KR100515587B1 - Acrylonitrile-butadiene-styrene graft copolymer composition and method for preparing thereof - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to acrylonitrile-butadiene-styrene graft copolymers and methods for preparing the same, in particular, inner layers and glass transition temperatures (Tg) having a glass transition temperature (Tg) of at least 0 ° C. and an average particle diameter of up to 2000 kPa. Is a multi-layered rubber polymer having an outer layer having a maximum particle size of -20 ° C. and an average particle diameter of 2500 to 5000 kPa, a large diameter rubber polymer having an average particle diameter of 2500 to 5000 kPa, a gel content of 60 to 95% and an swelling index of 18 to 40. Graft copolymerization of an aromatic vinyl compound and a vinyl cyan compound into the mixed rubber polymer mixed to provide acrylonitrile-butadiene-styrene graph with excellent impact resistance, tensile property, and gloss, and particularly excellent coloring and low temperature impact resistance. The present invention relates to a copolymer and a method for producing the same.

Description

Acrylonitrile-butadiene-styrene graft copolymer and its preparation method {ACRYLONITRILE-BUTADIENE-STYRENE GRAFT COPOLYMER COMPOSITION AND METHOD FOR PREPARING THEREOF}

The present invention relates to an acrylonitrile-butadiene-styrene graft copolymer and a method for producing the same, and more particularly, excellent impact resistance, tensile property, and gloss, and particularly excellent coloring and low temperature impact resistance. An acrylonitrile-butadiene-styrene graft copolymer and a method for producing the same are provided.

In general, acrylonitrile-butadiene-styrene (ABS) resins have relatively good physical properties such as impact resistance, mechanical strength, moldability, glossiness, and are widely used in electrical and electronic parts, office equipment, automobile parts, and the like. In particular, since these products require a variety of colors to meet the needs of the consumer, the colorability becomes more important than anything else.

Generally, ABS resins are prepared by continuous bulk polymerization and emulsion polymerization. ABS-based resins prepared by emulsion polymerization have relatively good impact resistance, good balance of physical properties such as fluidity, and excellent gloss, compared to resins prepared by continuous bulk polymerization. ABS-based resins are deteriorated in tensile properties and colorability, and are compounded with various acrylonitrile-styrene (SAN) resins to achieve physical property balance to diversify and specialize products.

Up to now, it is a situation that a resin that satisfies impact resistance, tensile properties, and colorability at the same time in manufacturing ABS resins has not been obtained.

Accordingly, various methods for improving colorability of ABS resins have been proposed. The first method is to reduce the input amount of graft ABS resin in the ABS resin by mixing rubber with a large rubber particle size. The second method is to minimize the use of additives such as emulsifiers in the emulsion graft polymerization. In order to minimize the difference in refractive index between the graft copolymer and the graft copolymer, the monomer of the graft copolymer is used to increase the refractive index of the rubber polymer, or the monomer using the monomer having a low refractive index when preparing the graft copolymer is used. This method minimizes the difference between the refractive indexes.

However, the first method may generate a large amount of coagulum during graft copolymerization, and the second method is not easy to apply due to inadequate conditions in the post-treatment process. In the third method, when the monomer of the graft copolymer is used in the manufacture of the rubber polymer, not only the impact resistance is inappropriate, but also when the monomer which decreases the refractive index in the manufacture of the graft copolymer is used, the amount thereof is insufficient to improve the colorability. There is this.

Accordingly, research on a rubber polymer capable of improving not only the colorability of the ABS resin, but also impact resistance, tensile properties, glossiness, and the like is required.

In order to solve the problems of the prior art as described above, the present invention is not only excellent in impact resistance, tensile properties, processability, and appearance characteristics of the ABS resin, but also excellent in colorability and low temperature impact resistance of acrylonitrile-butadiene-styrene It is an object to provide a graft copolymer.

Another object of the present invention is to provide a method for producing an acrylonitrile-butadiene-styrene graft copolymer that can significantly improve colorability, low temperature impact resistance, impact resistance, tensile properties, processability, and appearance characteristics.

Another object of the present invention is to provide an acrylonitrile-butadiene-styrene graft copolymer and an ABS resin having excellent colorability and low temperature impact resistance, including the graft copolymer and a SAN resin.

In order to achieve the above object, the present invention in the ABS graft copolymer composition,

a) iii) a) glass transition temperature (Tg) is at least 0 ℃, average particle diameter is maximum

         Inner layer of 2000 kPa; And

     B) The maximum glass transition temperature (Tg) is -20 ℃ and the average particle diameter

         2500 ~ 5000 square outer layer

     90 to 10% by weight of a multi-layered rubber polymer comprising a; And

  Ii) Average particle size 2500 ~ 5000Å, gel content 60 ~ 95%, swelling index 18 ~ 40

      Large diameter rubber polymer 10 to 90 wt%

  30 to 70 parts by weight of a mixed rubber polymer including;

b) 15 to 30 parts by weight of an aromatic vinyl compound; And

c) 10 to 25 parts by weight of the vinyl cyan compound

It provides an ABS graft copolymer composition comprising a.

