KR100497169B1 - Method for preparing rubber-copolymer and abs resin comprising thereof - Google Patents

Abstract

The present invention relates to a method for producing a rubber polymer and an ABS-based resin including the same, in particular, an inner layer having a glass transition temperature (Tg) of at least 0 ° C. and an average particle diameter of up to 2000 kPa, and a glass transition temperature (Tg) of up to It relates to a rubber polymer comprising an outer layer having a maximum particle size of 2500 to 5000 mm 3 at -20 ° C, a method for producing the same, an ABS graft polymer having a multilayer structure including the rubber polymer, and an ABS resin.

The rubber polymer prepared according to the present invention and including the inner layer and the outer layer can not only maximize the graft rate on the surface of the rubber polymer by preventing the graft polymer from penetrating into the rubber polymer when the ABS graft polymer is prepared, and at the same time, The coloring, impact resistance, tensile properties, and workability of the system resin can be significantly improved.

Description

Manufacturing method of rubber polymer and ABS resin comprising same {METHOD FOR PREPARING RUBBER-COPOLYMER AND ABS RESIN COMPRISING THEREOF}

The present invention relates to a method for producing a rubber polymer and an ABS resin comprising the same, and more particularly, a rubber polymer including an inner layer and an outer layer inhibits a graft polymer from penetrating into the rubber polymer when the ABS graft polymer is manufactured. The present invention relates to a method for preparing a rubber polymer that can maximize the graft ratio on the surface of the rubber polymer, and at the same time significantly improve the colorability, impact resistance, tensile properties, and processability of the ABS resin, and an ABS resin containing the same. will be.

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.

In addition, the ABS-based resin is because the ABS graft polymer is not grafted on the surface of the rubber polymer, a portion of the ABS graft polymer penetrates into the rubber polymer, thereby preventing the shape of the rubber polymer from being controlled. Problem of not controlling the thickness of the. Such a problem causes a problem in that the physical properties of the quality are nonuniform in terms of the product to maintain uniform physical properties of the produced ABS-based resin.

On the other hand, the mechanical properties of the ABS resin are known to depend on the shape of the rubber polymer, the dispersed particle diameter or particle diameter distribution in the matrix resin, the amount of ABS graft polymer on the surface of the rubber polymer, the thickness of the graft layer, and the like. In particular, the impact resistance of the ABS resin is determined by these factors.

In general, the rubber polymer used in the ABS resin is mainly used in the range of 1500 ~ 5000 평균 average particle diameter in consideration of impact resistance and appearance characteristics (surface gloss). However, when the average particle diameter of the rubber polymer is 5000 Å or more, a large amount of coagulum is generated during the polymerization, and when the average particle size is 2500 Å or less, a low temperature impact resistance is lowered. Thus, a rubber polymer having an average particle diameter of 2500 to 5000 사용 is used. Good to do.

Therefore, ABS graft polymer can be used to prevent the penetration of the ABS graft polymer into the rubber polymer, and the rubber polymer can improve the colorability, impact resistance, tensile properties, processability, and appearance properties of the ABS resin. More research is needed.

In order to solve the problems of the prior art as described above, the present invention is used in acrylonitrile-butadiene-styrene (ABS) -based resin to prevent the ABS graft polymer from penetrating into the rubber polymer to improve the graft rate on the rubber polymer surface It is an object of the present invention to provide a rubber polymer and a manufacturing method capable of maximizing and at the same time improving the colorability, impact resistance, tensile properties, processability, and appearance properties of ABS resins.

Another object of the present invention is to provide a ABS-based resin having a multilayer structure including the rubber polymer, and an ABS resin having excellent colorability, impact resistance, tensile properties, processability, and appearance properties, including the graft polymer and the SAN resin. To provide.

In order to achieve the above object, the present invention is a rubber polymer,

a) The glass transition temperature (Tg) is at least 0 ℃, the average particle diameter is up to 2000 Å

   Phosphorus inner layer; And

b) The glass transition temperature (Tg) is up to -20 ℃, the average particle diameter is up to

   2500 ~ 5000 square outer layer

It provides a rubber polymer comprising a.

