KR100668691B1 - Rubber-copolymer and method for preparing thereof - Google Patents

Abstract

The present invention relates to a rubber polymer for methyl methacrylate-butadiene-styrene graft copolymer and a method for preparing the same, and in particular, by controlling the swelling degree of the rubber polymer stepwise to emulsify the conjugated diene compound and the ethylenically unsaturated monomer to have a swelling degree of 7 After preparing the inner layer latex, emulsion conjugated conjugated diene compound and ethylenically unsaturated monomer to the inner layer latex to prepare an outer layer having a swelling degree of at least 14 to significantly improve the impact resistance and whitening resistance of methyl methacrylate-butadiene-styrene graft copolymerization. The present invention relates to a body rubber polymer and a method for producing the same.

Swelling degree, rubber polymer, multilayer structure, methyl methacrylate-butadiene-styrene, MBS graft copolymer, impact modifier, vinyl chloride resin, impact resistance, whitening resistance

Description

Rubber polymer and its manufacturing method {RUBBER-COPOLYMER AND METHOD FOR PREPARING THEREOF}

The present invention relates to a rubber polymer for methyl methacrylate-butadiene-styrene graft copolymer and a method of manufacturing the same, and more particularly, to controlling the swelling degree of the rubber polymer to prepare a rubber polymer having a multilayer structure, thereby providing impact resistance and whitening resistance. A remarkably improved rubber polymer for methyl methacrylate-butadiene-styrene graft copolymer and a process for preparing the same are provided.

Methyl methacrylate-butadiene-styrene (MBS) resin is an additive used to improve impact resistance, whitening resistance, processability and optical properties of vinyl chloride resin, and MBS resin is methyl in styrene-butadiene rubber polymer. It is prepared by graft emulsion polymerization of methacrylate and styrene.

The physical properties of the MBS-based resin depend on the content of each monomer to be grafted and the polymerization method, and among them, the physical properties of the rubber polymer used as the substrate of the MBS-based resin are the most important factors. In particular, the size, content, composition of the composition, etc. of the rubber polymer used as the substrate of the MBS resin directly affects the optical properties of the vinyl chloride resin.

Accordingly, there have been many studies to control the physical properties of the rubber polymer for MBS resins, such as adjusting the glass transition temperature. For example, the effect of the deep portion of the MBS-based rubber polymer resin on whitening by controlling the glass transition temperature (Korean Patent Application No. 1986-0001212), and the glass transition temperature of the MBS resin rubber polymer through the multi-step polymerization method There is a method for producing a rubber polymer of the core-cell form improved by low temperature impact behavior. However, the method of controlling the physical properties of the rubber polymer for MBS resin by adjusting the glass transition temperature can improve the impact resistance and low temperature of the MBS resin, but there is a problem that the whitening resistance is still not improved.

In addition, US Patent No. 4,431,772 discloses a method of controlling the swelling degree and the refractive index of the rubber polymer, and US Patent No. 4,352,910 discloses a method of applying a multi-stage polymerization method. U.S. Patent No. 4,857,592 discloses a method for controlling stepwise grafted monomers. All of the above methods have in common that a crosslinking agent is used in the graft polymerization.

However, despite these efforts, the physical properties of vinyl chloride resin products containing graft particles are limited by the formation of protrusions such as undispersed fish-eye due to processing factors such as processing conditions. .

Therefore, there is a need for further research on the manufacturing method of the rubber polymer for MBS-based resin which can improve impact resistance and whitening resistance at the same time.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a rubber polymer for MBS resin having excellent impact resistance and whitening resistance.

Another object of the present invention is to provide a method for producing a rubber polymer for MBS resin that can simultaneously improve impact resistance and whitening resistance.

It is another object of the present invention to provide an MBS graft copolymer composition having excellent impact behavior and whitening resistance at the same time.

It is another object of the present invention to provide a method for preparing MBS graft copolymers which can not only improve impact behavior but also improve whitening resistance.

The present invention provides a vinyl chloride resin having excellent impact resistance and whitening resistance, including the graft copolymer and vinyl chloride resin.

In order to achieve the above object, the present invention

a) 50 to 95 parts by weight of the conjugated diene compound; And an inner layer having a swelling degree of up to 7 containing 10 to 90 parts by weight of the monomer including 5 to 50 parts by weight of ethylenically unsaturated monomer, and 0.1 to 5 parts by weight of the graft crosslinking agent; And

b) 50 to 95 parts by weight of the conjugated diene compound; And an outer layer having a swelling degree of at least 14 containing 10 to 90 parts by weight of the remaining monomers including 5 to 50 parts by weight of the ethylenically unsaturated monomer.

