KR20050020200A - Graft Copolymer Composition and Method for Preparing Powder Thereof and Thermoplastic Resin Composition Using Thereof - Google Patents

Abstract

PURPOSE: Provided is a copolymer composition which uses a first graft copolymer including crosslinking alkyl acrylate rubber polymer as a seed component of a second graft copolymer so that it makes ease of coloring with improving shock resistance and intensity. CONSTITUTION: The graft copolymer composition comprises the components of: (based on 100wt% of a second graft copolymer), 0.1-10wt% of a first graft copolymer as the seed which is composed of 20-60wt% of crosslinking alkyl acrylate rubber polymer as core and 20-60wt% of aromatic vinyl compound and 10-30wt% of vinyl cyan compound as graft shell without crosslinking; and a second graft copolymer which is composed of 30-70wt% of crosslinking alkyl acrylate rubber polymer as core and 15-50wt% of aromatic vinyl compound and 5-25wt% of vinyl cyan compound as graft shell without crosslinking.

Description

Graft Copolymer Composition and Method for Preparing Powder Thereof and Thermoplastic Resin Composition Using Thereof

The present invention relates to a graft copolymer composition, a powder preparation method thereof, and a thermoplastic resin composition using the same. More specifically, using a first graft copolymer comprising a crosslinked alkyl acrylate rubber polymer as a seed component of the second graft copolymer comprising a crosslinked alkyl acrylate rubber polymer prepared by spray drying after polymerization The present invention relates to a graft copolymer composition having excellent rigidity, heat resistance, weather resistance, and particularly impact resistance by mixing a graft copolymer powder and a hard matrix resin, a powder manufacturing method thereof, and a thermoplastic resin composition using the same.

High impact thermoplastic resins are obtained by incorporating rubber in the form of particles into a styrene-acrylonitrile copolymer. This is usually done by graft copolymerization of styrene and acrylonitrile in the presence of rubber and then mixing the graft product with a hard matrix resin, which is a separately prepared hard component comprising a styrene-acrylonitrile copolymer. . The high impact thermoplastic resin has a variety of properties obtained according to the rubber used.

Conventionally, the rubber used in the acrylonitrile butadiene styrene (ABS) polymer is butadiene polymer. The product has good impact resistance, especially at very low temperatures, but has relatively low weathering and aging resistance. Therefore, in order to obtain a product having not only high impact strength but also excellent weatherability and aging resistance, there should be no ethylenically unsaturated polymer in the graft copolymerization. ASA polymers using typically crosslinked alkyl acrylate rubber polymers have proven to be suitable. The ASA polymer is mainly used in outdoor applications that require bright, glossy colored products such as garden furniture, boats, signs, street lamp covers, and the like.

In addition, German Patent Publication No. 1 260 135 discloses a method for producing weathering resistance and aging resistant ASA polymer, wherein the core used is 150 to 800 nm in average particle diameter, crosslinked narrow particle size distribution It is a large diameter latex of acrylate. The polymer comprising the large diameter polyacrylate latex has improved notch impact strength, greater hardness, and reduced shrinkage as compared to polymers prepared using small diameter polyacrylate latex. However, the large-diameter graft copolymer has a problem that coloring is difficult compared to the small-diameter graft copolymer. The use of corresponding ASA polymers to produce colored moldings to overcome the above problems is limited, i.e. a faint pastel color rather than a light color is obtained.

In addition, US Pat. No. 4,224,419 discloses a crosslinked acrylate polymer having an average particle diameter of about 50 to 150 nm as a core and a styrene and acrylonitrile as a graft shell in a weather resistant high impact thermoplastic resin that can be easily colored. First graft copolymer prepared from; A crosslinked acrylate polymer having an average particle diameter of about 200 to 500 nm as a core and a second graft copolymer separately prepared from styrene and acrylonitrile as a graft shell; And a hard component including a copolymer of acrylonitrile and styrene or α-methylstyrene, wherein the weight ratio between the core components in the molding material is 90:10 to 35:65, A molding material having a proportion of sum of about 10 to 35% by weight based on the mixture is disclosed.

