii) as the remaining content. It is more preferable to use the vinyl cyan monomer (A) (iii) in an amount of 5 to 15% by weight.

In particular, in the case of diene rubber polymer (A) (i), it is preferable that the particle size after final superposition | polymerization is 1000-4000 GPa, and it is more preferable that it is 2500-3500 GPa. If the particle size is less than 1000 착색 may be advantageous in colorability but may cause a problem that the impact resistance is lowered in the production of rubber-reinforced resin using the same. Due to the increase in the distance between the particles due to the drop in the impact strength and the deviation is bad.

In addition, the diene rubber polymer (A) (i) may be composed of a thermoplastic seed copolymer (A) (i) (a) and a diene monomer (A) (i) (b) to 100% by weight of the total In the case of the seed copolymer (A) (i) (a) 5 to 30% by weight relative to the total diene rubber polymer (A) (i) It is possible to use, and in the case of diene monomer (A) (i) (b), it is preferable to apply 70 to 95% by weight based on the total diene rubber polymer (A) (i). In the case of the seed copolymer (A) (i) (a), it is more preferable to use 10 to 20% by weight based on the total diene rubber polymer (A) (i), and the diene monomer (A) (i) ( In the case of b), it is more preferable to apply 80 to 90% by weight based on the total diene rubber polymer (A) (i). In this case, when the thermoplastic seed copolymer (A) (i) (a) is less than 5% by weight, it is difficult to show a color improving effect, and when it exceeds 30% by weight, the impact resistance of the rubber-reinforced thermoplastic resin using the same may be reduced. There are disadvantages.

[Preparation of Thermoplastic Seed Copolymer (A) (i) (a)]:

In the case of the thermoplastic seed copolymer (A) (i) (a), C ₁ 20 to 80% by weight of the aromatic vinyl monomer (a1) to C ₁₀ and C ₁ To C ₁₀ Copolymerizable Vinyl Cyan Monomer Or 10 to 70% by weight of C ₁ to C ₁₀ alkyl ester compound (a2) and C ₁ It is preferable to prepare by applying 10 to 60% by weight of the diene monomer (a3) of C to C ₁₀ in consideration of the final structure of the produced component. Also C ₁ To C ₁₀ 20 to 80% by weight of the aromatic vinyl monomer (a1) and C ₁ To C ₁₀ Copolymerizable Vinyl Cyan Monomer Or C ₁ To C ₁₀ alkyl ester compound (a2) 20 to 70% by weight and C ₁ It is preferable to prepare by applying 10 to 50% by weight of the diene monomer (a3) to C ₁₀ in consideration of the final structure of the produced component.

That is, referring to the TEM picture of the diene-based rubber polymer using the seed of Figure 1, rather than the conventional core-shell structure showing the structure or juxtaposed structure of the ottogi-shaped structure by adjusting the position of the seed particles through the control of the polymerization and composition From this, it is advantageous from the color resistance and impact resistance during the production of impact resistant rubber reinforced resin using the same.

Wherein R ₁ , R ₂ are hydrogen or C ₁ To C ₈ alkyl.)

Monomers of this kind include styrene, α-methylstyrene or C ₁ To C ₈ alkyl-ring-alkylated styrenes (eg, p-methylstyrene or o-ethylstyrene, p-ethylstyrene and vinyl toluene) and the like, with styrene being most preferred.

In addition, the monomer usable as (a2) is preferably a monomer having hydrophilicity among the monomers copolymerizable with the above-mentioned (a1) aromatic vinyl monomer. Examples thereof include acrylonitrile, methacrylonitrile and ethacryl. Vinyl cyanide monomers such as ronitrile and acrylic acid monomers such as acrylic acid and methacrylic acid or methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate to methyl acrylate, ethyl acrylate, Preference is given to using compounds such as acrylic acid esters such as butyl acrylate.

At this time, if the content of the monomer (a2) is less than 20% by weight, the seed particles tend to be located inside the rubber particles rather than the Ottogi shape, and thus, it is difficult to expect a target improvement in colorability. It is not preferable because the likelihood of being present alone rather than being located is considerable, since the coloring, impact resistance, transparency, etc. are inhibited and insufficient.

Examples of the kind usable as the monomer (a3) include butadiene, isoprene, chloroprene, pyrrylene or co-monomers thereof which are diene compounds copolymerizable with at least one of the above-mentioned (a1) and (a2). .

When the content of (a3) is less than 10% by weight, generally, the affinity between the formed particles and the inside of the rubber particles is weakened, making it difficult to obtain a desired particle shape, and when the content is more than 60% by weight, colorability and transparency may be degraded.

In general, the emulsion polymerization method is used to prepare the diene rubber polymer (A) (i). Briefly, the total solid content is 100% by weight based on 100 parts by weight of the total of (a1), (a2), and (a3). 20 to 50% of water was added thereto, and then stabilized by adding 1 to 3 parts by weight of an emulsifier. Then, 0.1 to 2 parts by weight of an initiator was added and polymerization was carried out at 40 to 80 ° C. to reach a conversion rate of 90 to 99%. The polymerization is terminated. In this case, batchwise or continuous dosing may be applied to each monomer, and in the case of double batch, all of (a1), (a2), and (a3) which satisfy 100% by weight of the total initial reaction may be added. In addition, 40 to 70% of the monomers and the emulsifier of the same composition based on the total amount of the batch to proceed with the reaction and then the polymerization of the remaining monomers and emulsifiers of the same composition at the conversion rate of 50 to 80%.