In addition, the present invention is a method for producing an ABS graft copolymer,

a) iii) a) glass transition temperature (Tg) is at least 0 ℃, average particle diameter is maximum

         Inner layer of 2000 kPa; And

     B) The maximum glass transition temperature (Tg) is -20 ℃ and the average particle diameter

         2500 ~ 5000 square outer layer

     90 to 10% by weight of a multi-layered rubber polymer comprising a; And

  Ii) Average particle size 2500 ~ 5000Å, gel content 60 ~ 95%, swelling index 18 ~ 40

      Large diameter rubber polymer 10 to 90 wt%

  Mixing a rubber to prepare a rubber polymer mixture;

b) aromatic vinylation in 30 to 70 parts by weight of the rubber polymer mixture of a)

   15-30 parts by weight of the compound and 10-25 parts by weight of the vinyl cyan compound

   Adding graft copolymerization step

It provides a method for producing an ABS graft copolymer comprising a.

In the ABS resin,

a) iii) a) glass transition temperature (Tg) is at least 0 ℃, average particle diameter is maximum

         Inner layer of 2000 kPa; And

     B) The maximum glass transition temperature (Tg) is -20 ℃ and the average particle diameter

         2500 ~ 5000 square outer layer

     90 to 10% by weight of a multi-layered rubber polymer comprising a; And

  Ii) Average particle size 2500 ~ 5000Å, gel content 60 ~ 95%, swelling index 18 ~ 40

      Large diameter rubber polymer 10 to 90 wt%

  ABS graft copolymer comprising a mixed rubber polymer comprising

  20 to 40 parts by weight; And

b) 60 to 80 parts by weight of styrene-acrylonitrile (SAN) resin

It provides an ABS resin comprising a.

Hereinafter, the present invention will be described in detail.

The inner layer described below shows a seed part which normally expresses the superposition | polymerization of a monomer, and an outer layer shows the shell part which expresses the normal expression which superposed | polymerized the conjugated diene compound to the inner layer polymer which is the said seed part. In addition, the mixed rubber polymer represents a mixed rubber polymer obtained by mixing a rubber polymer having a multilayer structure including an inner layer which is a normal seed part and an outer layer which is a cell part, and a large diameter rubber polymer polymerized with a conjugated diene compound. In addition, the ABS graft copolymer is a mixed rubber polymer in which a multi-layered rubber polymer and a large diameter rubber polymer including an inner layer and an outer layer are mixed, and an aromatic vinyl compound, a vinyl cyan compound, and a mixture thereof on the surface of the mixed rubber polymer. The ABS graft copolymer which grafted the monomer chosen from the group which consists of these is shown. In addition, ABS resins represent ABS graft copolymers including a mixed rubber polymer in which the multi-layered rubber polymer and the large-diameter rubber polymer including the inner layer and the outer layer are mixed, and the ABS resin in which the SAN resin is mixed.

The inventors of the present invention while studying the ABS graft copolymer excellent in colorability, the inner layer and the inner layer of the outer layer using a hard layer having a glass transition temperature (Tg) of at least 0 ℃ by varying the glass transition temperature (Tg) of each and To prepare a multi-layered rubber polymer containing an outer layer using a rubber layer having a glass transition temperature (Tg) of up to -20 ℃, the multi-layered rubber polymer and an average particle diameter of 2500 ~ 5000 Pa, gel content of 60 ~ 95%, After mixing the large-diameter rubber polymer having a swelling index of 18 to 40 and using the same to prepare an ABS resin, the impact resistance, tensile property, processability, and appearance characteristics are not only excellent, but particularly the coloring and low temperature impact resistance are remarkable. It was confirmed that the improvement, and based on this, the present invention was completed.

The present invention provides a multilayered structure comprising an inner layer having a glass transition temperature (Tg) of at least 0 ° C., an average particle diameter of up to 2000 kPa, and an outer layer having a glass transition temperature of up to −20 ° C., and an average particle diameter of up to 2500˜5000 Pa. The present invention provides an ABS graft polymer including a rubber polymer, and a mixed rubber polymer including an average particle diameter of 2500 to 5000 mm 3, a gel content of 60 to 95%, and a large diameter rubber polymer having an swelling index of 18 to 40, and a method for preparing the same.

The ABS graft copolymer of the present invention has a glass transition temperature (Tg) of at least 0 ° C. and an average particle diameter of up to 2000 kPa, after preparing a polymer for an inner layer, and then polymerizing a monomer in the polymer for the inner layer. Multi-layered rubber polymer containing an outer layer polymer having a maximum (Tg) of -20 ° C and an average particle diameter of 2500 to 5000 kPa, an average particle diameter of 2500 to 5000 kPa, a gel content of 60 to 95%, and an swelling index of 18 to 40 It is characterized in that it comprises a mixed rubber polymer mixed with a phosphorus large diameter rubber polymer. In addition, the ABS graft copolymer of the present invention is characterized by being prepared by grafting an aromatic vinyl compound and a vinyl cyan compound to the mixed rubber polymer.

ABS graft copolymer composition of the present invention can be prepared by the following method.

a) Manufacture of multi-layered rubber polymer

(Manufacture of polymer for inner layer)

The inner layer of this step represents the seed part normally expressed.