In addition, the present invention a) 50 to 95 parts by weight of the conjugated diene compound; And 10 to 90 parts by weight of the monomer comprising 5 to 50 parts by weight of ethylenically unsaturated monomer,

Emulsion polymerization under 0.1 to 5 parts by weight of the graft crosslinking agent to prepare an inner layer latex having a swelling degree of up to 7; And

b) emulsion-polymerizing the remaining 10 to 90 parts by weight of the remaining monomers at the time when the polymerization conversion rate is 90% by weight or more to the inner layer latex of step a) to prepare an outer layer having at least 14 swelling degrees located outside the inner layer.

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

In addition, the present invention

a) iv) 50 to 95 parts by weight of the conjugated diene compound; And an inner layer having a swelling degree of up to 7 containing 10 to 90 parts by weight of the monomer including 5 to 50 parts by weight of ethylenically unsaturated monomer, and 0.1 to 5 parts by weight of the graft crosslinking agent; And

  Ii) 50 to 95 parts by weight of the conjugated diene compound; And an outer layer having an swelling degree of at least 14 containing 10 to 90 parts by weight of the remaining monomers including 5 to 50 parts by weight of ethylenically unsaturated monomers.

b) aromatic vinyl compounds;

c) vinylcyan compounds; And

d) methyl methacrylate

It provides a MBS graft copolymer composition comprising a.

In addition, the present invention provides a method for producing MBS graft,

a) iii) conjugated diene compound; Ethylenically unsaturated monomers; And an inner layer having a swelling degree of up to 7 containing 0.1 to 5 parts by weight of a graft crosslinking agent; And

  Ii) conjugated diene compounds; Ethylenically unsaturated monomers; And a rubber polymer having an outer layer having a swelling degree of at least 14 containing 0.1 to 5 parts by weight of a graft crosslinking agent. And

b) graft copolymerizing an aromatic vinyl compound, a vinyl cyan compound, and methyl methacrylate on the rubber polymer of step a)

It provides a method for producing a MBS graft copolymer comprising a.

In addition, the present invention

a) iv) 50 to 95 parts by weight of the conjugated diene compound; And an inner layer having a swelling degree of up to 7 containing 10 to 90 parts by weight of the monomer including 5 to 50 parts by weight of ethylenically unsaturated monomer, and 0.1 to 5 parts by weight of the graft crosslinking agent; And

   50 to 95 parts by weight of the conjugated diene compound; And an outer layer having an swelling degree of at least 14 containing 10 to 90 parts by weight of the remaining monomers including 5 to 50 parts by weight of ethylenically unsaturated monomers.

  Ii) aromatic vinyl compounds;

  Iii) a vinylcyan compound; And

  Iii) methyl methacrylate

  MBS graft copolymer comprising a; And

b) vinyl chloride resin

It provides a vinyl chloride-based 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 the conjugated diene compound and the ethylenically unsaturated monomer, and the outer layer is emulsion-polymerized the conjugated diene compound and the ethylenically unsaturated monomer to the inner layer latex, which is the seed portion. It shows the shell part to express normally located outside. The rubber polymer also includes an inner layer which is a conventional seed portion and an outer layer which is a shell portion. In addition, the MBS graft copolymer is an MBS graft obtained by grafting a monomer selected from the group consisting of a rubber polymer including an inner layer and an outer layer and an aromatic vinyl compound, a vinyl cyan compound, and methyl methacrylate on the surface of the rubber polymer. The copolymer is shown. In addition, MBS-based resin represents MBS-based resin mixed with a vinyl chloride resin and MBS graft copolymer comprising a rubber polymer comprising the inner layer and the outer layer.

The inventors of the present invention while studying a method that can improve the impact resistance and whitening resistance of the rubber polymer for MBS-based resin at the same time, when the whitening degree is improved according to the swelling degree, the impact strength deteriorates, when the impact strength is improved In view of the problem that the degree of deterioration occurs, by adjusting the degree of swelling of the rubber polymer to prepare a rubber polymer including an inner layer and an outer layer, and graft polymerization of an aromatic vinyl compound, vinyl cyan compound, methyl methacrylate, etc. As a result of preparing the MBS graft copolymer having a multilayer structure, it was confirmed that the impact resistance and the whitening resistance could be improved at the same time, and thus, the present invention was completed.