In addition, European Patent Publication No. 0 534 212 and U.S. Patent No. 5,932,655 prepare large and small diameter graft copolymers, respectively, and as a seed component, the glass transition temperature is higher than room temperature. The method of manufacturing and improving coloring property and impact resistance is shown. In European Patent Publication No. 0 534 212, hard seeds were used only for small-diameter graft copolymers, and in US Pat. No. 5,932,655, both hard- and large-diameter graft copolymers were hard polystyrene seeds. Was used.

The conventionally known materials are easy to color and have a notch impact strength higher than the notch impact strength of the individual components. However, the heat deflection temperature and tensile strength achieved using the material are inadequate for certain applications requiring high heat resistance and stiffness, and in particular, the effect of improving impact resistance is inferior.

In addition, the above known materials are usually produced by emulsion polymerization, and it is necessary to recover the dry powder from the latex finally obtained by the emulsion polymerization. As mentioned above, the method of recovering a polymer from a latex as a dry powder includes a coagulation method for adding a coagulant to the latex and coagulating the polymer particles in the latex, and a spray drying method for spray drying the latex directly with hot air. In general, in order to agglomerate the polymer particles in water, the flocculation step, washing of the flocculant, dehydration and drying steps, etc. are required before the polymer is recovered as a dry powder, and there are problems in terms of equipment cost and operation management.

Compared with the flocculation method, the spray drying method is more preferable in terms of equipment cost and operation management because the dry powder of the polymer can be obtained at once from the latex after emulsion polymerization, and the manufacturing process can be simplified.

In order to solve the above problems, the present invention, in preparing the first graft copolymer and the second graft copolymer, as a seed component of the second graft copolymer comprising a crosslinked alkyl acrylate rubber polymer It is an object to provide a graft copolymer composition excellent in easy coloration, weather resistance, heat resistance, rigidity and impact resistance by using a first graft copolymer comprising a crosslinked alkyl acrylate rubber polymer.

In addition, by spray-drying the first graft copolymer and the second graft copolymer, respectively, to prepare a graft copolymer powder, compared to the conventional flocculation method, the flocculation process and washing, dehydration and drying process of the flocculant, etc. In addition, since the dry powder of a polymer can be obtained at once from the latex after emulsion polymerization, and the manufacturing process can be simplified, the graft copolymer powder manufacturing method which can further improve equipment cost, production speed, etc. is provided. For the purpose of

In addition, an object of the present invention is to provide a weather resistant, high-impact thermoplastic resin composition having excellent heat resistance and rigidity by mixing the graft copolymer powder and a hard matrix resin.

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

The present invention to achieve the above object,

In the graft copolymer composition, a powder preparation method thereof, and a thermoplastic resin composition using the same, the alkyl acrylate rubber polymer crosslinked as a core may be 20 to 60 parts by weight based on 100 parts by weight of the first graft copolymer; And the non-crosslinked graft shell has 20 to 60 parts by weight of the aromatic vinyl compound based on 100 parts by weight of the first graft copolymer and 10 to 30 parts by weight of the vinyl cyan compound based on 100 parts by weight of the first graft copolymer. The first graft copolymer is sequentially polymerized; And as a seed, the first graft copolymer is 0.1 to 10 parts by weight based on 100 parts by weight of the second graft copolymer; The alkyl acrylate rubber polymer crosslinked as a core may comprise 30 to 70 parts by weight based on 100 parts by weight of the second graft copolymer; And 15 to 50 parts by weight of the vinyl graft copolymer based on 100 parts by weight of the second graft copolymer and 5 to 25 parts by weight of the vinyl cyan compound based on 100 parts by weight of the second graft copolymer. part; It provides a graft copolymer composition comprising a; a second graft copolymer is sequentially polymerized.

The alkyl acrylate monomer of the core in the first and second graft copolymers may be composed of 2 to 8 carbon atoms in the alkyl portion.

The alkyl acrylate may be butyl acrylate or ethyl hexyl acrylate.

The crosslinked alkyl acrylate rubber polymer of the core in the first and second graft copolymers may have a glass transition temperature of -70 to -20 ° C.

The average particle diameter of the core in the first graft copolymer may be 50 to 150 nm, and the average particle diameter of the core in the second graft copolymer may be 200 to 600 nm.

The aromatic vinyl compound of the graft shell which is not crosslinked in the first and second graft copolymers may be selected from the group consisting of styrene monomer derivatives of styrene, α-methylstyrene, para methylstyrene or vinyltoluene.

