KR100626956B1 - Graft Copolymer Composition and Thermoplastic Resin Composition the Same - Google Patents

Abstract

The present invention relates to a graft copolymer composition, and a thermoplastic resin composition using the same, the copolymer composition of the present invention

A) based on 100 parts by weight of the first graft copolymer

a) 2 to 20 parts by weight of an alkyl acrylate-aromatic vinyl compound copolymer crosslinked as a seed;

b) 20 to 60 parts by weight of an alkyl acrylate rubber polymer crosslinked as core; And

c) a first graft copolymer containing 30 to 80 parts by weight of an aromatic vinyl compound-vinyl cyan compound copolymer not crosslinked as a graft shell; And

B) based on 100 parts by weight of the second graft copolymer

a) 0.1 to 10 parts by weight of the first graft copolymer as an internal seed;

b) 2 to 20 parts by weight of an alkyl acrylate-aromatic vinyl compound copolymer crosslinked as an external seed;

c) 30 to 70 parts by weight of an alkyl acrylate rubber polymer crosslinked as core; And

d) a second graft copolymer containing 15 to 50 parts by weight of an aromatic vinyl compound-vinyl cyan compound copolymer not crosslinked as a graft shell;

Characterized in that comprises a.

The thermoplastic resin composition using the graft copolymer composition according to the present invention has an effect excellent in rigidity, heat resistance, weather resistance, in particular scratch resistance and impact resistance.

Alkyl acrylate rubber, aromatic vinyl compound, vinyl cyan compound, rigidity, heat resistance, scratch resistance, impact resistance

Description

Graft copolymer composition and thermoplastic resin composition using same {Graft Copolymer Composition and Thermoplastic Resin Composition the Same}

The present invention relates to a graft copolymer composition and a thermoplastic resin composition using the same. More specifically, after polymerization using a first graft copolymer comprising an alkyl acrylate rubber polymer crosslinked with the inner seed component of the second graft copolymer comprising a crosslinked alkyl acrylate rubber polymer, respectively Graft copolymer composition and thermoplastic resin using the same graft copolymer, second graft copolymer and hard matrix resin to provide a thermoplastic resin having excellent rigidity, heat resistance and weather resistance, particularly scratch resistance and impact resistance It relates to a resin composition.

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. Acrylate-styrene-acrylonitrile (ASA) polymers, typically using crosslinked alkyl acrylate rubber polymers, have proven to be suitable. The ASA polymer is mainly used in outdoor applications requiring 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 is limited to produce colored moldings to overcome this problem, i.e. a faint pastel color rather than a light color is obtained.

In addition, U.S. Patent 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, do not exhibit a satisfactory level of scratch resistance and have a poor effect of improving impact resistance. .

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

In addition, an object of the present invention is to provide a high impact weather resistant thermoplastic resin composition having excellent heat resistance, rigidity, scratch resistance and the like by mixing the first graft copolymer, the second graft copolymer, and the 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,

A) based on 100 parts by weight of the first graft copolymer

a) 2 to 20 parts by weight of an alkyl acrylate-aromatic vinyl compound copolymer crosslinked as a seed;

b) 20 to 60 parts by weight of an alkyl acrylate rubber polymer crosslinked as core; And

c) a first graft copolymer containing 30 to 80 parts by weight of an aromatic vinyl compound-vinyl cyan compound copolymer which is not crosslinked as a graft shell; And

B) based on 100 parts by weight of the second graft copolymer

a) 0.1 to 10 parts by weight of the first graft copolymer as an internal seed;

b) 2 to 20 parts by weight of an alkyl acrylate-aromatic vinyl compound copolymer crosslinked as an external seed;

c) 30 to 70 parts by weight of an alkyl acrylate rubber polymer crosslinked as core; And

d) a second graft copolymer containing 15 to 50 parts by weight of an aromatic vinyl compound-vinyl cyan compound copolymer not crosslinked as a graft shell;

It provides a graft copolymer composition comprising a.

The alkyl acrylate monomers of the seed and core in the first graft copolymer and the external seed and core in the second graft copolymer may have an alkyl moiety of 2 to 8 carbon atoms.

The alkyl acrylates can be butyl acrylate or ethyl hexyl acrylates alone or mixtures thereof.

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 200 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 seed and graft shell in the first graft copolymer and the external seed and graft shell in the second graft copolymer is a styrene monomer derivative of styrene, α-methylstyrene, para methylstyrene and vinyltoluene. It may be selected from the group consisting of one or more.