The present invention provides a rubber polymer containing an inner layer having a swelling degree of up to 7 containing a conjugated diene compound and an ethylenically unsaturated monomer, and an outer layer having a swelling degree of at least 14 containing a conjugated diene compound and an ethylenically unsaturated monomer, and a method for preparing the same, the rubber polymer It is to provide a MBS graft polymer and a vinyl chloride-based resin comprising.

According to the present invention, in the method for preparing a rubber polymer, an emulsion-polymerized conjugated diene compound and an ethylenically unsaturated monomer are prepared to prepare an inner layer latex having a swelling degree of 7. The emulsion layer polymerizes the conjugated diene compound and an ethylenically unsaturated monomer to the inner layer latex, An outer layer having an swelling degree of at least 14 located on the outside is produced. In addition, the MBS graft copolymer of the present invention is characterized by being prepared by grafting an aromatic vinyl compound, a vinyl cyan compound, methyl methacrylate and the like to the rubber polymer.

The rubber polymer of the present invention emulsifies and polymerizes 10 to 90 parts by weight, preferably 15 to 60 parts by weight, of 100 parts by weight of the conjugated diene compound and the ethylene aromatic compound, which are added during the preparation of the rubber polymer, to obtain an inner layer latex having a swelling degree of up to 7. After the preparation, the inner layer latex is emulsified in the remaining conjugated diene compound and 10 to 90 parts by weight, preferably 40 to 85 parts by weight of the ethylene aromatic compound to prepare an outer layer having an swelling degree of at least 14 located outside of the inner layer. Are manufactured.

The rubber polymer of the present invention has various physical properties depending on the time point at which the polymer is administered to the conjugated diene compound, the ethylenically unsaturated monomer, and the graft crosslinking agent. In addition, the degree of swelling of the inner and outer layers is controlled by the ethylenically unsaturated monomer and graft crosslinker content in the multi-stage rubber polymer manufacturing process.

Referring to the manufacturing method of the rubber polymer of the present invention in detail.                     

a) inner layer latex manufacture

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

The inner layer may be prepared by emulsion polymerization of a conjugated diene compound, an aliphatic conjugated diene compound, a graft crosslinking agent, an emulsifier, a polymerization initiator, an electrolyte, and ion exchanged water.

The ethylenically unsaturated monomer may be included at least 20 parts by weight or more, and more preferably 30 parts by weight or more, based on 100 parts by weight of the monomer to be introduced during preparation of the inner layer. If the content is less than 20 parts by weight, it is not possible to maintain whitening resistance improvement properties.

As the conjugated diene compound, 1,3-butadiene, isoprene, chloroprene, pyrrylene, or a comonomer thereof may be used, and preferably 1,3-butadiene is used.

As the ethylenically unsaturated monomer, 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.

The graft crosslinking agent is preferably included in 0.1 to 5 parts by weight based on the monomer. If the content is less than 0.1 part by weight, the swelling degree of the rubber is increased, the improvement effect of the whitening resistance can not be expected.

The graft crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, triethylene glycol dimethacrylate, aryl methacrylate, 1,3-butylene glycol di An acrylate, a propylene glycol dimethacrylate, 1, 4- butylene glycol dimethacrylate, etc. can be used.

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 may be a water-soluble persulfate, a peroxy compound, an oxidation-reduction 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 is used to secure the stability of the rubber polymer, 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 polymerizable under conventional emulsion polymerization conditions and is not particularly limited, and is carried out until the polymerization conversion rate is 90% by weight or more.

Under the above conditions, the swelling degree of the emulsion-polymerized inner layer is preferably 7 at a weight ratio in which the coagulum absorbs toluene by drying the coagulum obtained by precipitating the rubber polymer in methyl alcohol and then immersing it in toluene for 24 hours.                     

b) outer layer manufacturing

The outer layer is prepared by the method of emulsion polymerization of a conjugated diene compound, an ethylenically unsaturated monomer, an emulsifier, a polymerization initiator, an electrolyte, and ion-exchanged water when the polymerization conversion rate of the inner layer is 90% by weight or more. Located outside of At this time, if necessary, the graft crosslinking agent may be further included in an amount of 0.1 to 5 parts by weight to perform polymerization.

The conjugated diene compound may be the same material as those used in the preparation of the inner layer.