The vinyl cyan compound of the graft shell which is not crosslinked in the first and second graft copolymers may be acrylonitrile or methacrylonitrile.

The solid weight fraction of the first graft copolymer may be 25 to 70% by weight.

The solid weight fraction of the second graft copolymer may be 30 to 75% by weight.

In addition, the present invention comprises the steps of preparing the first and second graft copolymer by the composition; And spray-drying the first graft copolymer and the second graft copolymer, respectively.

In addition, the present invention is 10 to 40 parts by weight of the first graft copolymer powder prepared by the above method; 15 to 45 parts by weight of the second graft copolymer powder prepared by the above method; And 15 to 75 parts by weight of the hard matrix resin; provides a thermoplastic resin composition comprising a.

The hard matrix resin may be at least one selected from the group of hard polymer forming monomers having a glass transition temperature of 60 to 140 ° C.

The hard matrix resin may mix at least one monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, compounds containing units derived from methyl methacrylate, and compounds capable of forming polycarbonate polymers. .

Hereinafter, the present invention will be described in detail.

In preparing the first graft copolymer, the core acrylate rubber polymer is a core. The crosslinking agent may be used in an amount of 20 to 60 parts by weight based on 100 parts by weight of the total monomers used to prepare the first graft copolymer. 0.1 to 1 parts by weight and 0.05 to 0.5 parts by weight of the grafting agent are added to polymerize.

The crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3 butanediol dimethacrylate, 1,6 nucleic acid diol dimethacrylate, neopentyl glycol dimethacrylate Acrylate, trimethylol propane trimethacrylate, or trimethylol methane triacrylate, and the like may be used, and the grafting agent may use allyl methacrylate, triallyl isocyanurate, triallyl amine or diallyl amine, or the like. Can be.

The reaction of the alkyl acrylate rubber polymer may be performed by reacting the emulsion polymerization alone or by mixing the emulsion-free polymerization and the emulsion polymerization as appropriate, and the monomer injection method may be used alone or in combination. It is possible to.

The average particle diameter of the alkyl acrylate rubber polymer crosslinked after the polymerization is preferably 50 to 150 nm, more preferably 60 to 130 nm, and narrow particle size distribution.

In the preparation of the first graft copolymer, the graft shell preparation is a graft shell. An uncrosslinked aromatic vinyl compound-vinyl cyan compound copolymer is used for preparing the first graft copolymer in the presence of the alkyl acrylate rubber polymer. 20 to 60 parts by weight of aromatic vinyl compound and 10 to 30 parts by weight of vinyl cyan compound are added based on 100 parts by weight of the total monomers.

The reaction of the graft shell is preferably emulsion polymerization, and the mixed monomer containing the emulsifier is preferably added in a continuous input method during the graft reaction.

In order to control the molecular weight of the graft copolymer, a molecular weight modifier may be used, and tertiary dodecyl mercaptan may be preferably used.

Although the final first graft copolymer latex comprising the core and the graft shell does not require a specific solid weight fraction, having a polymer concentration of at least 25% by weight is an economic advantage in the spray drying process. Therefore, in the practice of the present invention, the solid weight fraction of the first graft copolymer latex is 25 to 70% by weight, preferably 40 to 60% by weight.

In the said 1st graft copolymer powder manufacture, as a method of obtaining a polymer powder from the said 1st graft copolymer latex, spray drying method is preferable from a viewpoint of installation cost and operation management. Spray drying can be carried out in a number of ways. The graft copolymer latex is atomized by a wheel or nozzle, and dry gas can be injected from the top or bottom of the atomization chamber. Dry gas is also preferably heated air or nitrogen to provide the appropriate powder temperature.

In preparing the second graft copolymer, the seed during preparation of the seed was not separately prepared, and based on 100 parts by weight of the total monomers used in the preparation of the second graft copolymer, the first graft copolymer prepared according to the present invention was prepared. 0.1 to 10 parts by weight is used as it is.

In preparing the second graft copolymer, the alkyl acrylate rubber polymer crosslinked as the core component during the core preparation is 100 parts by weight of the total monomers used for the preparation of the second graft copolymer in the presence of the first graft copolymer. 30 to 70 parts by weight of the alkyl acrylate monomer, 0.05 to 0.5 parts by weight of the crosslinking agent, and 0.03 to 0.3 parts by weight of the grafting agent are added based on the polymerization.