The inner layer is based on monomer parts by weight iii) 60 to 100 parts by weight of aromatic vinyl compound, ii) up to 40 parts by weight of vinyl cyan compound, iii) up to 20 parts by weight of conjugated diene compound, iii) 0.1 to 10 parts by weight of graft crosslinker. And (iii) 1 to 4 parts by weight of an emulsifier, iii) 0.1 to 3 parts by weight of a polymerization initiator, iii) a maximum of 2 parts by weight of an electrolyte, and iii) 150 to 200 parts by weight of ion-exchanged water.

The aromatic vinyl compound of (iii) is preferably included in an amount of 60 to 100 parts by weight based on the monomer. If the content is less than 60 parts by weight, there is a problem that the colorability is lowered.

The aromatic vinyl compound may be a styrene monomer derivative, and examples thereof include styrene, α-methylstyrene, ο-ethylstyrene, ρ-ethylstyrene, or vinyl toluene.

The vinylcyan compound of ii) is preferably included in a maximum of 40 parts by weight based on the monomer. If the content exceeds 40 parts by weight, there is a problem that the impact resistance is lowered.

As the vinyl cyan compound, acrylonitrile, methacrylonitrile, ethacrylonitrile or the like can be used.

It is preferable that the conjugated diene compound of iii) is included in a maximum of 20 parts by weight based on the monomer. If the content exceeds 20 parts by weight, there is a problem that the colorability is lowered.

As the conjugated diene compound, 1,3-butadiene, isoprene, chloroprene, pyrrylene, or comonomers thereof may be used.

The graft crosslinking agent of i) may use allyl methacrylate, or triallyl isocyanurate, and the crosslinking agent may be ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol die. Methacrylate, 1, 4- butylene glycol dimethacrylate, divinylbenzene, etc. can be used.

The emulsifier of i) may be alkyl aryl sulfonate, alkali methyl alkyl sulfate, sulfonated alkyl ester, soap of fatty acid, alkali salt of rosin acid, or the like.

The polymerization initiator of iii) may use a water-soluble persulfate, a peroxy compound, an oxidation-reduction system, or the like. Specifically, water-soluble persulfates, such as sodium or potassium persulfate; Fat-soluble polymerization initiators such as cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, and benzoyl peroxide; Mixtures of water-soluble radical initiators and oil-soluble radical initiators.

The electrolyte of iii) is used to ensure the stability of the latex, for example KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , Na ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ , Na ₂ HPO ₄ and the like can be used.

The inner layer is preferably emulsion polymerization for 2 to 6 hours at a temperature of 60 to 80 ℃.

Under the above conditions, the emulsion-polymerized inner layer preferably has a glass transition temperature of at least 0 ° C. and an average particle diameter of 2000 μm (0.2 μm) or less in consideration of the average particle diameter of the final rubber latex.

(Manufacture of polymer for outer layer)

The outer layer of this step is based on the monomer iii) 5 to 30 parts by weight of the inner layer ii) 30 to 60 parts by weight of the conjugated diene compound, iii) 1.5 to 4 parts by weight of the emulsifier, iii) 0.1 to 3 parts by weight of the polymerization initiator, iii) 0.1 to 1 parts by weight of the molecular weight regulator, iv) 0.5 to 3 parts by weight of the electrolyte, and iii) 150 to 200 parts by weight of ion-exchanged water to polymerize at a temperature of 60 to 80 ℃ for 7 to 20 hours, and then to the polymer Ii) 20 to 50 parts by weight of the conjugated diene compound, and iii) 0.1 to 1 parts by weight of the molecular weight modifier may be prepared by a method of emulsion polymerization for 15 to 30 hours at a temperature of 60 to 80 ℃.

The inner layer of iii) is preferably included in 5 to 30 parts by weight based on the monomer. If the content is less than 5 parts by weight, there is a problem that the colorability is lowered, if it exceeds 30 parts by weight, the colorability is excellent, but there is a problem that the impact resistance at room temperature is significantly reduced.

The conjugated diene compound of ii) has sufficient crosslinking, and the conjugated diene compound having a sufficiently low glass transition temperature of −20 ° C. or lower may be used alone, or may be mixed with an ethylenically unsaturated monomer.

As the ethylenically unsaturated monomer copolymerizable, the conjugated diene compound may be an aromatic vinyl compound such as styrene or α-methylstyrene, a vinyl cyan compound such as acrylonitrile, an acrylic acid ester, or a methacrylic acid ester. In addition, the content is preferably used within 20 parts by weight of the total monomer mixture so that the glass transition temperature of the rubber polymer can be prepared below -20 ℃.

As the conjugated diene compound, 1,3-butadiene, isoprene, chloroprene, pyrrylene, or comonomers thereof may be used.

The emulsifier of i) may be the same as those used in the preparation of the inner layer, and in order to form a perfect outer layer of the rubber polymer on the inner layer, the type and amount of emulsifier used in the preparation of the inner layer should be appropriately selected. In addition, the content of the emulsifier is preferably used in the range that does not reduce the stability of the outer layer, preferably contained in 1.5 to 4 parts by weight based on 100 parts by weight of the conjugated diene compound.

In addition, the polymerization initiator, molecular weight regulator, and electrolyte used in the manufacture of the outer layer can be the same as those used in the production of the inner layer.