In addition, in the addition and composition of the monomer, (a1), (a2), and (a3) monomers (a1) and (a2) were initially added to the initial stage of the reaction in addition to the above-described method, and then the reaction was carried out. The method may be applied, (a1) and (a3) are added first to proceed with the reaction, and then (a2) is added after the reaction, or (a2) and (a3) are added first and then reacted ( a1) may be applied.

In addition, in the continuous method, it is possible to continuously prepare all of (a1), (a2), and (a3) which satisfy a total of 100% by weight, and partially prepare a monomer of 20 to 50% by weight in a batch method. It is also possible to apply them and apply them continuously for the remainder.

The average particle diameter of the seed copolymer (A) (i) (a) prepared in this way corresponds to 500 to 2000 mm 3. At this time, the emulsifier used is not a big pharmaceutical requirement, it is preferable to use an anionic emulsifier such as potassium rosin, potassium fatty acid, and sodium lauryl sulfate, alkyl benzene sulfonate, etc. It is preferable to apply a polymer type reactive emulsifier mixed with an adsorption type anionic emulsifier or singly. The emulsifier is preferably used in an amount of 0.5 to 3 parts by weight based on 100 parts by weight of the thermoplastic seed copolymer (A) (i) (a), since it is an appropriate amount to ensure the stability of the latex.

Initiators usable in the preparation of seed copolymers (A) (i) (a) include the use of persulfate-based initiators with strong hydrophilic properties, such as pyrolysis initiators such as potassium persulfate, ammonium persulfate and sodium persulfate. Hydroperoxide initiators such as diisopropylbenzene hydroperoxide, cumene hydroperoxide, tertiary butyl hydroperoxide, etc., which have hydrophobic tendencies are possible, such as ferrous sulfate, dextrose, sodium pyrrole phosphate, sodium sulfite, etc. It is also possible to use them with redox catalysts.

The initiator may be used according to the method and composition of the monomer to be added, it is preferable to use each of the initiators, it is preferable that the hydrophilic and hydrophobic initiator is used alone throughout the reaction, and the two initiators in the monomer input step It is preferred that the mixed application be used.

[Preparation of diene rubber polymer (A) (i)]:

When preparing the diene rubber polymer (A) (i), 5 to 30% by weight of the above-mentioned thermoplastic seed copolymer (A) (i) (a), and diene monomer (A) (i) (b) 70 It can be produced from to 95% by weight, and is not particularly limited in the manufacturing method, but is preferably prepared by the method of the emulsion polymerization described above.

The glass transition temperature of the diene rubber polymer (A) (i) latex is -10 ° C or less, preferably 1000 to 4000 Pa, and more preferably 2500 to 3500 Pa.

(A) 1,3-butadiene, isoprene, chloroprene, pyrrylene and comonomers thereof may be used as the diene monomer in the kind usable as (i) (b), wherein C ₁ To C ₁₀ Further alkyl esters may be added, examples being methyl acrylate, n-butyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-hexyl acrylate and the like.

The emulsion polymerization method described above is applied to the polymerization reaction. That is, a diene rubber composed of 70 to 95 parts by weight of 1,3-butadiene (A) (i) (b) and 5 to 30 parts by weight of the thermoplastic seed copolymer (A) (i) (a) among the above-described diene monomers. 1 to 3 parts by weight of the emulsifier, 0.2 to 1.5 parts by weight of the polymerization initiator, 0.1 to 1 parts by weight of the molecular weight regulator, and 0.2 to 2 parts by weight of the electrolyte are carried out in a batch based on 100 parts by weight of the polymer (A) (i). .

In the reaction, the thermoplastic seed copolymer (A) (i) (a) and the diene monomer (A) (i) (b) may be added at the initial stage of the reaction or separately.

The initiator used in the reaction is preferably a hydroperoxide-based initiator, which is a hydrophobic initiator using an oxidation-reduction catalyst, in the early stage of the reaction as the oxidation-reduction catalyst. It is also possible for water-soluble persulfate-based initiators to peroxide initiators to be used selectively, such as redox catalysts.

In general, when the oxidation-reduction catalyst initiator is applied, the polymerization temperature is preferably polymerized at 0 to 60 ° C, preferably 30 to 50 ° C. The use of such an oxidation-reduction catalyst initiator has advantages in that low-temperature initiation polymerization is easy, unlike pyrolysis initiators, so that the heat of reaction and pressure control of the polymerization are relatively advantageous, and the particle size of the final product is easy and uniform particles are obtained.

As a molecular weight regulator, it can be used as a molecular weight regulator of mercaptans, such as n-dodecyl mercaptan, n-decyl mercaptan, t-dodecyl mercaptan, etc., and the usage amount is diene rubber polymer (A) (i) 100 It is preferable to apply 0.1-2.0 weight part with respect to a weight part, Preferably it is preferable to apply 0.1-5.0 weight part.

In the diene rubber polymer (A) (i) (a), the electrolyte which can be used is prepared by using KCl, NaCl, KHCO ₃ , Na ₂ CO ₃ , Na ₂ SO ₄ , NaHSO _4, etc. To 2.0 parts by weight can be used, and it is more preferable to use 0.5 to 1.5 parts by weight.

The TEM photographed result of the diene rubber polymer thus produced is shown as FIG. 1. As shown in Figure 1, it can be clearly seen that the other types of seeds contained therein.