In the preparation of the first graft copolymer, the crosslinking agent and the graft agent may use the same material as used in the preparation of the alkyl acrylate rubber polymer.

The core reaction is preferably emulsion polymerization, and the mixed monomer containing the emulsifier is preferably added in a continuous input method during the graft reaction.

In the present invention, the particle size of the crosslinked alkyl acrylate rubber polymer is preferably 200 to 600 nm, more preferably 250 to 550 nm, and preferably a narrow particle size distribution.

In the preparation of the second graft copolymer, the graft shell preparation is a graft shell wherein an uncrosslinked aromatic vinyl compound-vinyl cyan compound copolymer is used to prepare the second graft copolymer in the presence of the alkyl acrylate rubber polymer. 15 to 50 parts by weight of aromatic vinyl compound and 5 to 25 parts by weight of vinyl cyan compound are added based on 100 parts by weight of the total monomers.

A molecular weight modifier may be used to control the molecular weight of the graft copolymer, and the molecular weight modifier may use the same material as used in the manufacture of the graft shell of the first graft copolymer, and may not be used at all. It may be.

The reaction of the graft shell is preferably emulsion polymerization, and the mixed monomer containing the emulsifier is preferably added in a continuous input method during the graft reaction.

Although the final second graft copolymer latex comprising the seed, core and graft shell does not require a specific solid weight fraction, having a polymer concentration of at least 30% by weight is an economic advantage in the spray drying process. . Therefore, in the practice of the present invention, the solid weight fraction of the second graft copolymer latex is 30 to 75% by weight, preferably 45 to 65% by weight.

In the preparation of the second graft copolymer powder, the method of obtaining the polymer powder from the second graft copolymer latex prepared by using the same method as the method of obtaining the polymer powder from the first graft copolymer latex Can be.

The core component is a suitable type of alkyl acrylate polymer having a glass transition temperature of less than 0 ° C each. The glass transition temperature of the crosslinked alkyl acrylate polymer is -70 to -20 ° C, preferably -60 to -30 ° C. The glass transition temperature of the alkyl acrylate polymer can be measured, for example, by DSC method.

The alkyl acrylate monomers are particularly suitable as butyl acrylate or ethyl hexyl acrylate as alkyl acrylates having 2 to 8 carbon atoms, preferably 4 to 8 carbon atoms in the alkyl moiety.

The aromatic vinyl compound is preferably a styrene monomer derivative, and examples thereof include styrene, α-methylstyrene, para methylstyrene, vinyl toluene, and the like.

As the vinyl cyan compound, acrylonitrile, methacrylonitrile or the like is preferably used.

As a method of obtaining a polymer powder from the said graft copolymer latex manufactured by this invention, the spray drying method is preferable from a viewpoint of installation cost or operation control.

In addition, the present invention is 10 to 40 parts by weight of the first graft copolymer powder prepared by the above method; 15 to 45 parts by weight of the second graft copolymer powder prepared by the above method; And 15 to 75 parts by weight of the hard matrix resin; provides a thermoplastic resin composition comprising a.

The hard matrix resin is composed of a hard polymer-forming monolayer having a glass transition temperature of 60 to 140 ° C., and includes a compound containing units derived from an aromatic vinyl compound, a vinyl cyan compound, methyl methacrylate, and a polycarbonate polymer. It is preferred to use a mixture of one or more monomers selected from the group consisting of compounds and the like.

The present invention is to prepare a graft copolymer by a method capable of improving the stiffness, heat resistance and impact resistance of the conventional weatherable ASA resin, the average particle diameter of the alkyl acrylate rubber polymer of the core component is 50 to 150 nm And 200 to 600nm are polymerized separately, wherein the seed component of the large-diameter graft copolymer is prepared as a small-diameter graft copolymer, and the graft copolymer powder is spray-dried on each graft copolymer latex. The thermoplastic resin produced by mixing the graft copolymer powder with the hard matrix resin significantly improves the rigidity, heat resistance and impact resistance while maintaining the conventional weather resistance, colorability and the like.