The vinyl cyan compound of the graft shell of the first graft copolymer and the second graft copolymer may be acrylonitrile or methacrylonitrile alone or in a mixture thereof.

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 described above, a method of recovering the polymer from the latex as a dry powder includes a coagulation method in which a coagulant is added to the latex and the polymer particles in the latex are coagulated and then washed, dehydrated and dried.

In addition, the present invention

A) 5 to 50 parts by weight of the first graft copolymer powder according to the present invention;

B) 5 to 50 parts by weight of the second graft copolymer powder according to the present invention; And

C) 10 to 80 parts by weight of the hard matrix resin

It provides a thermoplastic resin composition comprising a.

The hard matrix resin has a glass transition temperature of 60 to 140 ℃ It may be selected from the group of phosphorus hard polymer forming monomers.

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 the preparation of the first graft copolymer, the seed preparation is based on 100 parts by weight of the crosslinked alkyl acrylate-aromatic vinyl compound copolymer, which is a seed, based on 100 parts by weight of the first graft copolymer and aromatics 0.5 to 15 parts by weight of the vinyl compound is polymerized by adding 0.02 to 0.2 parts by weight of the crosslinking agent and 0.01 to 0.1 parts by weight of the grafting agent.

The crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol Dimethacrylate, trimethylol propane trimethacrylate, trimethylol methane triacrylate, or mixtures thereof, and the like, and the grafting agent may be allyl methacrylate, triallyl isocyanurate, triallyl amine, Diallyl amine, or a mixture thereof may be used.

The reaction of the crosslinked alkyl acrylate-aromatic vinyl compound copolymer may be a method of reacting the emulsion polymerization alone or by mixing the emulsion-free polymerization and the emulsion polymerization as appropriate. The monomer addition method may also be used alone or continuously. It is possible to do this or both.

The average particle diameter of the alkyl acrylate-aromatic vinyl compound copolymer crosslinked after the polymerization is preferably 30 to 150 nm, more preferably 40 to 140 nm, and narrow particle size distribution.

In the preparation of the first graft copolymer, the core is prepared from 20 to 60 parts by weight of the crosslinking alkyl acrylate rubber polymer, which is the core, based on 100 parts by weight of the first graft copolymer in the presence of the seed. The polymerization is carried out by adding 0.04 to 0.4 parts by weight and 0.02 to 0.2 parts by weight of the grafting agent.

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 crosslinked alkyl acrylate-aromatic vinyl compound copolymer.

The reaction of the crosslinked alkyl acrylate rubber polymer may be a method of reacting the emulsion polymerization alone or by mixing the emulsion-free polymerization and the emulsion polymerization as appropriate, and the monomer input method may be a single batch or a continuous batch alone or two. It is possible to parallel.

The average particle size of the alkyl acrylate rubber polymer crosslinked after the polymerization is preferably 50 to 200 nm, more preferably 60 to 180 nm, and narrow particle size distribution.

In preparing the first graft copolymer, the graft shell is manufactured by using a non-crosslinked aromatic vinyl compound-vinyl cyan compound copolymer, which is a graft shell, based on 100 parts by weight of the first graft copolymer in the presence of the core. 20 to 60 parts by weight and 10 to 30 parts by weight of the vinyl cyan compound are added to polymerize.                     

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 first graft copolymer, a molecular weight modifier may be used, and tertiary dodecyl mercaptan may be preferably used.

The first graft copolymer latex obtained can be aggregated with sulfuric acid, MgSO ₄ , CaCl ₂ or Al ₂ (SO ₄ ) ₃ , which are well known flocculants, and preferably CaCl ₂ . Atmospheric coagulation using an aqueous calcium chloride solution, followed by washing, dehydration and drying yields first graft copolymer powder particles.

In preparing the second graft copolymer, the inner seed is not separately prepared, and 0.1 to 10 parts by weight (solid content) of the first graft copolymer latex prepared according to the present invention based on 100 parts by weight of the second graft copolymer. Standard) is used as it is.

When the first graft copolymer is used below the above range as the internal seed of the second graft copolymer, the scratch resistance improvement effect is remarkably inferior, and when used beyond the above range, the impact strength is greatly reduced.