[Production of Graft Copolymer (A)]:

In order to ensure kneading with the thermoplastic copolymer resin (B) with respect to the diene rubber polymer (A) (i), it is generally necessary to graft polymerize monomers that are compatible with the thermoplastic copolymer resin (B). Preparation of such graft polymers is as follows:

The graft copolymer (A) is composed of (A) (ii) 5 to 50% by weight of aromatic vinyl monomer, and (A) (iii) vinyl cyanide compound based on 40 to 80% by weight of diene rubber polymer (A) (i). Or (methyl) acrylic acid ester compound 5 to 40% by weight, and as an effective polymerization method, it is preferable to take an emulsion polymerization method.

The (A) (ii) aromatic vinyl monomers that can be used at this time can be a kind of α-methyl styrene or o-ethyl styrene, p-ethyl styrene and vinyl toluene, and (A) (iii) as a vinyl cyanide compound Monomers such as nitrile and methacrylonitrile are available, and methacrylic acid esters include methyl methacrylate, ethyl methacrylate, and acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate. Available.

In the preparation of the graft copolymer (A) through an emulsion polymerization method, a separate graft copolymer (A) (i) is intended to form a graft copolymer with respect to 40 to 80% by weight of latex rubbery polymer (A) (i) latex. 20 to 60% by weight of the monomer is administered together with an emulsifier, a molecular weight modifier and an initiator, and the reaction is continued until the reaction conversion rate is 98 to 99%, and then ends. The emulsifiers usable here include carboxyl-type adsorption-type emulsifiers such as potassium rosin and potassium fatty acids, sulfonate-based adsorption-type emulsifiers such as sodium lauryl sulfate, alkyl benzenesulfonate, reactive emulsifiers or polymer-type reactive emulsifiers. It can be used alone or in combination.

At this time, the reactive emulsifier having a low molecular weight unsaturated double bond may be an anionic emulsifier or a neutral emulsifier having an allyl group, a (meth) acryloyl group, or a propenyl group. Examples of the anionic / neutral emulsifiers having a double allyl group include polyoxyethylene and allylglycidyl nonylphenyl ether series (sulfate salts, etc.), and alkenyl succinate salts may be used as anionic emulsifiers having alkenyl groups. As an anionic emulsifier which has a propenyl group, the ammonium sulfate salt of polyoxyethylene allyl glycidyl nonyl propenyl phenyl ether is mentioned.

In addition, an emulsifier having a high molecular weight unsaturated double bond can be basically used to have 0.8 to 1 unsaturated double bond capable of copolymerization with a monomer in the polymer backbone, the composition usable in these polymers are acrylate to methyl methacryl It is possible to polymerize acrylate monomers such as acrylate, butyl acrylate, ethyl acrylate, or acrylic acid type monomers such as methacrylate, acrylic acid, etc., either alone or in different copolymerization compositions, depending on the intended use. It is possible to use in the form of a polymer or in the form of an alternating or necessary block copolymer. In addition, these monomers and monoalkenyl aromatic monomers such as styrene, alphamethylstyrene vinyltoluene, quaternary butyl styrene, 2-chlorostyrene, paramethyl styrene, and ethyl acetate unsaturated vinyl vinyl acetate, vinyl pyrrolidone, What was manufactured with copolymers, such as maleic anhydride, can be used. Representative examples thereof include copolymers of styrene-maleic anhydride.

It is common for the weight average molecular weight of the emulsifier which has such a high molecular weight unsaturated double bond to exist in the range of 2,000-10,000, and it is preferable to exist in the range of 3,000-5,000. In addition, the position of the unsaturated double bond is not particularly limited, but in order to effectively react with the monomer forming the copolymer, it is preferably located at the end of the main chain, and more preferably, less steric hindrance.

The emulsifier is preferably used in an amount of 0.5 to 3 parts by weight based on 100 parts by weight of the total graft copolymer (A), and in general, when the amount of the emulsifier used in graft copolymerization is less than 0.5 parts by weight, the stability of the latex is effectively There is a disadvantage that it is difficult to secure, if the content exceeds 3 parts by weight excess of the emulsifier remaining in the final thermoplastic resin composition may cause deterioration of the molding surface due to gas generation and moisture adsorption. Therefore, the content of the emulsifier is preferably used 0.8 to 1.5 parts by weight, it is possible to selectively use a reactive emulsifier to a polymer type reactive emulsifier is optionally mixed.

In preparing the graft copolymer (A), a molecular weight regulator of mercaptans such as n-dodecyl mercaptan, n-decyl mercaptan, t-dodecyl mercaptan, and the like may be used. 0.2 to 1.0 parts by weight of tertiary dodecyl mercaptan is preferably applied.

The initiator may be used in the range of 0.01 to 1.00 parts by weight, and the usable types include, but are not limited to, peroxide initiators such as tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide and oxidation- It is advantageous to use a reduction catalyst together in order to secure impact resistance and latex stability in graft copolymerization.

In addition, in the preparation of the graft copolymer (A), the monomer input is selected from the method of directly inputting the monomer into the reactor, the method of adding the monomer mixture, the method of adding the monomer emulsion prepared by mixing the emulsifier, water, and the initiator. When the monomer is added, optionally 0 to 20% by weight of the initial reaction of the monomer may be added in a batch input method, and the remaining monomers may be added in a continuous input method. In addition, it is also possible to insert the whole quantity continuously or batchwise feeding method at regular intervals three or four times.

After completion of the reaction, the graft copolymer (A) may be added to an antioxidant such as sulfuric acid, phosphoric acid or acetic acid, and then aggregated through a metal salt such as calcium chloride, magnesium sulfate or aluminum sulfate to separate solids. It can be washed, dehydrated and dried to form a powder.