The ethylenically unsaturated monomer may be included in an amount of 30 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the monomer to be added during the manufacture of the outer layer. When the content is more than 30 parts by weight, after being manufactured as an impact modifier due to an increase in the glass transition temperature (Tg) of the manufactured outer layer, there is a problem that the impact characteristics may be lowered.

The ethylenically unsaturated monomer may be the same material as those used in the preparation of the inner layer.

In addition, graft crosslinking agents, emulsifiers, polymerization initiators, and electrolytes used in the production of the outer layer may be the same as those used in the production of the inner layer.

The swelling degree of the emulsion-polymerized outer layer under the above conditions is preferably at least 14 by weight ratio of the coagulum absorbed toluene by drying the coagulum obtained by precipitating the rubber polymer in methyl alcohol, and then immersed in toluene for 24 hours.

In the present invention, in order to obtain a composition having excellent impact resistance and transparency at the same time, the monomer and the graft crosslinking agent may be divided into 1 to 4 cycles during the preparation of the outer layer, and may be polymerized in 1 to 4 steps while being continuously added to form the outer layer.

When the monomer is divided into two portions during the preparation of the outer layer by the multistage polymerization,

a) emulsifying and polymerizing 15 to 60 parts by weight of 100 parts by weight of the conjugated diene compound and the ethylenically unsaturated monomer, which are introduced during the preparation of the rubber polymer, to prepare an inner layer latex having a maximum swelling degree of 7;

b) emulsion-polymerizing 20 to 60 parts by weight of the conjugated diene compound and 100 parts by weight of the ethylenically unsaturated monomer in the inner layer latex of step a) to prepare a primary outer layer latex having a swelling degree of at least 14; And

c) emulsion-polymerizing 20 to 60 parts by weight of the conjugated diene compound and 100 parts by weight of the ethylenically unsaturated monomer in the primary outer layer latex of step b) to prepare a secondary outer layer having a swelling degree of at least 14.

The rubber polymer may be manufactured by a method including the same.

The rubber polymer prepared according to the present invention preferably has a refractive index in the range of 1.530 to 1.635 in order to be used as a rubber polymer for transparent MBS resin.

The present invention comprises a graft copolymerization of at least one monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and methyl methacrylate to a rubber polymer including an inner layer and an outer layer prepared as described above. To provide a MBS graft copolymer prepared by.

The MBS graft copolymer is

a) the above rubber polymer; b) aromatic vinylcyan compounds; c) vinyl cyan compound moiety; d) methyl methacrylate; e) 0.6 to 2.0 parts by weight of an emulsifier; f) 0.2 to 1.0 parts by weight of molecular weight modifier; And g) 0.05 to 0.5 parts by weight of the polymerization initiator is preferably prepared by graft copolymerization.

In the preparation of the MBS graft copolymer, the monomers may be added in a method of totally administering each component, in a multi-stage divided administration, or in a continuous administration. In particular, when multi-stage divided administration, It may be added in different contents.

The monomer is preferably added in such a way that the refractive index of the final rubber polymer is the same as that of the vinyl chloride resin, and it is particularly preferable that the refractive index is less than ± 0.003 based on the vinyl chloride resin.

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, and the methyl methacrylate of d). As the acrylate, a methyl methacrylate, ethyl acrylate, butyl acrylate monomer or the like of divinylbenzene alkyl acrylate can be used.

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

As the molecular weight modifier of f), tertiary dodecyl mercaptan may be used.

The polymerization initiator of g) is a peroxide such as tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, persulfate, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, and 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, an acid, or a salt is added to the MBS graft copolymer prepared as described above, followed by heat treatment, followed by dehydration and drying in a centrifuge to obtain a MBS graft copolymer in powder form.

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 rubber polymer surface by inhibiting the graft polymer penetrates into the rubber polymer when manufacturing the MBS graft polymer.

In another aspect, the present invention provides a vinyl chloride-based resin prepared by mixing the MBS graft copolymer with a vinyl chloride resin.