In addition, the present invention is a method for producing a rubber polymer,

a) emulsion polymerization of an ethylenically unsaturated monomer, so that the glass transition temperature (Tg) is at least

   To prepare an inner layer polymer having an average particle diameter of up to 2000 mm 3

   step;

b) emulsion-polymerizing the conjugated diene monomer to the inner polymer of step a)

   The maximum transition temperature (Tg) is -20 ℃ and the average particle diameter is up to 2500 ~ 5000

   Steps to prepare a thin outer layer

It provides a method for producing a rubber polymer comprising a.

The present invention also provides a multi-layer ABS graft polymer comprising a rubber polymer produced by the above method, a method for producing the same, and an ABS resin containing the ABS graft polymer.

Specifically, in the ABS graft polymer of the multilayer structure,

a) The glass transition temperature (Tg) is at least 0 ℃, the average particle diameter is up to 2000 Å

   Phosphorus inner layer; And

b) The glass transition temperature (Tg) is up to -20 ℃, the average particle diameter is up to

   2500 ~ 5000 square outer layer

It provides a multi-layer ABS graft polymer comprising a rubber polymer comprising a.

In the manufacturing method of the ABS graft polymer of the multilayer structure,

a) i) Emulsification polymerization of ethylenically unsaturated monomers to reduce the glass transition temperature (Tg)

      An inner layer of at least 0 ° C. and an average particle diameter of at most 2000 mm 3; And

  Ii) The glass transition temperature (Tg) is up to -20 ℃, the average particle diameter is up to

      2500 ~ 5000 square outer layer

   Preparing a rubber polymer comprising a;

b) an aromatic vinyl compound, a vinyl cyan compound, and

   Graphene monomer selected from the group consisting of these mixtures

   Step copolymerization

It provides a method for producing a multilayer ABS graft polymer comprising a.

In the ABS resin,

a) i) Emulsification polymerization of ethylenically unsaturated monomers to reduce the glass transition temperature (Tg)

      An inner layer of at least 0 ° C. and an average particle diameter of at most 2000 mm 3; And

  Ii) The glass transition temperature (Tg) is up to -20 ℃, the average particle diameter is up to

      2500 ~ 5000 square outer layer

  ABS graft polymerization of a multilayer structure comprising a rubber polymer comprising a

  sieve; And

b) styrene-acrylonitrile resins

It provides an ABS resin comprising a.

Hereinafter, the present invention will be described in detail.

The inner layer described below represents a seed portion which is usually expressed by emulsion polymerization of an ethylenically unsaturated monomer, and the outer layer is a shell portion which is usually expressed by emulsion polymerization of a conjugated diene monomer on the inner layer polymer which is the seed portion. To indicate. The rubber polymer also includes an inner layer which is a conventional seed portion and an outer layer which is a cell portion. In addition, the ABS graft polymer having a multi-layered structure is a rubber polymer comprising an inner layer and an outer layer, and an ABS grafted monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, and mixtures thereof on the surface of the rubber polymer. Graft polymer is shown. In addition, ABS resin represents the ABS resin which mixed the ABS graft polymer of the multilayered structure containing the rubber polymer containing the said inner layer and outer layer, and SAN resin.

The present invention maintains the morphology of the rubber polymer used in the ABS resin uniformly to solve the quality deviation during production, can maximize the graft of the ABS graft polymer on the rubber polymer surface, as well as impact resistance and colorability While studying this excellent rubber polymer, the inner layer and the glass transition temperature having a glass transition temperature (Tg) of at least 0 ° C. and an average particle diameter of up to 2000 kPa were obtained by varying the components of the inner layer polymer and the outer layer polymer, respectively. As a result of preparing a rubber polymer containing an outer layer having an average particle diameter of 20 ° C. and a maximum particle size of 2500 to 5000 mm 3, and producing an ABS resin, the ABS graft polymer can be prevented from penetrating into the rubber polymer. In addition, it was confirmed that the colorability, impact resistance, tensile properties, processability, and appearance properties of the ABS resin were remarkably improved, and based on this, the present invention was completed. It was good.