In the present invention, it is preferable that the monomer is emulsion-polymerized by partially dosing the monomer during preparation of the outer layer, and then emulsion-polymerizing the remainder by batch or continuous dosing to the reactants. When the entire amount of the monomer is administered, there is a problem in that a phenomenon in which a perfect outer layer is not formed on the surface of the inner layer, that is, the average particle diameter of the rubber polymer is much smaller than the desired average particle diameter.

The outer layer may be prepared by a method of reacting one step at a temperature of 60 to 80 ° C. for 7 to 20 hours and then performing two steps of reaction at a temperature of 60 to 80 ° C. for 15 to 30 hours.

The glass transition temperature of the outer layer prepared according to the present invention is preferably at most -20 ℃, in order to obtain an ABS resin excellent in colorability and impact resistance at room temperature, the average particle diameter (including the inner layer) of the rubber polymer including the inner layer and the outer layer is 2500 It is preferable that it is -5000 kPa (0.25-0.5 micrometer).

b) Manufacture of large diameter rubber polymer

The large diameter rubber polymer having an average particle diameter of 2500 to 5000 mm, gel content of 60 to 95%, and swelling index of 18 to 40 is 50 to 95 parts by weight of the total 100 parts by weight of the conjugated diene compound, and ii) 1 to 4 weight of the emulsifier. Iv) 0.2 to 1.5 parts by weight of the polymerization initiator, iii) 0.1 to 0.5 parts by weight of the molecular weight regulator, iii) 0.5 to 2 parts by weight of the electrolyte, and iii) 75 to 120 parts by weight of ion-exchanged water to react in a batch. After the preparation to 1 to 65%, i) may be prepared by the method of reacting the remaining conjugated diene compound by batch administration or continuous administration.

The conjugated diene compound of (i) may have sufficient crosslinking, and the conjugated diene compound having a sufficiently low glass transition temperature of −20 ° C. or lower may be used alone, or may be mixed with an ethylenically unsaturated monomer.

As the ethylenically unsaturated monomer copolymerizable with the conjugated diene compound, an aromatic vinyl compound such as styrene or α-methylstyrene, a vinyl cyan compound such as acrylonitrile, an acrylic acid ester, or a methacrylic acid ester may be used. In addition, the content is preferably used within 20 parts by weight of the total monomer mixture so that the glass transition temperature of the rubber polymer can be prepared below -20 ℃.

As the conjugated diene compound, 1,3-butadiene, isoprene, chloroprene, pyrrylene, or comonomers thereof may be used.

The emulsifier of ii) may use the same material as those used in the preparation of the inner layer.

In addition, the polymerization initiator, the molecular weight regulator, and the electrolyte used in the preparation of the large-diameter rubber polymer may use the same materials as those used in the preparation of the inner and outer layers.

In the preparation of the large-diameter rubber polymer of this step, a part of the monomers is emulsified in a batch to prepare the gel content so as to have a gel content of 1 to 65%, and then the remainder is subjected to a batch or continuous dosing to the reactant to be emulsion polymerized. When the entire amount of the monomer is administered, there is a problem in that the average particle diameter of the rubber polymer is much smaller than the desired average particle diameter.

The large-diameter rubber polymer may be prepared by a method of reacting one step at a temperature of 60 to 80 ° C. for 7 to 20 hours and then performing two steps of reaction at a temperature of 60 to 80 ° C. for 15 to 30 hours.

The large-diameter rubber polymer prepared according to the present invention preferably has an average particle diameter of 2500 to 5000 mm (0.25 to 0.5 µm), and a standard deviation of the particle size is preferably 25% or less. In addition, the glass transition temperature (Tg) is a maximum of -20 ℃, the gel content is 60 to 95%, the swelling index is preferably 18 to 40. If the average particle diameter is less than 2500 kPa, low-temperature impact resistance is lowered, and if the average particle diameter exceeds 5000 kPa, the stability of the polymer is reduced when applied to the ABS resin, there is a problem that a large amount of coagulation is produced.

c) ABS graft copolymer composition preparation

The ASA graft copolymer of this step is a multi-layered rubber polymer including the inner layer and the outer layer prepared as described above, a large diameter rubber polymer having an average particle diameter of 2500 ~ 5000 Å, gel content 60 ~ 95%, swelling index 18 ~ 40 After mixing to prepare a rubber polymer mixture, 15 to 30 parts by weight of the aromatic vinyl compound and 10 to 25 parts by weight of the vinyl cyan compound may be prepared by graft copolymerization in 30 to 70 parts by weight of the rubber polymer mixture.

The ABS graft copolymer composition

a) iii) a multi-layered rubber polymer 90 to 10 comprising an inner layer and an outer layer

      weight%;

  Ii) Average particle size 2500 ~ 5000Å, gel content 60 ~ 95%, swelling index 18 ~ 40

      Phosphorus large diameter rubber polymer 10 to 90 wt%

  30 to 70 parts by weight of a mixed rubber polymer including;

b) 15 to 30 parts by weight of an aromatic vinyl compound;

c) 10 to 25 parts by weight of the vinyl cyan compound;

d) 0.6 to 2.0 parts by weight of emulsifier;

e) 0.2 to 1.0 parts by weight of molecular weight modifier; And

f) 0.05 to 0.5 parts by weight of polymerization initiator

It is preferable to prepare by graft copolymerization.