The vinyl chloride-based resin prepared as described above has an effect excellent in impact resistance and whitening 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

(Layer Inner Latex)

In a 120 L high-pressure polymerization vessel equipped with a stirrer, 180 parts by weight of ion-exchanged water, 0.5 parts by weight of buffer solution, 0.8 parts by weight of potassium oleate as emulsifier, 0.065 parts by weight of sodium pyrophosphate, 0.0047 parts by weight of ethylenediamine tetrasodium acetate, polymerization As an initiator, 0.003 parts by weight of ferrous sulfate, 0.02 parts by weight of sodium formaldehyde sulfoxylate, and 0.11 parts by weight of diisopropylbenzene hydroperoxide were added. Then, 12 parts by weight of butadiene, 36 parts by weight of styrene, and 2 parts by weight of divinylbenzene with a graft crosslinking agent were added and reacted at a reaction temperature of 35 ° C., when the polymerization conversion of the monomer was measured to be 90% by weight or more. (Measured by Gravimetric Method) The reaction was terminated to prepare an inner layer latex having a swelling degree of five.

(Outer layer production)

50 parts by weight of butadiene as a monomer, 0.2 parts by weight of potassium oleate as an emulsifier, 0.02 parts by weight of sodium formaldehyde sulfoxylate as a polymerization initiator and 0.11 parts by weight of diisopropylbenzene hydroperoxide were added to the inner layer latex, followed by polymerization for 10 hours. An outer layer of 950 mm 3 and swelling degree of 20 was produced. At this time, the polymerization conversion rate of the final rubber polymer was 98% by weight.

Example 2

(Layer Inner Latex)                     

Except for adding 12 parts by weight of butadiene and 37 parts by weight of styrene as a monomer, 1 part by weight of divinylbenzene as a graft crosslinking agent in Example 1 was carried out in the same manner as in Example 1 to the inner layer latex having a swelling degree of 7 Prepared.

(Outer layer production)

Except that 50 parts by weight of butadiene as a monomer to the inner layer latex was carried out in the same manner as in Example 1 to prepare an outer layer having an average particle diameter of 1000 kPa, swelling of 21. At this time, the polymerization conversion rate of the final rubber polymer was 99% by weight.

Comparative Example 1

(Layer Inner Latex)

12 parts by weight of butadiene and 38 parts by weight of styrene was added as a monomer in Example 1, except that the graft crosslinking agent was not added to prepare an inner layer latex having a swelling degree of 15.

(Outer layer production)

Except that 50 parts by weight of butadiene as a monomer to the inner layer latex was carried out in the same manner as in Example 1 to prepare an outer layer having an average particle diameter of 1000 mm 3, the degree of swelling of 25. At this time, the polymerization conversion rate of the final rubber polymer was 99% by weight.

Comparative Example 2

(Layer Inner Latex)

12 parts by weight of butadiene and 36 parts by weight of styrene as a monomer in Example 1 was added, except that the graft crosslinking agent was not added, the same procedure as in Example 1 was performed to prepare an inner layer latex having a swelling degree of 14. .

(Outer layer production)

An outer layer having an average particle diameter of 1000 mm and a swelling degree of 9 was carried out in the same manner as in Example 1 except that 50 parts by weight of butadiene was used as the monomer and 2 parts by weight of divinylbenzene as the graft crosslinking agent. Prepared. At this time, the polymerization conversion rate of the final rubber polymer was 99% by weight.

Comparative Example 3

(Layer Inner Latex)

Except for adding 50 parts by weight of butadiene as a monomer in Example 1, 2 parts by weight of the graft crosslinking agent was carried out in the same manner as in Example 1 to prepare an inner layer latex having a swelling degree of 8.

(Outer layer production)

Except for using 12 parts by weight of butadiene and 36 parts by weight of styrene as a monomer in the inner layer latex was carried out in the same manner as in Example 1 to prepare an outer layer having an average particle diameter of 950 mm 3, the swelling degree 11. At this time, the polymerization conversion rate of the final rubber polymer was 97% by weight.

Comparative Example 4

In a 120 L high-pressure polymerization vessel equipped with a stirrer, 180 parts by weight of ion-exchanged water, 0.5 parts by weight of buffer solution, 0.8 parts by weight of potassium oleate as emulsifier, 0.065 parts by weight of sodium pyrophosphate, 0.0047 parts by weight of ethylenediamine tetrasodium acetate, polymerization As an initiator, 0.003 part by weight of ferrous sulfate, 0.02 part by weight of sodium formaldehyde sulfoxylate, and 0.11 part by weight of diisopropylbenzene hydroperoxide were added. Then, 62 parts by weight of butadiene, 36 parts by weight of styrene and 2 parts by weight of divinylbenzene as a graft crosslinking agent were polymerized at a reaction temperature of 35 ° C. for 16 hours, and an average particle diameter of 950 mm 3 was obtained. Was prepared. At this time, when the polymer conversion rate of the monomer was 30% by weight and 70% by weight, 0.2 parts by weight of potassium oleate was further added as an emulsifier, respectively, and the final polymerization conversion of the finally obtained rubber polymer was 98% by weight.