[Production of Rubber Reinforced Thermoplastics]

The graft copolymer (A) in powder form described above may be used in admixture with a thermoplastic resin copolymer (B) generally made by solution polymerization.

Commonly used thermoplastic resin copolymer (B) is acrylonitrile-styrene copolymer (SAN), acrylonitrile-styrene-methyl methacrylate (MS resin), polycarbonate (PC), polybutylene tere The resin is not particularly limited as long as it is a resin such as phthalate (PBT) or polyvinyl chloride (PVC) that requires impact resistance.

In addition, these graft copolymers (A) may use lubricants, thermal stabilizers and other processing additives during melt molding through the extrusion and injection processes with the thermoplastic resin copolymer (B).

According to the present invention, the rubber-reinforced thermoplastic resin excellent in impact resistance and colorability can be obtained from the rubber-reinforced thermoplastic resin composition as described above in the following examples.

Rubber-reinforced thermoplastic resin composition according to the present invention has a feature that can improve the impact resistance and colorability, weather resistance, transparency and the like unlike the conventional manufacturing method.

Example 1:

This Example was prepared according to the composition shown in Table 1 below, specifically as follows:

(Preparation of Thermoplastic Seed Copolymer A-1):

60 parts by weight of ion-exchanged water was added to a nitrogen-substituted pressurized reactor, and then 1 part by weight of fatty acid potassium, 0.5 part by weight of potassium rosinate and 0.5 part by weight of potassium carbonate were stirred for 30 minutes, followed by 40 parts by weight of styrene and 5 parts by weight of acrylonitrile. 5 parts by weight of 1,3-butadiene, 0.2 parts by weight of tertiary dodecyl mercaptan and 0.1 parts by weight of potassium persulfate were added continuously, and the reaction temperature was raised to 65 ° C. and maintained for 30 minutes, followed by 70 ° C. The reaction was carried out for 4 hours under elevated temperature and isothermal conditions.

Then, 55 parts by weight of ion-exchanged water, 1 part by weight of fatty acid potassium, 0.5 part by weight of potassium rosinate and 0.5 part by weight of potassium carbonate were added thereto, followed by further reaction for 2 hours, 40 parts by weight of styrene, 5 parts by weight of acrylonitrile, 5 parts by weight of 1,3-butadiene and 15 parts by weight of ion-exchanged water were added, and the reaction was continued for 3 hours and then maintained at 82 ° C. for 3 hours.

The polymerization conversion rate of the seed copolymer obtained at this time was 99%, and the particle diameter was 1200 GPa.

( Diene  Preparation of Rubbery Polymer B-1):

50 parts by weight of ion-exchanged water was added to a nitrogen-substituted pressurized reactor, followed by stirring by adding 0.8 parts by weight of fatty acid potassium, 1.0 parts by weight of potassium rosinate, and 1.0 parts by weight of potassium carbonate at room temperature, followed by preparing a thermoplastic seed copolymer (A- 1) 10 parts by weight, 1,3-butadiene, 60 parts by weight, tertiary dodecyl mercaptan 0.3 part by weight, potassium persulfate 0.3 part by weight was added and the reaction temperature was raised to 72 ℃ for 6 hours and the reaction polymerization conversion rate was When it reached 60%, 15 parts by weight of 1,3-butadiene was further added, and the reaction temperature was raised to 80 ° C. for 7 hours.

Then, 15 parts by weight of 1,3-butadiene, 0.4 parts by weight of potassium persulfate and 4 parts by weight of ion exchange were added, followed by further reaction for 4 hours, and finally 0.1 parts by weight of potassium rosinate and tert-butyl hydroperoxide. 0.3 parts by weight of ferrous sulfide, 0.0003 parts by weight of dextrose, 0.05 parts by weight of dextrose, and 0.04 parts by weight of sodium pyrophosphate were further administered to sustain the reaction for 4 hours, and then the reaction was terminated.

The polymerization conversion rate of the diene rubber latex obtained at this time was 98%, and the particle diameter was 3200 GPa.

( Graft  Preparation of Copolymer C-1):

60 parts by weight of the diene rubber polymer (B-1), 80 parts by weight of ion-exchanged water, 0.5 parts by weight of fatty acid potassium, 7.5 parts by weight of styrene, and 2.5 parts by weight of acrylonitrile were added to a reactor substituted with nitrogen. It heated up to 50 degreeC after stirring.

Then, 0.05 part by weight of tertiary butyl hydroperoxide, 0.0003 part by weight of ferric sulfide, 0.002 part by weight of dextrose, 0.015 part by weight of sodium pyrophosphate, and 2.5 parts by weight of ion-exchanged water, and the reaction temperature was raised to 65 ° C. for 1 hour. The reaction proceeded while the temperature was raised.

Subsequently, an emulsion comprising 0.5 parts by weight of fatty acid potassium, 22.5 parts by weight of styrene, 7.5 parts by weight of acrylonitrile, 0.4 parts by weight of tertiary dodecyl mercaptan, 0.1 parts by weight of diisopropyl benzene peroxide, and 20 parts by weight of ion-exchanged water was continuously The reactor was administered for 1 hour.