The present invention is a rubber polymer containing an inner layer having a glass transition temperature (Tg) of at least 0 ° C. and 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 to 5000 kPa. And to provide a method of manufacturing, a multi-layered ABS graft polymer comprising the same, and an ABS resin.

The present invention is a method for producing a rubber polymer by emulsion polymerization of an ethylenically unsaturated monomer to produce an inner layer polymer having a glass transition temperature (Tg) of at least 0 ° C. and an average particle diameter of at most 2000 kPa, and then conjugated to the inner layer polymer. Emulsification polymerization of the diene monomer, characterized in that for producing an outer layer polymer having a glass transition temperature of at least 20 ℃, the average particle diameter of 2500 ~ 5000 kPa. In addition, the polymer for the outer layer is characterized in that the polymerization is carried out by the partial polymerization of the monomers in a batch polymerization, and then the remaining monomers in a batch or continuous continuous administration to emulsion polymerization.

The rubber latex of the present invention can be produced by the following method.

a) Preparation of polymer for inner layer

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

The inner layer is in the reactor iii) 100 parts by weight of ethylenically unsaturated monomers, ii) 0 to 40 parts by weight of aliphatic conjugated diene monomers, iii) 0.1 to 10 parts by weight of graft crosslinkers or crosslinkers, iii) 1 to 4 parts by weight of emulsifiers, 1) 0.1 to 3 parts by weight of a polymerization initiator, iii) a maximum of 2 parts by weight of an electrolyte, and iii) 300 to 450 parts by weight of ion-exchanged water, and then reacting at a temperature of 60 to 80 ° C. for 2 to 4 hours. have.

The ethylenically unsaturated monomer of the above-mentioned i) can be used individually or in mixture of 2 or more types of aromatic vinyl compound, vinyl cyan compound, acrylic acid ester, or methacrylic acid ester.

In addition, in order to make the glass transition temperature of an inner layer into 0 degreeC or more, it is good to mix and use the ethylenically unsaturated monomer of (i) and the conjugated diene monomer of ii). The conjugated diene monomer mixed with the ethylenically unsaturated monomer is preferably used in an amount of up to 40 parts by weight.

The graft crosslinking agent or crosslinking agent of (iii) may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the ethylenically unsaturated monomer. The graft crosslinking agent may be allyl methacrylate, or triallyl isocyanurate, and the crosslinking agent may be ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate. , 1,4-butylene glycol dimethacrylate, divinylbenzene and the like can be used.

The emulsifier of iii) may be used in an amount of 1 to 4 parts by weight based on 100 parts by weight of the ethylenically unsaturated monomer. The emulsifier 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 be used in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the ethylenically unsaturated monomer, and examples thereof may include water-soluble persulfate, peroxy compound, redox system, and 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 ℃.

The average particle size of the emulsion-polymerized inner layer under the above conditions is preferably 2000 kPa (0.2 μm) or less in consideration of the average particle diameter of the final rubber latex.

b) Manufacture of outer layer polymer

The outer layer at this stage

A) in the reactor

   Iii) 5 to 30 parts by weight of the inner layer;

   Ii) 30 to 60 parts by weight of the conjugated diene monomer;

   Viii) 1.5 to 4 parts by weight of emulsifier;

   Iii) 0.1 to 3 parts by weight of a polymerization initiator;

   Iii) 0.1 to 1 parts by weight of molecular weight modifier;

   Iii) 0.5 to 3 parts by weight of electrolyte; And

   I) 150 to 200 parts by weight of ion-exchanged water

   In a batch for 7 to 20 hours at a temperature of 60 to 80 ℃

   Emulsion polymerization; And

B) the reactants of step a)

   Iii) 20 to 50 parts by weight of the remaining conjugated diene compound monomers; And

   Ii) 0.1 to 1 part by weight of molecular weight modifier

   In a batch or continuous dose within 15 at a temperature of 60 to 80 ℃

   Emulsification step for 30 hours

  It may be prepared by a method comprising a.