Experimental Example 1

100 parts by weight of water, 0.0047 parts by weight of ethylenediamine tetrasodium acetate, 0.003 parts by weight of ferrous sulfate, and sodium formaldehyde sulfoxyl in 88 parts by weight of the rubber polymer solids prepared in Examples 1 or 2 and Comparative Examples 1 to 4 A rate of 0.02 part by weight and 0.13 part of potassium peroxide were added, followed by 12 parts by weight of methyl methacrylate. The mixture was heated at a temperature of 80 ° C. for 30 minutes and polymerized for 60 minutes to give an MBS graft copolymer. The obtained MBS graft copolymer was stirred with antioxidant, magnesium sulfate salt, and heat to separate the copolymer and water, followed by dehydration and drying to obtain MBS graft copolymer powder.

100 parts by weight of polyvinyl chloride (polymerization degree 180), 1.8 parts by weight of tanmalate stabilizer, 1.5 parts by weight of internal lubricant, in 7 parts by weight of the MBS graft copolymer powder of Examples 1 or 2, and Comparative Examples 1 to 4 obtained above , A mixture of 0.4 part by weight of the external lubricant, 1.0 part by weight of the processing aid, and 0.5 part by weight of the blue pigment were added. The mixture was kneaded in a roll-mill at 190 ° C. for 3 minutes to fully melt, and then made into a sheet of 0.5 mm thickness.

After measuring the physical properties by the following method using the sheet of Example 1 or 2, and Comparative Examples 1 to 4 prepared above, the results are shown in Table 1 below.

a) Whitening resistance-The prepared sheet was cut to 20 mm x 50 mm and measured at room temperature with a bending speed of 150 rpm and a bending angle of 130 °.

b) impact-measuring the rpm at which the non-saw blade part breaks when the prepared sheet is cut into 50 mm x 100 mm and the circular saw blade with a radius of 100 mm and a thickness of 1.5 mm is applied to the saw blade at 15 mm / sec. It was.

division Example Comparative example One 2 One 2 3 4 Polymerization stage Stage 1 butadiene 12 12 12 12 50 62 Styrene 36 37 38 36 - 36 Divinylbenzene 2 One - - 2 2 Tier 2 butadiene 50 50 50 50 12 - Styrene - - - - 36 - Divinylbenzene - - - 2 - - Swelling degree Stage 1 5 7 15 14 8 7 Tier 2 20 21 25 9 11 - Whitening resistance 600 700 500 20 300 150 Impact (rpm) Very good good Very bad good Bad good

Through the above Table 1, MBS graft copolymers of Examples 1 or 2 comprising a rubber polymer comprising an inner layer having a maximum swelling degree of 7 and an outer layer having a swelling degree of at least 14 according to the present invention. As compared with the coalescence, it was confirmed that the whitening resistance and the impact resistance were excellent.                     

Example 3

(Layer Inner Latex)

In a 120 L high-pressure polymerization vessel equipped with a stirrer, 180 parts by weight of ion-exchanged water, 0.5 parts by weight of buffer solution, 0.8 parts by weight of potassium oleate as emulsifier, 0.065 parts by weight of sodium pyrophosphate, 0.0047 parts by weight of ethylenediamine tetrasodium acetate, polymerization As an initiator, 0.003 parts by weight of ferrous sulfate, 0.02 parts by weight of sodium formaldehyde sulfoxylate, and 0.11 parts by weight of diisopropylbenzene hydroperoxide were added. Then, 20 parts by weight of butadiene, 20 parts by weight of styrene, 1.5 parts by weight of divinylbenzene as a graft crosslinking agent were added and reacted at a reaction temperature of 35 ° C., and when the polymerization conversion of the monomer was measured to be 90% by weight or more. (Measured by Gravimetric Method) The reaction was terminated to prepare an inner layer latex having a swelling degree of five.

(First outer layer latex production)

25 parts by weight of butadiene and 5 parts by weight of styrene, 0.2 parts by weight of potassium oleate as an emulsifier, 0.02 parts by weight of sodium formaldehyde sulfoxylate as a polymerization initiator and 0.11 parts by weight of diisopropylbenzene hydroperoxide were added to the inner layer latex. After the emulsion polymerization, the reaction was terminated when the polymerization conversion rate of the monomer was measured at 80% by weight or more to prepare a primary outer layer latex having a swelling degree of 12.