That is, the large-diameter graft copolymer is a cross-linked rubber component / non-crosslinked hard component / crosslinked rubber component / non-crosslinked hard component sequentially polymerized to form a multi-layer structure, in particular, the hard component in the crosslinked rubber component Since the non-crosslinked intermediate layer is formed, the impact phenomenon is remarkably improved when the external impact is more likely to occur within the rubber particles.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

Example 1

<First graft copolymer is being manufactured-Core manufacturing step>

10 parts by weight of butyl acrylate, 1.5 parts by weight of sodium dodecyl sulfate, 0.04 parts by weight of ethylene glycol dimethacrylate, 0.02 parts by weight of allyl methacrylate, 0.1 part by weight of sodium hydrogen carbonate, and 40 parts by weight of distilled water were collectively administered. After heating up to 70 degreeC, 0.05 weight part of potassium persulfates were put and the reaction was started.

After the reaction for 1 hour, 30 parts by weight of butyl acrylate, 0.5 parts by weight of sodium dodecyl sulfate, 0.1 parts by weight of ethylene glycol dimethacrylate, 0.05 parts by weight of allyl methacrylate, 0.1 parts by weight of sodium hydrogen carbonate, A mixture of 20 parts by weight of distilled water and 0.05 parts by weight of potassium persulfate was continuously added at 70 ° C. for 3 hours, and polymerization was further performed for 1 hour after the completion of the addition. The particle size of the rubber polymer obtained after completion of the reaction showed 100 nm.

<Manufacturing of the first graft copolymer-graft shell manufacturing step>

A mixture of 45 parts by weight of styrene, 15 parts by weight of acrylonitrile, 1.5 parts by weight of potassium rosinate, 0.1 part by weight of potassium persulfate, 0.1 part by weight of tertiary dodecyl mercaptan and 50 parts by weight of distilled water was added to the acrylate rubber polymer. The polymerization was carried out while continuously input at 70 ° C. for 3 hours. In addition, in order to increase the polymerization conversion rate, after the addition was completed, the temperature was raised to 75 ° C, and then further reacted for 1 hour, and cooled to 60 ° C. The particle size of the final graft copolymer obtained after completion of the reaction was 140nm, the total solid weight fraction in the latex was 48%.

<During the preparation of the second graft copolymer-seed preparation step>

The seed of the second graft copolymer was not separately prepared, and 3 parts by weight of the first graft copolymer latex prepared according to the present invention was added to the reactor along with 35 parts by weight of distilled water based on a solid weight fraction.

<Second graft copolymer is being manufactured-Core manufacturing step>

50 parts by weight of butyl acrylate, 0.4 parts by weight of sodium dodecyl sulfate, 0.1 parts by weight of ethylene glycol dimethacrylate, 0.05 parts by weight of allyl methacrylate, 0.1 parts by weight of sodium hydrogen carbonate, and distilled water to the first graft copolymer. A mixture of parts by weight and 0.05 parts by weight of potassium persulfate was continuously added at 70 ° C. for 5 hours, and polymerization was further performed for 1 hour after completion of the addition. The particle size of the rubber polymer obtained after completion of the reaction showed 400 nm.

<Manufacturing 2nd Graft Copolymer-Graft Shell Manufacturing Step>

A mixture of 34 parts by weight of styrene, 13 parts by weight of acrylonitrile, 1.5 parts by weight of potassium rosinate, 0.1 parts by weight of potassium persulfate, 0.05 parts by weight of tertiary dodecyl mercaptan and 35 parts by weight of distilled water in the alkyl acrylate rubber polymer The polymerization was carried out while continuously feeding at 70 ℃ for 4 hours. In addition, in order to increase the polymerization conversion rate, after the addition was completed, the temperature was raised to 75 ° C, and then further reacted for 1 hour, and cooled to 60 ° C. The particle size of the final graft copolymer obtained after completion of the reaction was 550nm, the total solid weight fraction in the latex was 53%.

<Graft copolymer powder manufacturing step>

The obtained first and second graft copolymer latexes were sprayed using a spray dryer equipped with a spray wheel, that is, the rotation speed of the spray wheel was 10,000 rpm, the latex feed rate was 40 g / min, and the dry air temperature. Was 180 ° C., and the powder temperature was 60 ° C., without mixing, and spray drying each.

The water content of the spray dried graft copolymer powder was less than 0.1%, and the powder density was at least 0.5 g / cm 3.