In the preparation of the second graft copolymer, the preparation of the external seed is performed by using a crosslinked alkyl acrylate-aromatic vinyl compound copolymer which is an external seed based on 100 parts by weight of the alkyl acrylate monomer in the presence of the inner seed. 0.5 to 15 parts by weight and 0.5 to 15 parts by weight of the aromatic vinyl compound are polymerized by adding 0.02 to 0.2 parts by weight of the crosslinking agent and 0.01 to 0.1 parts by weight of the grafting agent.

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 crosslinked alkyl acrylate-aromatic vinyl compound copolymer.

The reaction for preparing the external seed may be a method of using either emulsion polymerization or non-emulsion polymerization alone or by appropriately mixing the two. It is possible to parallel.

The particle size of the alkyl acrylate-aromatic vinyl compound copolymer crosslinked after the polymerization is preferably 100 to 500 nm, more preferably 150 to 400 nm, and narrow particle size distribution.

In preparing the second graft copolymer, the core preparation includes 30 to 70 parts by weight of an alkyl acrylate monomer based on 100 parts by weight of the second graft copolymer in the presence of the outer seed, the crosslinked alkyl acrylate rubber polymer serving as the core. The polymerization is carried out by adding 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.

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 crosslinked alkyl acrylate-aromatic vinyl compound copolymer.

Emulsion polymerization is preferably used for the production of the core, and the mixed monomer containing the emulsifier is preferably added in a continuous input method during the reaction.                     

It is preferable that the particle size of the alkyl acrylate rubber polymer crosslinked after the polymerization is 200 to 600 nm, more preferably 250 to 550 nm, and the particle size distribution is preferably narrow.

In preparing the second graft copolymer, the graft shell preparation is based on 100 parts by weight of the non-crosslinked aromatic vinyl compound-vinyl cyan compound copolymer which is a graft shell in the presence of the alkyl acrylate rubber polymer. 10 to 45 parts by weight of the aromatic vinyl compound and 5 to 25 parts by weight of the vinyl cyan compound are added to polymerize.

A molecular weight regulator may be used to control the molecular weight of the second graft copolymer, and the molecular weight regulator may use the same material as used in the manufacture of the graft shell of the first graft copolymer.

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 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 of the first graft copolymer and the second graft copolymer is an appropriate type of alkyl acrylate rubber polymer having a glass transition temperature of less than 0 ° C., respectively. The glass transition temperature of the crosslinked alkyl acrylate rubber polymer is from -70 to -20 deg. C, preferably from -65 to -25 deg. The glass transition temperature of the alkyl acrylate rubber polymer can be measured, for example, by DSC method.

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

It is preferable to use a styrene monomer derivative as the aromatic vinyl compound, and for example, styrene, α-methyl styrene, para methyl styrene or vinyl toluene may be used alone or in combination.

It is preferable that the said vinyl cyan compound uses acrylonitrile, methacrylonitrile, etc. individually or in mixture.

In addition, the present invention

A) 5 to 50 parts by weight of the first graft copolymer powder according to the present invention;

B) 5 to 50 parts by weight of the second graft copolymer powder prepared by the above method; And

C) provides a thermoplastic resin composition comprising 10 to 80 parts by weight of the hard matrix resin.

The hard matrix resin is composed of a hard polymer forming monomer having a glass transition temperature of 60 to 140 ° C., and a compound containing a unit 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 a method for improving the stiffness, heat resistance, scratch resistance and impact resistance of the conventional weather-resistant ASA resin, the average particle diameter of the alkyl acrylate rubber polymer of the core component is 50 To 200 nm (first graft copolymer) and 200 to 600 nm (second graft copolymer) are polymerized separately, wherein the inside of the large diameter graft copolymer (second graft copolymer) The seed component was prepared as a small diameter graft copolymer (first graft copolymer), and each graft copolymer latex was agglomerated, washed, dehydrated and dried to obtain a graft copolymer powder. The thermoplastic resin produced by mixing the copolymer powder with the hard matrix resin has rigidity, heat resistance, scratch resistance and impact resistance while maintaining the conventional weather resistance and colorability. It is significantly improved.

That is, the large-diameter graft copolymer is a cross-linked hard-soft mixed component / crosslinked rubber component / non-crosslinked hard component / crosslinked hard-soft mixed component / crosslinked rubber component / non-crosslinked hard component sequentially polymerized To form a multi-layered structure, and in particular, the crosslinked rubber component forms a non-crosslinked intermediate layer or is mixed with a soft component to increase the hardness of the rubber component, thereby improving scratch resistance, and Cavitation occurs well, and the impact resistance is significantly improved.