The conjugated diene compound monomers of (a) ii) and (b) iii) have sufficient crosslinking, and the conjugated diene monomer having a sufficiently low glass transition temperature of -20 ° C. or less may be used alone, and may be mixed with a monomer copolymerizable therewith. It can also be used.

As the monomer copolymerizable with the conjugated diene compound monomer, an aromatic vinyl compound such as styrene or α-methylstyrene, or a vinyl cyan compound such as acrylonitrile 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 a) i) may be the same as those used in the manufacture 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 manufacture 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 monomer.

It is preferable to use mercaptans for the molecular weight modifiers of a) iii) and b) ii).

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 average particle diameter (including the inner layer) of the rubber polymer including the inner layer and the outer layer prepared according to the present invention is preferably 2500 to 5000 mm (0.25 to 0.5 µm).

The present invention is a multilayer prepared by a method comprising graft copolymerization of a monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, and mixtures thereof in a rubber polymer comprising an inner layer and an outer layer prepared as described above. It provides an ABS graft polymer of structure.

The multilayer ABS graft polymer is

a) 30 to 70 parts by weight of a rubber polymer including an inner layer and an outer layer;

b) 15 to 30 parts by weight of an aromatic vinyl cyan 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.

When preparing the ABS graft polymer having a multilayer structure, the 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 generation of coagulated products, the monomer may be divided in multiple stages. The administration method or 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, sulfuric acid first Oxidation-reduction catalysts which are mixtures of reducing agents such as iron, dextrose, sodium pyrrolate, sodium sulfite and the like can be used.

In addition, an antioxidant and a stabilizer are administered to the multilayered ABS graft polymer 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.

The rubber polymer including the inner layer and the outer layer of the present invention has an effect of maximizing the graft rate on the surface of the rubber polymer by inhibiting the graft polymer from penetrating into the rubber polymer when manufacturing the ABS graft polymer having a multilayer structure.

In another aspect, the present invention provides an ABS resin prepared by mixing the above-described multilayer ABS graft polymer 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.

ABS-based resins prepared as described above have excellent effects on colorability, impact resistance, tensile properties, and workability.

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

Examples 1-4. Manufacture of inner layer polymer

Example 1

150 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 100 parts by weight of styrene as an ethylenically unsaturated monomer, 1.5 parts by weight of potassium oleate as an emulsifier, 3 parts by weight of allyl methacrylate as a graft crosslinker, and 0.3 parts of potassium persulfate as a polymerization initiator. Parts by weight were administered in batches. 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.

Examples 2-5

An inner layer polymer was prepared in the same manner as in Example 1, except that the same components and composition ratios as in Table 1 were used in Example 1.

Experimental Example 1

Using the polymer for the inner layer prepared in Examples 1 to 5, the glass transition temperature and the particle diameter were measured by the following method, and the results are shown in Table 1 below.

A) glass transition temperature (DSC)-obtained by solidifying the prepared inner layer with sulfuric acid

    11 mg of powder was heated up to 150 degreeC on DSC, and then 150 degreeC to -40 degreeC

    After cooling to / min to remove the thermal history, increase to 10 ℃ / min again

    It was turned on to measure the glass transition temperature.

B) Drop size and drop size distribution-by dynamic laser light

    Measured using Nicomp 370 HPL.

division Example 1 Example 2 Example 3 Example 4 Example 5 Ion exchange water 150 143 180 130 110 Monomer Styrene 100 72 72 80 80 1,3-butadiene - - - 20 20 Acrylonitrile - 28 28 - - Emulsifier Oleic acid potassium salt 1.5 2.1 3.5 2.5 1.0 Rosin acid potassium salt - 0.5 1.8 0.4 0.25 Graft crosslinking agent Allyl methacrylate 3 2.5 2.0 - - Divinylbenzene - - - One 0.8 Polymerization initiator Potassium persulfate 0.3 0.2 0.2 0.3 0.25 Glass transition temperature (Tg) 105 ℃ 107 ℃ 107 ℃ 61 ℃ 61 ℃ Average particle size of inner layer 1300 Å 1200 Å 700 Å 1100 Å 1800 Å