In the production of the ABS graft copolymer, monomers may be added by a method of totally administering each component, a method of divided administration in multiple stages, or a method of continuous administration, and in particular, in order to minimize the formation of coagulated products, the method of divided administration in multiple stages. However, the method of continuous administration is preferable.

As the aromatic vinyl compound of b), styrene, alphamethyl styrene, or vinyl toluene may be used, and the vinyl cyan compound of c) may use acrylonitrile or methacrylonitrile.

The emulsifier of d) may be alkylarylsulfonate, alkali methyl alkylsulfonate, sulfonated alkyl ester, fatty acid soap, or rosin acid alkali salt.

The molecular weight regulator of e) may use tertiary dodecyl mercaptan.

The polymerization initiator of f) is a peroxide such as tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, persulfate, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, formaldehyde sodium Oxidation-reduction catalysts which are a mixture of reducing agents such as sulfoxylate, ferrous sulfate, dextrose, sodium pyrrolate, sodium sulfite and the like can be used.

In addition, an antioxidant and a stabilizer are administered to the ABS graft copolymer prepared as described above, aggregated into an aqueous sulfuric acid solution at a temperature of 90 ° C. or higher, and then dehydrated and dried to obtain a powdered ABS graft polymer.

In another aspect, the present invention provides an ABS resin prepared by mixing the ABS graft copolymer with a styrene-acrylonitrile (SAN) resin.

The ABS graft polymer of the multilayer structure is preferably included in an amount of 20 to 40 parts by weight, and the SAN resin is preferably included in an amount of 60 to 80 parts by weight based on 100 parts by weight of the ABS resin.

It is preferable that the said SAN resin is prepared by bulk-polymerizing monomers, such as an aromatic mono alkenyl monomer, a vinyl cyan monomer, an acrylic acid alkylester monomer, or an alkylester monomer of methacrylic acid.

The ABS-based resin prepared as described above has an excellent effect of impact resistance, tensile properties, glossiness, colorability, and low temperature impact resistance.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

(Manufacture of rubber polymer of multi-layer structure)

Manufacture of inner layer polymer

150 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 100 parts by weight of styrene as monomer, 2.0 parts by weight of potassium oleate as emulsifier, 3 parts by weight of allyl methacrylate as graft crosslinker, 0.3 parts by weight of potassium persulfate as polymerization initiator The batch was administered. After reacting the mixture at a reaction temperature of 70 ° C. for 4 hours, the reaction was terminated to prepare an inner layer polymer having an average particle diameter of 1300 mm 3.

Manufacture of outer layer polymer

10 parts by weight of the inner layer polymer prepared in Example 1, 75 parts by weight of ion-exchanged water, 72 parts by weight of 1,3-butadiene as a monomer, 1.2 parts by weight of potassium rosin salt as an emulsifier and potassium oleate 1.0 parts by weight of salt, 0.7 parts by weight of sodium carbonate and 0.8 parts by weight of potassium hydrogen carbonate, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as the molecular weight regulator, and 0.3 parts by weight of potassium persulfate as the polymerization initiator, followed by 70 ° C The reaction was carried out at a reaction temperature of 13 hours. 18 parts by weight of the remaining monomer 1,3-butadiene, and 0.03 parts by weight of tertiary dodecylmercaptan with a molecular weight control agent were reacted at 75 ° C. for 27 hours, and then the reaction was terminated to give a multi-layered rubber polymer (A) Was prepared.

(Manufacture of large diameter rubber polymer)

75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 80 parts by weight of 1,3-butadiene as monomer, 1.2 parts by weight of potassium rosin salt as emulsifier, 1.5 parts by weight of potassium oleate salt, 0.7 parts by weight of sodium carbonate as electrolyte and hydrogen carbonate 0.8 parts by weight of potassium, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, and 0.3 parts by weight of potassium persulfate as a polymerization initiator were reacted at a reaction temperature of 70 ° C. for 15 hours. 20 parts by weight of the remaining monomer 1,3-butadiene and 0.05 parts by weight of tertiary dodecylmercaptan with a molecular weight control agent were collectively reacted at 75 ° C. for 28 hours, and then the reaction was terminated to prepare a large diameter rubber polymer.

(ABS graft copolymer production)

30 parts by weight of a multi-layered rubber polymer (A) comprising the inner layer and the outer layer prepared in the nitrogen-substituted polymerization reactor (A), 20 parts by weight of large diameter rubber polymer, 65 parts by weight of ion-exchanged water, 0.35 parts by weight of potassium rosinate as an emulsifier, 0.1 parts by weight of sodium ethylenediaminetetraacetate, 0.005 parts by weight of ferrous sulfate, and 0.23 parts by weight of formaldehyde sodium sulfoxylate were collectively administered as a polymerization initiator, and then the reaction temperature was raised to 70 ° C. Then, 50 parts by weight of ion-exchanged water, 0.65 parts by weight of potassium rosin as an emulsifier, 35 parts by weight of styrene as an aromatic vinyl compound, 15 parts by weight of acrylonitrile as a vinyl cyan compound, and 0.4 parts by weight of tertiary dodecylmercaptan as a molecular weight regulator , 0.4 parts by weight of a mixed emulsion solution of diisopropylene benzene hydroperoxide as a polymerization initiator was continuously administered for 3 hours, and then the reaction temperature was raised to 80 ° C. for 1 hour, and the reaction was terminated to prepare an ABS graft copolymer. It was.