(2nd outer layer manufacture)

28.5 parts by weight of butadiene as a monomer, 0.2 parts by weight of potassium oleate as an emulsifier, 0.02 parts by weight of sodium formaldehyde sulfoxylate as a polymerization initiator and 0.11 parts by weight of diisopropylbenzene hydroperoxide were added to the primary outer layer latex, followed by polymerization for 6 hours. A secondary outer layer having an average particle diameter of 920 mm 3 and a degree of swelling of 18 was prepared. At this time, the polymerization conversion rate of the final rubber polymer was 98% by weight.

Comparative Example 5

(Layer Inner Latex)

Except not using the graft crosslinking agent in Example 3 was carried out in the same manner as in Example 1 to prepare an inner layer latex having a swelling degree of 15.

(First outer layer latex production)

A first outer layer latex having a swelling degree of 10 was prepared in the same manner as in Example 3 except that 25 parts by weight of butadiene and 5 parts by weight of styrene and 1.5 parts by weight of divinylbenzene were used as a graft crosslinking agent. Prepared.

(2nd outer layer manufacture)

28.5 parts by weight of butadiene as a monomer was added to the first outer layer latex, and a second outer layer having an average particle diameter of 950 mm 3 and a swelling degree of 18 was prepared in the same manner as in Example 3. At this time, the polymerization conversion rate of the final rubber polymer was 98% by weight.

Comparative Example 6

(Layer Inner Latex)

Except not using the graft crosslinking agent in Example 3 was carried out in the same manner as in Example 1 to prepare an inner layer latex having a swelling degree of 15.

(First outer layer latex production)

A first outer layer latex having a swelling degree of 25 was prepared in the same manner as in Example 3, except that 25 parts by weight of butadiene and 5 parts by weight of styrene were used as monomers in the inner layer latex.

(2nd outer layer manufacture)

Except that 28.5 parts by weight of butadiene as a monomer and 15 parts by weight of divinylbenzene as a graft crosslinking agent were used in the first outer layer latex. A tea outer layer was prepared. At this time, the polymerization conversion rate of the final rubber polymer was 98% by weight.

Experimental Example 2

70 parts by weight of the rubber polymer solids prepared in Examples 3 and Comparative Examples 5 or 6, 100 parts by weight of water, 0.0047 parts by weight of ethylenediaminetetrasodium acetate, ferrous sulfate 0.003 parts, sodium formaldehyde sulfoxylate 0.02 Parts by weight, and 0.13 parts by weight of potassium peroxide were added. A mixture of 3 parts by weight of styrene and 12 parts by weight of methyl methacrylate was added thereto at 80 ° C. for 30 minutes, followed by primary polymerization for 60 minutes. A mixture of 12 parts by weight of styrene and 3 parts by weight of ethyl acrylate was added to the primary polymer at 80 ° C. for 1 hour, followed by secondary polymerization for 120 minutes to obtain an MBS graft copolymer. The obtained MBS graft copolymer was stirred with antioxidant, magnesium sulfate salt, and heat to separate the copolymer and water, followed by dehydration and drying to obtain MBS graft copolymer powder.

100 parts by weight of polyvinyl chloride (polymerization degree 800), 1.8 parts by weight of tanmalate stabilizer, 1.5 parts by weight of internal lubricant, and 7 parts by weight of the MBS graft copolymer powder of Example 3 and Comparative Example 5 or 6 obtained above. A mixture of 0.4 part by weight of lubricant, 1.0 part by weight of processing aid and 0.5 part by weight of blue pigment was added. The mixture was kneaded in a roll-mill at 190 ° C. for 3 minutes to fully melt, and then made into a sheet of 0.5 mm thickness.

After measuring the physical properties in the same manner as in Experiment 1 using the sheet of Example 3, and Comparative Example 5 or 6 prepared above, the results are shown in Table 2 below.

division Example 3 Comparative Example 5 Comparative Example 6 Polymerization stage Stage 1 butadiene 20 20 20 Styrene 20 20 20 Divinylbenzene 1.5 - - Tier 2 butadiene 25 25 25 Styrene 5 5 5 Divinylbenzene - 1.5 - Tier 3 butadiene 28.5 28.5 28.5 Styrene - - - Divinylbenzene - - 1.5 Swelling degree Stage 1 5 15 15 Tier 2 12 10 25 Tier 3 18 18 15 Whitening resistance 550 200 250 Impact (rpm) Very good Bad Very bad

Through the above Table 2, MBS graft copolymer of Example 3 comprising a rubber polymer comprising an inner layer, a primary outer layer, and a secondary outer layer according to the present invention compared with the copolymer of Comparative Example 5 or 6 It was confirmed that the chemical resistance and impact resistance is excellent.