Examples 6-11. Manufacture of outer layer polymer and rubber polymer

Example 6

70 parts by weight of ion-exchanged water, 50 parts by weight of 1,3-butadiene as monomer, 1.0 part by weight of potassium oleate as emulsifier and potassium rosinate in 10 parts by weight of the inner layer polymer prepared in Example 1 in a nitrogen-substituted polymerization reactor 1.2 parts by weight of salt, 0.9 parts by weight of sodium carbonate and 0.8 parts by weight of potassium hydrogen carbonate, 0.25 parts by weight of tertiary dodecyl mercaptan (TDDM) with a molecular weight regulator, and 0.25 parts by weight of potassium persulfate with a polymerization initiator, followed by 70 ° C The reaction was carried out at a reaction temperature of 9 hours. 40 parts by weight of the remaining monomer 1,3-butadiene, and 0.03 parts by weight of tertiary dodecylmercaptan with a molecular weight regulator were continuously administered for 7 hours and reacted at 75 ° C. for 19 hours, and then the reaction was terminated to prepare a rubber polymer. .

Example 7

70 parts by weight of ion-exchanged water, 10 parts by weight of ion-exchanged water, 72 parts by weight of 1,3-butadiene as monomer, 1.0 part by weight of potassium oleate as emulsifier and potassium rosinate in 10 parts by weight of the inner layer polymer prepared in Example 1 in a nitrogen-substituted polymerization reactor. 1.2 parts by weight of salt, 0.9 parts by weight of sodium carbonate and 0.8 parts by weight of potassium hydrogen carbonate, 0.25 parts by weight of tertiary dodecyl mercaptan (TDDM) with a molecular weight regulator, and 0.25 parts by weight of potassium persulfate with a 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 collectively administered for 7 hours to react at 75 ℃ for 27 hours, and then the reaction was terminated to prepare a rubber polymer. .

Examples 8-11

A rubber polymer was prepared in the same manner as in Example 2, except that the same ingredients and composition ratios as in Table 2 were used in Example 6.

Comparative Example 1

75 parts by weight of ion-exchanged water, 80 parts by weight of 1,3-butadiene as monomer, 1.2 parts by weight of potassium oleate salt and 1.5 parts by weight of potassium rosin salt as emulsifier, sodium carbonate as electrolyte ₂ CO ₃ ) 0.7 parts by weight and 0.8 parts by weight of potassium hydrogen carbonate (KHCO ₃ ), 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) with a molecular weight regulator, 0.3 parts by weight of potassium persulfate with an initiator, and then 70 ℃ The reaction was carried out for 15 hours at the reaction temperature. 20 parts by weight of the remaining monomers 1,3-butadiene, and 0.05 parts by weight of tertiary dodecylmercaptan with a molecular weight modifier were collectively reacted at a reaction temperature of 75 ° C. for 28 hours, and then the reaction was completed to prepare a rubber polymer. .

Experimental Example 2

Using the rubber polymer prepared in Examples 6 to 11 and Comparative Example 1, the particle size and the particle size distribution were measured by the method of using Nicomp 370 HPL by the dynamic laser light scattering method, and the results are shown in Table 2 below. Shown in

division Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Inner layer 10 parts by weight of the inner layer of Example 1 10 parts by weight of the inner layer of Example 1 9 parts by weight of the inner layer of Example 2 9 parts by weight of the inner layer of Example 3 6 parts by weight of the inner layer of Example 4 17 parts by weight of the inner layer of Example 5 - Dosing method Batch administration Ion exchange water 70 70 73 72 76 74 75 1,3-butadiene 50 72 68 50 60 43 80 Oleic acid potassium salt One One 1.1 0.4 One 0.9 1.2 Rosin acid potassium salt 1.2 1.2 1.4 1.5 1.5 1.4 1.5 Sodium carbonate 0.9 0.9 0.8 1.2 0.9 1.0 0.7 Potassium bicarbonate 0.8 0.8 0.7 1.3 0.8 1.1 0.8 Class 3 dodecyl mercaptan 0.25 0.25 0.3 0.2 0.2 0.28 0.3 Potassium persulfate 0.25 0.25 0.3 0.25 0.25 0.29 0.3 Dosing method 9 hours after start of continuous dosing reaction 13 hours after the start of the batch administration reaction 13 hours after the start of the batch administration reaction 9 hours after the start of the batch administration reaction 11 hours after the start of the batch administration reaction 10 hours after the start of the batch administration reaction 15 hours after the start of the batch administration reaction 1,3-butadiene 40 18 23 41 34 40 20 Class 3 dodecyl mercaptan 0.03 0.03 0.02 0.03 0.03 0.03 0.05 Average particle size 3000 3100 3000 3100 3300 3500 3300