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                     

<Seed manufacturing step in preparing the first graft copolymer>

7 parts by weight of styrene, 3 parts by weight of butyl acrylate, 1 part by weight of sodium dodecyl sulfate, 0.04 part by weight of ethylene glycol dimethacrylate, 0.02 part by weight of allyl methacrylate, 0.1 part by weight of sodium hydrogen carbonate and 60 parts by weight of distilled water Parts were collectively administered, the temperature was raised to 70 ° C, and 0.06 parts by weight of potassium persulfate was added to initiate the reaction.

After reacting for 1 hour thereafter, the obtained seed had a particle size of 50 nm.

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

40 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, 50 parts by weight of distilled water and 0.05 parts by weight of potassium persulfate were mixed with the seed latex. The mixture 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 core obtained after the completion of the reaction was 100 nm.

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

A mixture of 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, 1.5 parts by weight of potassium rosinate, 0.1 parts by weight of potassium persulfate, 0.1 part by weight of tertiary dodecyl mercaptan and 60 parts by weight of distilled water was mixed to the core latex at 70 ° C. The polymerization reaction was carried out while continuously input 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 the completion of the reaction was 140 nm.

<Step of preparing internal seed during preparation of second graft copolymer>

The inner 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 50 parts by weight of distilled water based on a solid weight fraction.

<Step of preparing external seed during preparation of second graft copolymer>

7 parts by weight of styrene, 3 parts by weight of butyl acrylate, 0.04 parts by weight of ethylene glycol dimethacrylate and 0.02 parts by weight of allyl methacrylate were collectively administered to the inner seed latex, and heated to 70 ° C., followed by 0.06 weight of potassium persulfate. Part was added to initiate the reaction.

After the reaction for 3 hours, the particle size of the obtained external seed was 250 nm.

<Manufacturing 2nd Graft Copolymer-Core Manufacturing Step>

50 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, and 60 parts by weight of distilled water in the external seed latex. And a mixture of 0.05 parts by weight of potassium persulfate was continuously added at 70 ° C. for 3 hours, and further polymerized for 1 hour after the addition was completed. The particle size of the rubber polymer obtained after completion of the reaction showed 450 nm.

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

A mixture of 27 parts by weight of styrene, 10 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 50 parts by weight of distilled water was mixed to the core latex at 70 ° C. The polymerization was carried out while continuously input 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 the completion of the reaction was 550 nm.

<Graft copolymer powder manufacturing step>

The obtained first and second graft copolymer latex were each subjected to atmospheric coagulation at 80 ° C. using an aqueous calcium chloride solution, and then aged at 95 ° C., washed and dehydrated, and dried for 30 minutes with hot air at 90 ° C. ASA graft copolymer powder particles were obtained.

The moisture content of the dried graft copolymer powder was less than 0.5%, and the powder density was at least 0.4 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 of the precursor chemical product, EBS, 0.5 parts by weight of antioxidant (Ciba-Geigy, product name: Irganox 1076) and 0.5 parts by weight of UV stabilizer (Ciba-Geigy, product name: Tinuvin 327) were added and mixed. . The mixture was prepared in pellet form using a 40 pie extrusion kneader at a cylinder temperature of 220 ° C., and injected into the pellet to prepare a physical specimen.

Example 2

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

Example 3

1 part by weight of the first graft copolymer latex, based on the solid weight fraction, as the inner seed of the second graft copolymer, and 28.5 parts by weight of styrene and 10.5 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 that parts were used. The particle size of the core of the second graft copolymer obtained in Example 3 was 480 nm.

Example 4

The same procedure as in Example 1 was carried out except that 5 parts by weight of styrene and 5 parts by weight of butyl acrylate were used in the seed polymerization step of the first graft copolymer and the external seed polymerization step of the second graft copolymer. The particle size of the core of the first graft copolymer obtained in Example 4 was 95 nm, and the particle size of the core of the second graft copolymer was 400 nm.

Comparative Example 1

A core latex of the first graft copolymer was used as the internal seed of the second graft copolymer in the same manner as in Example 1, except that 3 parts by weight of the core latex was used. The particle size of the core of the second graft copolymer obtained in Comparative Example 1 was 450 nm.

Comparative Example 2

The same procedure as in Example 1 was performed except that the first graft copolymer was not used as an inner seed of the second graft copolymer, and an inner seed prepared separately as follows was used.

The separately prepared inner seed 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 55 parts of distilled water. After the batch was administered, 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 internal seed of the second graft copolymer obtained in Comparative Example 2 was 140 nm, and the particle size of the core was 450 nm.