Example 2

(Manufacture of rubber polymer of multi-layer structure)

Manufacture of inner layer polymer

Example 1, except that 4 parts by weight of the potassium oleate salt was used as an emulsifier when preparing the polymer for the inner layer was carried out in the same manner as in Example 1.

Manufacture of outer layer polymer

Except that 5 parts by weight of the prepared inner layer polymer in Example 1 was carried out in the same manner as in Example 1 to prepare a rubber polymer (B) of a multi-layer structure.

(Manufacture of large diameter rubber polymer)

It carried out in the same manner as in Example 1.

(ABS graft copolymer production)

The same method as in Example 1 was performed except that 35 parts by weight of the prepared multilayer polymer rubber (B) and 15 parts by weight of the large-diameter rubber latex were used.

Example 3

(Manufacture of rubber polymer of multi-layer structure)

Manufacture of outer layer polymer

In the same manner as in Example 1 except that 10 parts by weight of the inner layer polymer prepared in Example 2 in Example 1, and 0.8 parts by weight of potassium oleate salt as an emulsifier was used in the same manner as in Example 1 of the multi-layered rubber polymer (C ) Was prepared.

(Manufacture of large diameter rubber polymer)

It carried out in the same manner as in Example 1.

(ABS graft copolymer production)

The same method as in Example 1 was carried out except that 25 parts by weight of the rubber polymer (C) having the multilayered structure and 25 parts by weight of the large-diameter rubber latex prepared in Example 1 were used.

Example 4

(Manufacture of rubber polymer of multi-layer structure)

Manufacture of inner layer polymer

In Example 1, 80 parts by weight of styrene and 20 parts by weight of 1,3-butadiene as monomers, 2.5 parts by weight of potassium oleate salt, 0.4 parts by weight of potassium rosin acid salt, and 1 part by weight of divinyl benzene as graft crosslinking agent were used. Except that was carried out in the same manner as in Example 1.

Manufacture of outer layer polymer

Except for using 6 parts by weight of the prepared inner layer polymer in Example 1 was carried out in the same manner as in Example 1 to prepare a rubber polymer (D) of a multi-layer structure.

(Manufacture of large diameter rubber polymer)

It carried out in the same manner as in Example 1.

(ABS graft copolymer production)

The same method as in Example 1 was performed except that 30 parts by weight of the manufactured rubber polymer (D) of the multilayer structure was used in Example 1.

Example 5

(Manufacture of rubber polymer of multi-layer structure)

It carried out in the same manner as in Example 1.

(Manufacture of large diameter rubber polymer)

It carried out in the same manner as in Example 1.

(ABS graft copolymer production)

The same method as in Example 1 was performed except that 30 parts by weight of the rubber polymer (A) having a multilayer structure was used in Example 1.

Example 6

(Manufacture of rubber polymer of multi-layer structure)

It carried out in the same manner as in Example 1.

(Manufacture of large diameter rubber polymer)

It carried out in the same manner as in Example 1.

(ABS graft copolymer production)

The same method as in Example 1 was performed except that 10 parts by weight of the multi-layered rubber polymer (A) and 40 parts by weight of the large-diameter rubber latex prepared in Example 1 were used.

Comparative Example 1

In Example 1, except that only 50 parts by weight of the multi-layered rubber polymer (A) was used in the manufacture of the ABS graft copolymer was carried out in the same manner as in Example 1.

Comparative Example 2

In Example 1, except that only 50 parts by weight of large diameter rubber latex was used to prepare the ABS graft copolymer was carried out in the same manner as in Example 1.

Experimental Example 1

The glass transition temperature and the particle diameter were measured by the following method using the multi-layered rubber polymer and the large-diameter rubber polymer prepared in Examples 1 to 6, and the results are shown in Table 1 below.

A) Glass transition temperature (DSC)-11 mg of the powder obtained by solidifying the prepared inner layer with sulfuric acid was heated to 150 ° C on DSC, cooled to -40 ° C to 150 ° C / min to remove the thermal history, and then to 10 The glass transition temperature was measured by raising the temperature to ° C / min.

B) Average particle diameter-Dynamic laser light was measured by using Nicomp 370 HPL.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Multi-layered Rubber Polymer Inner layer Glass transition temperature 105 ℃ 105 ℃ 105 ℃ 61 ℃ 105 ℃ 105 ℃ Average particle diameter 1300 Å 90 Å 900 Å 1100 Å 1300 Å 1300 Å usage 10 parts by weight 5 parts by weight 10 parts by weight 6 parts by weight 10 parts by weight 10 parts by weight Outer layer Average particle diameter 3100 yen 3150 yen 3050 Å 3200 Å 3100 yen 3100 yen Large Diameter Rubber Polymer Average particle diameter 3300 yen 3300 yen 3300 yen 3300 yen 3300 yen 3300 yen

Experimental Example 2

30 parts by weight of the ABS graft copolymer powder prepared in Examples 1 to 6 and Comparative Examples 1 or 2 and 70 parts by weight of a SAN (LG Chemical, product name: 80HF) resin were mixed in a mixer, and then used in an extruder. After the pelletized to prepare a specimen using an injection machine and measured the physical properties in the following manner, the results are shown in Table 2 below.