Examples 12-17. Manufacture of Multi-layer ABS Graft Polymer

Example 12

65 parts by weight of ion-exchanged water, 0.1 parts by weight of sodium ethylenediaminetetraacetate, 0.005 parts by weight of ferrous sulfate, formaldehyde, in 50 parts by weight of a rubber polymer including an inner layer and an outer layer, prepared in a nitrogen-substituted polymerization reactor. 0.23 parts by weight of sodium sulfoxylate and 0.35 parts by weight of potassium rosinate were collectively administered, and then the temperature was raised to 70 ° C. 50 parts by weight of ion-exchanged water, 0.65 parts by weight of potassium rosinate, 35 parts by weight of styrene, 15 parts by weight of acrylonitrile, 0.4 parts by weight of tertiary dodecyl mercaptan, and 0.4 parts by weight of diisopropylenebenzenehydroperoxide The solution was continuously administered for 3 hours, the temperature was raised to 80 ° C., and then aged for 1 hour to terminate the reaction, thereby obtaining an ABS graft polymer having a multilayer structure. The polymerization conversion rate of the ABS graft polymer of the multilayer structure obtained at this time was 98%, the graft rate was 40%, and the product coagulant ratio was about 0.25%.

Examples 13-17

In Example 12, except that only the rubber polymer including the inner layer and the outer layer was carried out in the same manner as in Example 12, except that as shown in Table 3 to produce a multi-layer ABS graft polymer.

Comparative Example 2. ABS Graft Polymer Preparation

The same procedure as in Example 10 was repeated except that the rubber polymer prepared in Comparative Example 1 was used instead of the rubber polymer prepared in Example 10 to Example 5.

Examples 18 to 23, and Comparative Example 3. ABS resin production

30 parts by weight of a powder obtained by washing the multilayered ABS graft polymer prepared in Examples 12 to 17 and Comparative Example 2 by coagulating with an aqueous sulfuric acid solution and a styrene-acrylonitrile copolymer (SAN resin, LG Chemical Products) , Product name: 92HR) 70 parts by weight of the mixture was put in a mixer, pelletized by using an extruder and then prepared by using an injection machine.

Experimental Example 3

After preparing the TEM specimens of the resins prepared in Example 18 and Comparative Example 3, the TEM was measured and the results are shown in FIGS. 1 and 2.

As shown in Figure 1 and 2, when manufacturing the ABS-based resin using the rubber polymer of Example 10 according to the present invention there is no internal penetration of the ABS graft polymer, while the general rubber polymer of Comparative Example 2 When the ABS-based resin was prepared, it was confirmed that the internal penetration of the ABS graft polymer occurred.

Experimental Example 4

The physical properties of the ABS specimens prepared in Examples 19 to 23 and Comparative Example 3 were measured by the following method, and the results are shown in Table 3 below.

A) Izod Impact Strength-The thickness of the specimen was measured by ASTM 256 method with 1/4 "thickness.