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 410 nm.

[Comparative Example 4]

Except that 15 parts by weight of the first graft copolymer latex was used as a solid weight fraction as an internal seed of the second graft copolymer, and 18 parts by weight of styrene and 7 parts by weight of acrylonitrile were used to prepare the graft shell. It carried out in the same manner as in Example 1. The particle size of the core of the second graft copolymer obtained in Comparative Example 4 was 200 nm.

[Comparative Example 5]

45 parts by weight of the first graft copolymer powder was used and the second graft copolymer powder was not used in the preparation of the thermoplastic resin.

Comparative Example 6

The same procedure as in Example 1 was performed except that the first graft copolymer powder was not used and only 45 parts by weight of the second graft copolymer powder was used to prepare the thermoplastic resin.

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 30 28 31 32 18 15 16 8 2 21 Pencil strength B B B B 4B 4B 3B 3B 4B 3B The tensile strength 550 575 535 525 420 450 465 485 490 395 Heat deflection temperature 98 99 97 96 84 88 89 89 89 79

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

Pencil Hardness (300 g · f) Measured according to ASTM D3363.

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.

As can be seen in Table 1 above, the comparative examples are generally inferior in impact strength and low in pencil hardness, which is very inferior in scratch resistance, and significantly inferior in tensile strength and thermal deformation temperature. On the other hand, there is a problem that does not fit, the embodiments according to the present invention was found to be excellent in physical properties such as impact strength, pencil hardness, tensile strength and heat deformation temperature than the comparative examples.

As described above, the graft copolymer composition and the thermoplastic resin composition using the same improve physical properties such as tensile strength, heat deformation temperature and scratch resistance, and have an effect of obtaining a weather resistant thermoplastic resin having excellent impact resistance. It is a useful invention.

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 (10)

A) based on 100 parts by weight of the first graft copolymer a) 2 to 20 parts by weight of an alkyl acrylate-aromatic vinyl compound copolymer crosslinked as a seed; b) 20 to 60 parts by weight of an alkyl acrylate rubber polymer crosslinked as core; And c) a first graft copolymer containing 30 to 80 parts by weight of an aromatic vinyl compound-vinyl cyan compound copolymer not crosslinked as a graft shell; And B) based on 100 parts by weight of the second graft copolymer a) 0.1 to 10 parts by weight of the first graft copolymer as an internal seed; b) 2 to 20 parts by weight of an alkyl acrylate-aromatic vinyl compound copolymer crosslinked as an external seed; c) 30 to 70 parts by weight of an alkyl acrylate rubber polymer crosslinked as core; And d) a second graft copolymer containing 15 to 50 parts by weight of an aromatic vinyl compound-vinyl cyan compound copolymer not crosslinked as a graft shell; Graft copolymer composition comprising a. The graft copolymer composition of claim 1, wherein the alkyl group of the alkyl acrylate monomer is an alkyl group having 2 to 8 carbon atoms. The graft copolymer composition of claim 2, wherein the alkyl acrylate monomer is butyl acrylate, ethyl hexyl acrylate or a mixture thereof. The graft copolymer of claim 1, wherein the crosslinked alkyl acrylate rubber polymer of the core of the first graft copolymer and the second graft copolymer has a glass transition temperature of -70 to -20 ° C. Composition. The graft copolymer composition of claim 1, wherein the average particle diameter of the core in the first graft copolymer is 50 to 200 nm, and the average particle diameter of the core in the second graft copolymer is 200 to 600 nm. The graft copolymer composition according to claim 1, wherein the aromatic vinyl compound is selected from the group consisting of styrene monomer derivatives of styrene, α-methylstyrene, para methylstyrene and vinyltoluene. The graft copolymer composition of claim 1, wherein the vinyl cyan compound is acrylonitrile or methacrylonitrile, or a mixture thereof. A) 5 to 50 parts by weight of the first graft copolymer powder according to claim 1; B) 5 to 50 parts by weight of the second graft copolymer powder according to claim 1; And C) 10 to 80 parts by weight of the hard matrix resin Thermoplastic resin composition, characterized in that comprises a. 9. The thermoplastic resin composition of claim 8, wherein the hard matrix resin is selected from the group of hard polymer forming monomers having a glass transition temperature of 60 to 140 ° C. The monomer according to claim 8, wherein the hard matrix resin is 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. The thermoplastic resin composition characterized by using the above.