Subsequently, 0.05 part by weight of cumene hydroperoxide, 0.0003 part by weight of ferrous sulfide, 0.002 part by weight of dextrose, 0.015 part by weight of sodium pyrophosphate, and 2.5 parts by weight of ion-exchanged water were added, and the polymerization temperature was raised to 80 ° C. for 1 hour. The reaction was continued for a while before the reaction was terminated. The final reaction conversion rate was 98%.

(Preparation of rubber-reinforced thermoplastic resin D-1):

75 parts by weight of styrene-acrylonitrile copolymer resin (92HR-LG Chemical) based on 25 parts by weight of rubber-reinforced graft copolymer (C-1) prepared through the coagulation drying process, and lubricant (N, N-ethylenebissteaar) Amide) 1.5 parts by weight and 0.2 parts by weight of a primary heat stabilizer (product name Wingstay-L) were added and extruded and injected under a general single extruder at 200 ° C. to prepare a sample for evaluation of physical properties. It is summarized together in Table 2.

Example 2

This Example was prepared according to the composition shown in Table 1 below, specifically as follows:

(Preparation of Seed Copolymer A-2):

Example 1 (Preparation of Seed Copolymer A-1) The same procedure was repeated except that 35 parts by weight of styrene and 10 parts by weight of methyl methacrylate were used instead of acrylonitrile.

The polymerization conversion rate of the seed copolymer obtained at this time was 99.5%, and the particle diameter was 1150 GPa.

( Diene  Preparation of Rubbery Polymer B-2):

Example 1 (Preparation of diene rubber polymer B-1) The same method was used except that 5 parts by weight of the seed copolymer (A-2) was used as the seed copolymer and 65 parts by weight of 1,3-butadiene was used. Repeated.

The polymerization conversion rate of the diene rubber latex thus obtained was 98.5%, and the particle size was 3100 mm 3.

( Graft  Preparation of Copolymer C-2):

55 parts by weight of the diene rubber polymer (B-2), 80 parts by weight of ion-exchanged water, 0.5 parts by weight of fatty acid potassium, 10 parts by weight of styrene, 5 parts by weight of acrylonitrile, tertiary dodecyl mer in a reactor substituted with nitrogen 0.3 parts by weight of captan, 0.05 parts by weight of cumene hydroperoxide, 0.001 parts by weight of ferrous sulfide, 0.012 parts by weight of dextrose, 0.045 parts by weight of sodium pyrrole phosphate, and 25 parts by weight of ion-exchanged water at a reaction temperature of 75 ° C. Was carried out.

Subsequently, the temperature was raised to 80 ° C. and then aged for 1 hour to terminate the reaction.

The final reaction conversion was 99.1%.

(Preparation of rubber-reinforced thermoplastic resin D-2):

The same method as in Example 1 except that the final rubber content was equally adjusted to 15% by applying acrylonitrile-styrene-methylmethacrylate copolymer resin (LG Chemistry, XT500) instead of the styrene-acrylonitrile copolymer. Was repeated to prepare a sample. The measurement results of the physical properties are summarized in Table 2.

Example 3

This Example was prepared according to the composition shown in Table 1 below, specifically as follows:

(Preparation of Seed Copolymer A-3):

Example 2 (Preparation of Seed Copolymer A-2) The same procedure was repeated except that 10 parts by weight of styrene and 35 parts by weight of methyl methacrylate were used.

The polymerization conversion rate of the seed copolymer obtained at this time was 99.2%, and the particle diameter was 1050 GPa.

( Diene  Preparation of Rubbery Polymer B-3):

Example 2 (Preparation of diene rubber polymer B-2) The same procedure except that 20 parts by weight of the seed copolymer (A-3) and 50 parts by weight of 1,3-butadiene were used as the seed copolymer. The method was repeated.

The polymerization conversion rate of the diene rubber latex obtained at this time was 99.7%, and the particle diameter was 3020 GPa.

( Graft  Preparation of Copolymer C-3):

Example 2 (Preparation of Graft Copolymer C-2) The same method was repeated except that the diene rubbery polymer (B-3) was used in the process.

At this time, the reaction conversion rate was 98.0%.

(Preparation of rubber reinforced thermoplastic resin D-3):

Example 2 (Preparation of rubber-reinforced thermoplastic resin D-2) By repeating the same process as in the process to prepare a sample of the same rubber content, the physical properties obtained therefrom are summarized together in Table 2 below.

Example 4

This Example was prepared according to the composition shown in Table 1 below, specifically as follows:

(Preparation of Seed Copolymer A-4):

Example 2 (Preparation of Seed Copolymer A-2) The same procedure was repeated except that 30 parts by weight of styrene and 15 parts by weight of n-butyl acrylate were used instead of acrylonitrile.

The polymerization conversion rate of the seed copolymer obtained at this time was 99.5%, and the particle diameter was 1250 GPa.

( Diene  Preparation of Rubbery Polymer B-4):

Example 2 (Preparation of diene rubber polymer B-2) The same method as the seed copolymer except that 30 parts by weight of the seed copolymer (A-4) and 40 parts by weight of 1,3-butadiene were used. Was repeated.

The polymerization conversion rate of the diene rubber latex thus obtained was 99.6%, and the particle size was 3320 mm 3.

( Graft  Preparation of Copolymer C-4):

Example 1 (Preparation of graft copolymer C-1) The same method was repeated except that the diene rubbery polymer (B-4) was used in the process.

At this time, the reaction conversion rate was 98.9%.

(Preparation of rubber reinforced thermoplastic resin D-4):

Example 1 (Preparation of rubber-reinforced thermoplastic resin D-1) By repeating the same process as in the process to prepare a sample having the same rubber content, the physical properties obtained therefrom are summarized together in Table 2 below.