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 19 Example 20 Example 21 Example 22 Example 23 Comparative Example 3 ABS graft latex Graft Latex of Example 13 Graft Latex of Example 14 Graft Latex of Example 15 Graft Latex of Example 16 Graft Latex of Example 17 Graft Latex of Comparative Example 2 Izod impact strength (kgcm / cm) 31 32 30 33 31 30 Fluidity (g / 10min) 22 23 23 22 21 23 Tensile Strength (㎏ / ㎠) 478 482 480 478 483 480 Surface gloss (%) 96 93 94 93 96 94 Colorant Usage 0.12 0.11 0.12 0.13 0.11 0.23 Coloring L 30.8 30.4 30.6 30.9 30.7 30.6 Coloring a 52.9 53.1 53 53.1 53.3 53

Through Table 3, it can be confirmed that the ABS resin of Examples 19 to 23 prepared according to the present invention is superior to the Izod impact strength, fluidity, tensile strength, surface gloss, and colorability compared to the ABS resin of Comparative Example 3 there was.

The rubber polymer including the inner layer and the outer layer prepared according to the present invention can maximize the graft rate on the rubber polymer surface by inhibiting the graft polymer penetrates into the rubber polymer when the ABS graft polymer is prepared. In addition, the ABS-based resin including the ABS graft polymer having a multilayer structure including the rubber polymer has excellent colorability, impact resistance, tensile properties, and workability.

1 is a photograph showing a morphology of an ABS-based resin prepared using a rubber polymer including an inner layer and an outer layer prepared according to an embodiment of the present invention.

Figure 2 is a photograph showing the morphology of the ABS-based resin prepared using a general rubber polymer.

Claims (17)

delete delete delete delete delete delete delete delete delete delete delete In a multilayer ABS graft polymer, a) The glass transition temperature (Tg) is at least 0 ℃, the average particle diameter is up to 2000 Å    Phosphorus inner layer; And b) The glass transition temperature (Tg) is up to -20 ℃, the average particle diameter is up to    2500 ~ 5000 square outer layer ABS graft polymer of a multi-layer structure comprising a rubber polymer comprising a. The method of claim 12, a) i) Glass transition temperature (Tg) of at least 0 ° C and average particle diameter of up to 2000       Thin inner layer; And   Ii) The glass transition temperature (Tg) is up to -20 ℃, the average particle diameter is up to        2500 ~ 5000 square outer layer    Rubber polymer comprising; And b) an aromatic vinyl compound, a vinyl cyan compound, and    A monomer selected from the group consisting of mixtures thereof    Rafted polymer layer ABS graft polymer of a multi-layer structure comprising a. The method of claim 12, a) i) Glass transition temperature (Tg) of at least 0 ° C and average particle diameter of up to 2000       Thin inner layer; And   Ii) The glass transition temperature (Tg) is up to -20 ℃, the average particle diameter is up to        2500 ~ 5000 square outer layer    30 to 70 parts by weight of a rubber polymer including; b) iv) 15 to 30 parts by weight of an aromatic vinyl cyan compound; And   Ii) 10 to 25 parts by weight of a vinyl cyan compound ABS graft polymer of a multi-layer structure comprising a. In the manufacturing method of the ABS graft polymer of the multilayer structure, a) i) Emulsification polymerization of ethylenically unsaturated monomers to reduce the glass transition temperature (Tg)       An inner layer of at least 0 ° C. and an average particle diameter of at most 2000 mm 3; And   Ii) The glass transition temperature (Tg) is up to -20 ℃, the average particle diameter is up to       2500 ~ 5000 square outer layer    Preparing a rubber polymer comprising a; b) an aromatic vinyl compound, a vinyl cyan compound, and    Graphene monomer selected from the group consisting of these mixtures    Step copolymerization Method for producing a multi-layer ABS graft polymer comprising a. In ABS resin, a) i) Emulsification polymerization of ethylenically unsaturated monomers to reduce the glass transition temperature (Tg)       An inner layer of at least 0 ° C. and an average particle diameter of at most 2000 mm 3; And   Ii) The glass transition temperature (Tg) is up to -20 ℃, the average particle diameter is up to       2500 ~ 5000 square outer layer   ABS graft polymerization of a multilayer structure comprising a rubber polymer comprising a   sieve; And b) styrene-acrylonitrile resins ABS-based resin comprising a. The method of claim 16, a) 20 to 40 parts by weight of a multilayer ABS graft polymer; And b) 60 to 80 parts by weight of the SAN resin ABS-based resin comprising a.