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

B) melt flow index (MI)-measured by ASTM D1238 under the condition of 220 ° C. · 10 kg.

C) Tensile strength-measured by ASTM D638 method.

D) Surface gloss-measured by ASTM D528 method at a 45 ° angle.

ㅁ) Colorability-Coloration was measured based on green color sensitive to human eyes using SUGA Color Computer and expressed as L, a, b values. At this time, it was assumed that the lower the L value and the higher the a value, the better the red value was. Coloring experiments were performed to vary the amount of colorant to have similar values.

division Example Comparative example One 2 3 4 5 6 One 2 Powder type (part by weight) ABS graft copolymer Multi-layered Rubber Polymer A: 30 parts by weight B: 35 parts by weight C: 25 parts by weight D: 30 parts by weight A: 40 parts by weight A: 10 parts by weight A: 50 parts by weight - Daegu Light Rubber Polymer 20 parts by weight 15 parts by weight 25 parts by weight 20 parts by weight 10 parts by weight 40 parts by weight - 50 parts by weight Total usage 30 parts by weight 30 parts by weight 30 parts by weight 30 parts by weight 30 parts by weight 30 parts by weight 30 parts by weight 30 parts by weight SAN resin 70 parts by weight 70 parts by weight 70 parts by weight 70 parts by weight 70 parts by weight 70 parts by weight 70 parts by weight 70 parts by weight Izod impact strength (23 ℃, ㎏cm / ㎝) 32 32 30 33 32 33 31 33 Izod impact strength (-20 ℃, ㎏cm / ㎝) 21 21 20 22 19 22 15 23 Fluidity (g / 10min) 22 21 22 21 21 21 22 23 Tensile Strength (㎏ / ㎠) 480 485 479 479 483 480 481 480 Surface gloss (%) 95 94 96 95 95 94 96 94 Colorant Usage 0.15 0.16 0.14 0.17 0.12 0.18 0.12 0.23 Coloring L 30.3 30.2 30.5 30 30.7 30.6 30.8 30.6 Coloring a 53 53.3 52.8 52.9 53.1 52.9 52.9 53

Through Table 2, the ABS resin of Examples 1 to 6 prepared in accordance with the present invention compared to the ABS resin of Comparative Example 1 or 2 Izod impact strength, fluidity, tensile strength, surface gloss at room temperature and low temperature, and It was confirmed that the colorability was excellent.

According to the present invention, the ABS graft copolymer not only has excellent impact resistance at room temperature, tensile property, processability, and appearance, but also has excellent coloring and low temperature impact resistance, and colorability and low temperature including the copolymer and the SAN resin. An ABS resin having excellent impact resistance can be produced.

Claims (23)