Comparative Example 1

Comparative Examples were prepared according to the compositions shown in Table 1 below, specifically as follows:

(Preparation of Seed Copolymer A-5):

In the monomer composition, the same method as in Example 1 (preparation of seed copolymer A-1) was repeated except that 75 parts by weight of the initial reaction of styrene and 25 parts by weight of acrylonitrile were prepared by a batch method.

The polymerization conversion rate of the seed copolymer obtained at this time was 97.5%, and the particle diameter was 1200 GPa.

( Diene  Preparation of Rubbery Polymer B-5):

Example 1 (Preparation of diene rubber polymer B-1) The same method was repeated except that 9 parts by weight of the seed copolymer (A-5) was applied as the seed copolymer.

The polymerization conversion rate of the diene rubber latex thus obtained was 97.2%, and the particle size was 3220 mm 3.

( Graft  Preparation of Copolymer C-5):

Example 1 (Preparation of Graft Copolymer C-1) The same procedure was repeated except that the diene rubbery polymer (B-5) was used.

At this time, the reaction conversion rate was 97.5%.

(Preparation of rubber reinforced thermoplastic resin D-5):

Example 1 (Preparation of rubber-reinforced thermoplastic resin D-1) By repeating the same method as in the process to prepare a sample of the same rubber content level, the physical properties obtained therefrom are summarized together in Table 2 below.

Comparative Example 2

Comparative Examples were prepared according to the compositions shown in Table 1 below, specifically as follows:

( Diene  Preparation of Rubbery Polymer B-6):

50 parts by weight of ion-exchanged water was added to a nitrogen-substituted pressurized reactor, followed by stirring by adding 0.8 parts by weight of fatty acid potassium, 1.0 parts by weight of potassium rosinate, and 1.0 parts by weight of potassium carbonate at room temperature, followed by 6.75 parts of styrene and 2.25 parts of acrylonitrile. 61 parts by weight of 1 part and 1,3-butadiene, 0.3 parts by weight of tertiary dodecyl mercaptan, and 0.3 parts by weight of potassium persulfate were added. The reaction temperature was raised to 72 ° C. for 6 hours, and the reaction polymerization conversion reached 60%. 15 parts by weight of 1,3-butadiene was further added, and the reaction temperature was raised to 80 ° C. for 7 hours.

Then, 15 parts by weight of 1,3-butadiene, 0.4 parts by weight of potassium persulfate and 4 parts by weight of ion-exchanged water were added, followed by further reaction for 4 hours, and finally 0.1 parts by weight of potassium rosinate and tert-butyl hydroperoxide. 0.3 parts by weight of ferric sulfide, 0.0003 parts by weight of dextrose, 0.05 parts by weight of dextrose, and 0.04 parts by weight of sodium pyrrolephosphate were further administered to sustain the reaction for 4 hours, and then the reaction was terminated.

The polymerization conversion rate of the diene rubber latex obtained at this time was 98%, and the particle diameter was 3150 GPa.

( Graft  Preparation of Copolymer C-6):

Example 1 (Preparation of Graft Copolymer C-1) The same procedure was repeated except that the diene rubbery polymer (B-6) was used.

At this time, the reaction conversion rate was 97.5%.

(Preparation of rubber reinforced thermoplastic resin D-6):

Example 1 (Preparation of rubber-reinforced thermoplastic resin D-1) By repeating the same method as in the process to prepare a sample of the same rubber content level, the physical properties obtained therefrom are summarized together in Table 2 below.

Comparative Example 3

Comparative Examples were prepared according to the compositions shown in Table 1 below, specifically as follows:

( Diene  Preparation of Rubbery Polymer B-7):

In the preparation of Comparative Example 2 (diene-based rubber polymer B-6), the same method was repeated except that 2 parts by weight of styrene, 7 parts by weight of methyl methacrylate, and 61 parts by weight of 1,3-butadiene were collectively applied during the polymerization. .

The polymerization conversion rate of the diene rubber latex obtained at this time was 98.2%, and the particle diameter was 3020 GPa.

( Graft  Preparation of Copolymer C-7):

Example 1 (Preparation of Graft Copolymer C-1) The same procedure was repeated except that the diene rubbery polymer (B-7) was used.

At this time, the reaction conversion rate was 98.3%.

(Preparation of rubber reinforced thermoplastic resin D-7):

Example 2 (Preparation of rubber-reinforced thermoplastic resin D-2) By repeating the same method as the process to prepare a sample having the same rubber content, the physical properties obtained therefrom are summarized together in Table 2 below.

Property evaluation method:

The physical properties of the rubber-reinforced thermoplastic resin pellets prepared in Examples and Comparative Examples described above were evaluated as follows.

1) Izod impact strength-The thickness of the specimen was measured by STM 256 method with 1/4 '.

2) Flowability (MI)-measured by ASTM 256 method under the condition of 220 ° C., 10 kg.

3) Tensile strength-measured by ASTM D638 method.

4) Surface gloss-measured by ASTM D528 method at an angle of 45 ° C.

5) Colorability-0.2 parts by weight of a black color, easily identified using a color computer (Suga Color Computer), was added to 100 parts by weight of the resin, and color values were determined by comparing the respective L values. When the L value was low, it was judged that the colorability was good.