<Thermoplastics Manufacturing Step>

15 parts by weight of the obtained first graft copolymer powder, 30 parts by weight of the second graft copolymer powder and 55 parts by weight of styrene-acrylonitrile copolymer (LG Chemical, product name: 92HR) with a hard matrix resin 1 part by weight, 0.5 part by weight of antioxidant and 0.5 part by weight of UV stabilizer were added and mixed. The pellets were prepared in pellet form using a 40 pie extrusion kneader at a cylinder temperature of 220 ° C., and injected into the pellets to prepare physical specimens.

Example 2

Extrusion was performed in the same manner as in Example 1 except that 20 parts by weight of the first graft copolymer powder and 25 parts by weight of the second graft copolymer powder were used.

Example 3

2 parts by weight of the first graft copolymer latex, based on the solid weight fraction, as a seed of the second graft copolymer, 34.5 parts by weight of styrene and 13.5 parts by weight of acrylonitrile as the graft shell of the second graft copolymer The same procedure as in Example 1 was carried out except for use. The particle size of the core of the second graft copolymer obtained in Example 3 was 450 nm.

Example 4

In the core polymerization step of the first graft copolymer was carried out in the same manner as in Example 1, except that 5 parts by weight of butyl acrylate was used at the time of batch feeding, and 35 parts by weight of butyl acrylate was used during continuous feeding. The particle size of the core of the first graft copolymer obtained in Example 4 was 70 nm, and the particle size of the core of the second graft copolymer was 350 nm.

Comparative Example 1

A core latex of the first graft copolymer was used as the seed of the second graft copolymer in the same manner as in Example 1 except that 3 parts by weight based on the solid weight fraction was used. The particle size of the core of the second graft copolymer obtained in Comparative Example 1 was 350 nm.

Comparative Example 2

A seed was prepared in the same manner as in Example 1, except that the first graft copolymer was not used as a seed of the second graft copolymer, and a seed prepared separately as follows was used.

The separately prepared seed is a batch of 3 parts by weight of styrene, 0.1 parts by weight of sodium dodecyl sulfate, 0.04 parts by weight of ethylene glycol dimethacrylate, 0.02 parts by weight of allyl methacrylate, 0.1 parts by weight of sodium hydrogen carbonate and 35 parts by weight of distilled water. After the administration, the temperature was raised to 70 ° C, 0.05 parts by weight of potassium persulfate was added to initiate the reaction, and the polymerization was further performed for 1 hour.

The particle size of the seed obtained in Comparative Example 2 was 140nm, the particle size of the core was 400nm.

Comparative Example 3

Except that 0.2 parts by weight of ethylene glycol dimethacrylate was added to prepare a graft shell of the first graft copolymer, the crosslinked graft shell was prepared in the same manner as in Example 1. The particle size of the core of the second graft copolymer obtained in Comparative Example 3 was 380 nm.

[Comparative Example 4]

15 parts by weight of the first graft copolymer latex was used as a seed of the second graft copolymer based on the solid weight fraction, and 25 parts by weight of styrene and 10 parts by weight of acrylonitrile were used in the manufacture of the graft shell. It carried out by the same method as Example 1. The particle size of the core of the second graft copolymer obtained in Comparative Example 4 was 190 nm.

[Comparative Example 5]

45 parts by weight of the first graft copolymer powder was used in the extrusion, and the second graft copolymer powder was used in the same manner as in Example 1 except that the second graft copolymer powder was not used.

Comparative Example 6

Extrusion was carried out in the same manner as in Example 1 except that the first graft copolymer powder was not used and only 45 parts by weight of the second graft copolymer powder was used.

In the above examples and comparative examples, the average particle diameter of the latex was measured using an intensity gaussian distribution of Nicomp 370HPL by dynamic laser light scattering.

The physical property measurement results of Examples 1 to 4 and Comparative Examples 1 to 6 are summarized in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Impact strength 28 26 29 27 19 17 11 10 3 25 The tensile strength 550 580 540 570 460 490 510 520 530 390 Heat deflection temperature 95 97 94 96 88 89 91 91 92 81 Polish 95 98 93 99 89 89 85 80 90 75

Izod impact strength (1/4 ”notched at 23 ° C., kg · cm / cm) —measured according to ASTM D256.