a) 60 to 100 parts by weight of an aromatic vinyl compound, up to 40 parts by weight of a vinyl cyan compound, and 5 to 30 parts by weight of an inner layer containing up to 20 parts by weight of a conjugated diene compound,   90 to 10 wt% of a multi-layered rubber polymer including 70 to 95 parts by weight of the conjugated diene compound to form an outer layer; And   Large diameter rubber polymer with average particle size 2500 ~ 5000 고무, gel content 60 ~ 95%, swelling index 18 ~ 40 10 ~ 90% by weight   30 to 70 parts by weight of a mixed rubber polymer including; b) 15 to 30 parts by weight of an aromatic vinyl compound; And c) 10 to 25 parts by weight of a vinyl cyan compound, The inner layer is ABS graft having a glass transition temperature (Tg) of at least 0 ° C., an average particle diameter of up to 2000 kPa, and an outer layer of a glass transition temperature (Tg) of up to −20 ° C., and an average particle diameter of up to 2500 ~ 5000 kPa. Copolymer composition. delete The method of claim 1, ABS graft copolymer composition wherein the aromatic vinyl compound is selected from the group consisting of styrene, α-methylstyrene, ο-ethylstyrene, p-ethylstyrene, and vinyl toluene. The method of claim 1, ABS graft copolymer composition wherein the vinyl cyan compound is selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. The method of claim 1, ABS graft copolymer composition wherein the conjugated diene compound is selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, pyrrylene, and comonomers thereof. delete The method of claim 1, ABS conjugated diene compound of the outer layer is a conjugated diene compound having a glass transition temperature of up to -20 ℃ alone, or a mixture of a conjugated diene compound and an ethylenically unsaturated monomer having a glass transition temperature of up to -20 ℃. The method of claim 1, ABS graft copolymer composition wherein the conjugated diene compound of the outer layer is selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, parylene, and comonomers thereof. The method of claim 7, wherein ABS graft copolymer composition wherein the ethylenically unsaturated monomer is selected from the group consisting of styrene, α-methylstyrene, acrylonitrile, acrylic acid ester, and methacrylic acid ester. The method of claim 1, ABS graft copolymer composition wherein the large-diameter rubber polymer comprises 100 parts by weight of the conjugated diene compound based on the monomer. The method of claim 1, ABS graft copolymer composition wherein the aromatic vinyl compound of b) is selected from the group consisting of styrene, alphamethyl styrene, and vinyl toluene. The method of claim 1, ABS graft copolymer composition of the cyan compound of c) is acrylonitrile or methacrylonitrile. In the manufacturing method of the ABS graft copolymer, a) i) 60 to 100 parts by weight of an aromatic vinyl compound, up to 40 parts by weight of a vinyl cyan compound, up to 20 parts by weight of a conjugated diene compound, 0.1 to 10 parts by weight of a graft crosslinker, 1 to 4 parts by weight of an emulsifier, and 0.1 to 4 polymerization initiator Emulsion-polymerization of 3 parts by weight, up to 2 parts by weight of electrolyte, and 150-200 parts by weight of ion-exchanged water to prepare an inner layer; And   5 to 30 parts by weight of the inner layer 70 to 95 parts by weight of the conjugated diene compound, 1.5 to 4 parts by weight of emulsifier, 0.1 to 3 parts by weight of polymerization initiator, 0.2 to 2 parts by weight of molecular weight regulator, 0.5 to 3 parts by weight of electrolyte, and ion exchange 90 to 10 parts by weight of a multi-layered rubber polymer including an outer layer prepared by emulsion polymerization of a number of 150 to 200 parts by weight; And   ii) preparing a rubber mixture by mixing 10 to 90% by weight of a large diameter rubber polymer having an average particle diameter of 2500 to 5000 mm 3, a gel content of 60 to 95%, and a swelling index of 18 to 40; And b) graft copolymerizing by adding 15 to 30 parts by weight of aromatic vinyl compound and 10 to 25 parts by weight of vinyl cyan compound to 30 to 70 parts by weight of the rubber polymer mixture of a), The inner layer is ABS graft having a glass transition temperature (Tg) of at least 0 ° C., an average particle diameter of up to 2000 kPa, and an outer layer of a glass transition temperature (Tg) of up to −20 ° C., and an average particle diameter of up to 2500 ~ 5000 kPa. Method of Preparation of Copolymer. delete The method of claim 13, The graft crosslinker is allyl methacrylate, triallyl isocyanurate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol A method for producing an ABS graft copolymer selected from the group consisting of dimethacrylate and divinylbenzene. The method of claim 13, The method of producing an ABS graft copolymer, wherein the emulsifier is selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, soaps of fatty acids, and alkali salts of rosin acid. The method of claim 13, The polymerization initiator is a group consisting of sodium, potassium persulfate, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, and benzoyl peroxide Method for producing an ABS graft copolymer is selected from one or more. The method of claim 14, The electrolyte is KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , Na ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ A method for producing an ABS graft copolymer selected from the group consisting of PO ₄ , K ₂ HPO ₄ , and Na ₂ HPO ₄ . delete The method of claim 13, 100 parts by weight of the large diameter rubber polymer of a) conjugated diene compound based on the monomer; 1 to 4 parts by weight of an emulsifier; 0.2 to 1.5 parts by weight of a polymerization initiator; 0.1 to 0.5 parts by weight of molecular weight modifier; 0.5 to 2 parts by weight of an electrolyte; And 75 to 120 parts by weight of ion-exchanged water to prepare an ABS graft copolymer composition prepared by emulsion polymerization. The method of claim 13, The large-diameter rubber polymer of a) is 50 to 95 parts by weight of a total of 100 parts by weight of the conjugated diene compound is prepared by emulsion polymerization to prepare a gel content of 1 to 65%, the remaining conjugated diene compound 5 to 50 to the reactant A method for producing an ABS graft copolymer prepared by the method of emulsion polymerization by mass administration or continuous administration of parts by weight. In ABS resin, a) i) 60 to 100 parts by weight of the aromatic vinyl compound, up to 40 parts by weight of the vinyl cyan compound, and 5 to 30 parts by weight of the inner layer containing up to 20 parts by weight of the conjugated diene compound are included in the range of 70 to 95 parts by weight of the conjugated diene compound. 90 to 10% by weight of the multi-layered rubber polymer constituting the outer layer, and 10 to 90% by weight of the large diameter rubber polymer having an average particle diameter of 2500 to 5000 mm 3, gel content of 60 to 95%, and swelling index of 18 to 40; And ii) 10 to 90% by weight of large-diameter rubber polymer having an average particle diameter of 2500 to 5000 Pa, gel content of 60 to 95%, and swelling index of 18 to 40 20 to 40 parts by weight of an ABS graft copolymer including a mixed rubber polymer containing a; And b) 60 to 80 parts by weight of styrene-acrylonitrile (SAN) resin The inner layer has a glass transition temperature (Tg) of at least 0 ° C., an average particle diameter of up to 2000 kPa, and an outer layer of a glass transition temperature (Tg) of up to −20 ° C., and an average particle diameter of up to 2500˜5000 kPa. ABS resin. The method of claim 22, The ABS resin of the said b) is selected from the group which consists of an aromatic mono alkenyl monomer, a vinyl cyan monomer, an acrylic acid alkyl ester monomer, and the alkyl ester monomer of methacrylic acid.