6) Residual thermal stability (injection retention gloss)-Insert the prepared pellet-type resin into the injection molding machine at 210 ℃ condition without injection time and measure the chromaticity using the color computer described above and then 270 ℃ condition for the same resin After leaving for 15 minutes, the chromaticity of the specimen obtained by injection was measured, and the difference was calculated by the following Equation 1. In general, the closer the value ΔE is to 0, the better the thermal stability.

7) Weather Resistance-Test the resin for 72 hours at 83 ℃, water spray cycle at 18 ° C / 120 minutes on weather-o-meter (ATLAS Ci35A), and then discoloration ( △ E ) Value was calculated by the above formula 1. The closer to 0, the better the weather resistance.

8) Transparency (Haze)-measured by ASTM 1003 method

Kinds Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Seed copolymer (A) A-1 A-2 A-3 A-4 A-5 A-6 A-7 ST (80)
AN (10)
BD (10) ST (70)
MMA (20)
BD (10) ST (20)
MMA (70)
BD (10) ST (60)
BA (30)
BD (10) ST (75)
AN (25)
- -
-
- -
-
- Diene copolymer (B) B-1 B-2 B-3 B-4 B-5 B-6 B-7 A-1 (10)
BD (90)
-
- A-2 (5)
BD (95)
-
- A-3 (20)
BD (80)
-
- A-4 (30)
BD (70)
-
- A-5 (10)
BD (90)
-
- -
BD (91)
ST (6.75)
AN (2.25) -
BD (91)
ST (2)
MMA (7) Graft Copolymer (C) B-1 (60)
ST (30)
-
AN (10) B-2 (55)
SM (10)
MMA (30)
AN (5) B-3 (55)
SM (10)
MMA (30)
AN (5) B-4 (60)
ST (30)
-
AN (10) B-5 (60)
ST (30)
-
AN (10) B-6 (60)
ST (30)
-
AN (10) B-7 (55)
ST (10)
MMA (30)
AN (5) Rubber reinforced thermoplastic P (ST-AN) P (ST-MMA) P (ST-MMA) P (ST-AN) P (ST-AN) P (ST-AN) P (ST-MMA) Rubber content in resin 15% 15% 15% 15% 15% 15% 15%

* Styrene (ST), acrylonitrile (AN), 1,3-butadiene (BD), n-butyl acrylate (BA), methyl methacrylate (MMA), polystyrene acrylonitrile copolymer (P (ST- AN)), polystyrene methylmethacrylate copolymer (P (ST-MMA)).

Item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Izod
Impact Strength (1/4 ') 30 18 16 28 26 27 15 liquidity 22 20 22 23 22 21 20 The tensile strength 490 550 570 500 520 515 590 Surface gloss 99 100 100 98 96 94 - Injection Molding Gloss ( △ E ) 2.5 3.5 3.0 2.1 4.5 4.0 5.0 Colorability (L) 8.5 7.0 6.5 8.7 136 11.5 10.2 Weatherability 3.1 4.0 4.2 2.1 6.5 7.0 6.8 transparency - 3.5 2.5 - - - 4.3

As shown in Table 2, in the case of Examples 1 to 4, it is possible to secure basic mechanical properties and processing characteristics such as impact resistance and flowability, as well as requirements for using products such as thermal stability, colorability, and weather resistance compared to Comparative Examples 1 to 3. It could be confirmed that it has an effect that is differentiated in terms of emotional quality.

In addition, in order to contrast the shape of the manufactured product TEM image (200nm) of the product obtained by dispersing the powder obtained by solidifying the latex prepared in Example 1 (500nm TEM picture: see Figure 1) through the compression / injection process (200nm) 2, a TEM photograph (1 μm) after the compression / injection process of Comparative Example 2 is illustrated as an existing product as FIG. 3. In FIG. 2, it is clearly confirmed that other kinds of seeds are included, whereas in FIG. 3, it is not possible to confirm that other types of seeds are added inside the spherical particles.

In conclusion, from such a difference in shape, while securing the basic mechanical properties and processing characteristics, such as impact resistance and flowability of the above-described Examples 1 to 4, products such as thermal stability, colorability, weatherability compared to Comparative Examples 1 to 3 It is believed to produce a differentiating effect in terms of emotional quality required for use.

Although the above has been described in detail with reference to the described embodiments of the present invention, it is apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention, and such variations and modifications belong to the appended claims. It is natural.

1 is a transmission electron microscope (TEM) photograph (500 nm) of a diene rubber polymer latex (Example 1) obtained by an embodiment of the present invention.

FIG. 2 is a TEM photograph (200 nm) of a rubber-reinforced thermoplastic resin product (Example 1) in which the powder obtained by solidifying the latex of FIG. 1 is dispersed through an extrusion and injection process.

3 is a TEM photograph (1 μm) of a rubber-reinforced thermoplastic resin product obtained by extruding and injecting an existing product (Comparative Example 2).