Tensile strength (50 mm / min, kg / cm 2)-measured according to ASTM D638.

Heat deflection temperature (18.5 kg / cm &lt; 2 &gt; & 1/4 &quot;, &lt; 0 &gt; C)-measured according to ASTM D648.

Gloss (45 ° Angle) —Measured according to ASTM D528.

As can be seen in Table 1, Comparative Examples are inferior in overall impact strength as in Comparative Examples 1 to 5, and Comparative Example 6 is significantly inferior in tensile strength, heat deformation temperature and gloss, so that physical properties are not balanced. On the other hand, the embodiments according to the present invention were found to be superior to the physical properties such as impact strength, tensile strength, heat deformation temperature and gloss compared to the comparative examples.

As described above, the graft copolymer composition according to the present invention, the powder manufacturing method thereof, and the thermoplastic resin composition using the same improve physical properties such as tensile strength, heat deformation temperature and gloss, and have excellent weather resistance, such as heat resistance, rigidity, It is a useful invention with the effect of obtaining a high impact thermoplastic resin.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

Claims (13)

The alkyl acrylate rubber polymer crosslinked as core has 20 to 60 parts by weight based on 100 parts by weight of the first graft copolymer; And The non-crosslinked graft shell has 20 to 60 parts by weight of the aromatic vinyl compound based on 100 parts by weight of the first graft copolymer and 10 to 30 parts by weight of the vinyl cyan compound based on 100 parts by weight of the first graft copolymer. The first graft copolymer is sequentially polymerized; And The first graft copolymer as a seed is 0.1 to 10 parts by weight based on 100 parts by weight of the second graft copolymer; The alkyl acrylate rubber polymer crosslinked as a core may comprise 30 to 70 parts by weight based on 100 parts by weight of the second graft copolymer; And The non-crosslinked graft shell has 15 to 50 parts by weight of the aromatic vinyl compound based on 100 parts by weight of the second graft copolymer and 5 to 25 parts by weight of the vinyl cyan compound based on 100 parts by weight of the second graft copolymer. Graft copolymer composition comprising a; second graft copolymer is sequentially polymerized. The method of claim 1, Graft copolymer composition, characterized in that the alkyl acrylate monomer of the core of the first and second graft copolymer is composed of 2 to 8 carbon atoms in the alkyl portion. The method of claim 2, The alkyl acrylate is graft copolymer composition, characterized in that butyl acrylate or ethyl hexyl acrylate. The method of claim 1, The crosslinked alkyl acrylate rubber polymer of the core in the first and second graft copolymers has a glass transition temperature of -70 to -20 ° C. The method of claim 1, Graft copolymer composition, characterized in that the average particle diameter of the core in the first graft copolymer is 50 to 150nm, the average particle diameter of the core in the second graft copolymer is 200 to 600nm. The method of claim 1, The aromatic vinyl compound of the graft shell which is not crosslinked in the first and second graft copolymers is selected from the group consisting of styrene monomer derivatives of styrene, α-methylstyrene, para methylstyrene or vinyltoluene. Graft copolymer composition. The method of claim 1, The graft copolymer composition of the graft shell which is not crosslinked in the first and second graft copolymers is acrylonitrile or methacrylonitrile. The method of claim 1, Graft copolymer composition, characterized in that the solid weight fraction of the first graft copolymer is 25 to 70% by weight. The method of claim 1, Graft copolymer composition, characterized in that the solid weight fraction of the second graft copolymer is 30 to 75% by weight. Preparing the first and second graft copolymers of claim 1; And Spray drying the first graft copolymer and the second graft copolymer, respectively; Graft copolymer powder production method comprising a. 10 to 40 parts by weight of the first graft copolymer powder prepared according to claim 9; 15 to 45 parts by weight of the second graft copolymer powder prepared according to claim 9; And 15 to 75 parts by weight of the hard matrix resin; Thermoplastic resin composition, characterized in that comprises a. The method of claim 11, The hard matrix resin is a thermoplastic resin composition, characterized in that at least one selected from the group of hard polymer forming monomer having a glass transition temperature of 60 to 140 ℃. The method of claim 11, The hard matrix resin is characterized by mixing at least one monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, compounds containing units derived from methyl methacrylate, and compounds capable of forming polycarbonate polymers. Thermoplastic resin composition.