Claims (15)

(A) 10 to 40% by weight of the graft copolymer; And (B) 60 to 90 weight percent of the thermoplastic copolymer; As a rubber-reinforced thermoplastic resin composition comprising a, The (A) graft copolymer is (i) 40 to 80% by weight of diene rubber polymer; (ii) 5 to 50 weight percent of an aromatic vinyl monomer; And (iii) 5 to 40% by weight of a vinyl cyan monomer, a (meth) acrylic acid ester monomer or a mixture thereof; The diene rubber polymer (i) (a) 5 to 30% by weight thermoplastic seed copolymer having an average particle diameter of 500 to 2000 mm 3; And (b) 70 to 95 wt% of a diene monomer; And, The (a) thermoplastic seed copolymer (a1) 20 to 80 wt% of an aromatic vinyl monomer; (a2) 10 to 70% by weight of a vinyl cyan monomer, a (meth) acrylic acid ester monomer or a mixture thereof; And (a3) 10 to 60 wt% of a diene monomer; Rubber reinforced thermoplastic resin composition comprising a. The method of claim 1, The rubber reinforced thermoplastic resin composition (A) 20 to 40% by weight of the graft copolymer; And (B) 60 to 80 wt% of the thermoplastic copolymer; As a rubber-reinforced thermoplastic resin composition comprising a, The (A) graft copolymer is (i) 40 to 80% by weight of diene rubber polymer; (ii) 15 to 45 weight percent of an aromatic vinyl monomer; And (iii) 5 to 15% by weight of a vinyl cyan monomer, a (meth) acrylic acid ester monomer or a mixture thereof; The diene rubber polymer (i) (a) 10 to 20 weight percent of the thermoplastic seed copolymer; And (b) 80 to 90 wt% of a diene monomer; And, The (a) thermoplastic seed copolymer (a1) 20 to 70 wt% of an aromatic vinyl monomer; (a2) 20 to 70% by weight of a vinyl cyan monomer, a (meth) acrylic acid ester monomer or a mixture thereof; And (a3) 10 to 50 wt% of a diene monomer; Rubber reinforced thermoplastic resin composition comprising a. 3. The method according to claim 1 or 2, The (A) (ii) aromatic vinyl monomer and the (a1) aromatic vinyl monomer are each one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene and vinyl toluene. Rubber reinforced thermoplastic resin composition, characterized in that independently selected above. 3. The method according to claim 1 or 2, The vinyl cyan monomer in (A) (iii) and the vinyl cyan monomer in (a2) are each independently selected from one or more selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile. A rubber reinforced thermoplastic resin composition. 3. The method according to claim 1 or 2, The (meth) acrylic acid ester monomer in (A) (iii) and the (meth) acrylic acid ester monomer in (a2) are each methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, Rubber reinforced thermoplastic resin composition, characterized in that at least one selected from the group consisting of ethyl acrylate, butyl acrylate. 3. The method according to claim 1 or 2, The (A) (i) (b) diene monomer and the (a3) diene monomer are each independently selected from at least one member selected from the group consisting of butadiene, isoprene, chloroprene and pyrrylene. A rubber reinforced thermoplastic resin composition. delete 3. The method according to claim 1 or 2, The (A) (i) (a) thermoplastic seed copolymer, (A) (i) diene rubber polymer and (A) graft copolymer are isopropylbenzene hydroperoxide, cumene hydroperoxide, tertiary butyl At least one initiator selected from the group consisting of hydroperoxides is independently further included in an amount of 0.01 to 1.00 parts by weight based on 100 parts by weight of a thermoplastic seed copolymer, a diene rubber polymer or a graft copolymer under a redox catalyst. Rubber reinforced thermoplastic resin composition. 3. The method according to claim 1 or 2, The (A) (i) (a) thermoplastic seed copolymer, (A) (i) diene rubber polymer and (A) graft copolymer are each composed of potassium persulfate, ammonium persulfate and sodium persulfate. A rubber-reinforced thermoplastic resin composition comprising the selected persulfate-based initiator independently from 0.01 to 1.00 parts by weight based on 100 parts by weight of the thermoplastic seed copolymer, the diene rubber polymer or the graft copolymer. 3. The method according to claim 1 or 2, The (A) (i) (a) thermoplastic seed copolymer, (A) (i) diene rubber polymer and (A) graft copolymer are potassium rosin, fatty acid potassium, sodium lauryl sulfate, alkyl benzenesulfo One or more emulsifiers selected from the group consisting of nates, reactive emulsifiers, and polymer reactive emulsifiers are further independently included in an amount of 0.5 to 3.0 parts by weight based on 100 parts by weight of the thermoplastic seed copolymer, the diene rubber polymer, or the graft copolymer. Rubber reinforced thermoplastic resin composition, characterized in that. 3. The method according to claim 1 or 2, The (A) (i) diene rubber polymer and (A) graft copolymer are diene-based molecular weight modifiers selected from the group consisting of n-dodecyl mercaptan, n-decyl mercaptan and t-dodecyl mercaptan, respectively. Rubber-reinforced thermoplastic resin composition further comprises 0.1 to 2.0 parts by weight based on 100 parts by weight of the rubbery polymer or graft copolymer independently. 3. The method according to claim 1 or 2, The (A) (i) diene rubber polymer is 0.1 to 2.0 based on 100 parts by weight of an diene rubber polymer electrolyte selected from the group consisting of KCl, NaCl, KHCO ₃ , Na ₂ CO ₃ , Na ₂ SO ₄ , NaHSO ₄ A rubber reinforced thermoplastic resin composition comprising more by weight. 3. The method according to claim 1 or 2, The particle diameter of the (A) (i) diene rubber polymer is in the range of 1000 to 4000 mm 3 rubber reinforced thermoplastic resin composition. 3. The method according to claim 1 or 2, The thermoplastic polymer (B) is an acrylonitrile-styrene copolymer, acrylonitrile-styrene-methyl methacrylate, polycarbonate, polybutylene terephthalate or polyvinyl chloride, rubber-reinforced thermoplastic resin composition. The rubber reinforced thermoplastic resin excellent in impact resistance and coloring property manufactured from the rubber reinforced thermoplastic resin composition of Claim 1 or 2.

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