According to the present invention, not only the MBS graft copolymer having excellent whitening resistance and impact resistance can be produced, but also the control of the heat of polymerization reaction is better than that of the MBS graft copolymer including the rubber polymer polymerized in one conventional step. In addition, it has a uniform particle size distribution has an excellent optical properties of the vinyl chloride-based resin containing the final impact modifier.

Claims (15)

a) 50 to 95 parts by weight of the conjugated diene compound; And an inner layer having a swelling degree of up to 7 containing 10 to 90 parts by weight of the monomer including 5 to 50 parts by weight of ethylenically unsaturated monomer, and 0.1 to 5 parts by weight of the graft crosslinking agent; And b) 50 to 95 parts by weight of the conjugated diene compound; And an outer layer having an swelling degree of at least 14 containing 10 to 90 parts by weight of the remaining monomers including 5 to 50 parts by weight of ethylenically unsaturated monomers. The method of claim 1, The rubber polymer in which the said conjugated diene compound is selected from the group which consists of 1, 3- butadiene, isoprene, chloroprene, pyrrylene, and these comonomers. The method of claim 1, The rubber polymer in which the said ethylenically unsaturated monomer is selected from the group which consists of styrene, (alpha) -methylstyrene, acrylonitrile, acrylic acid ester, and methacrylic acid ester. The method of claim 1, The rubber polymer has a refractive index of 1.530 to 1.635. a) 50 to 95 parts by weight of the conjugated diene compound; And 10 to 90 parts by weight of the monomer comprising 5 to 50 parts by weight of ethylenically unsaturated monomer, Emulsion polymerization under 0.1 to 5 parts by weight of the graft crosslinking agent to prepare an inner layer latex having a swelling degree of up to 7; And b) emulsion-polymerizing the remaining 10 to 90 parts by weight of the remaining monomers at the time when the polymerization conversion rate is 90% by weight or more to the inner layer latex of step a) to prepare an outer layer having at least 14 swelling degrees located outside the inner layer. Method for producing a rubber polymer comprising a. The method according to claim 5, wherein the polymerization in step b) is performed further comprising 0.1 to 5 parts by weight of a graft crosslinking agent. The method of claim 5, The graft crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, triethylene glycol dimethacrylate, aryl methacrylate, 1,3-butylene glycol diacryl A method for producing a rubber polymer, wherein the rubber polymer is one or more selected from the group consisting of latex, propylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate. The method of claim 5, wherein the inner layer of a) is conjugated diene compound; Aliphatic conjugated diene compounds; Graft crosslinkers; Emulsifiers; Polymerization initiator; Electrolyte; And preparing a rubber polymer by emulsion polymerization of ion-exchanged water. The method of claim 8, And wherein said emulsifier is at least one 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 8, 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 A method for producing a rubber polymer selected from the group consisting of at least one. The method of claim 8, 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 a rubber polymer selected from the group consisting of PO ₄ , K ₂ HPO ₄ , and Na ₂ HPO ₄ . The method of claim 5, wherein the outer layer of b) is conjugated diene compound; Ethylenically unsaturated monomers; Emulsifiers; Polymerization initiator; Electrolyte; And preparing a rubber polymer by emulsion polymerization of ion-exchanged water. The method of claim 5, The conjugated diene compound and the ethylenically unsaturated monomer of step b) is divided into 1 to 4 times the rubber polymer production method. a) iv) 50 to 95 parts by weight of the conjugated diene compound; And an inner layer having a swelling degree of up to 7 containing 10 to 90 parts by weight of the monomer including 5 to 50 parts by weight of ethylenically unsaturated monomer, and 0.1 to 5 parts by weight of the graft crosslinking agent; And   Ii) 50 to 95 parts by weight of the conjugated diene compound; And an outer layer having an swelling degree of at least 14 containing 10 to 90 parts by weight of the remaining monomers including 5 to 50 parts by weight of ethylenically unsaturated monomers. b) aromatic vinyl compounds; c) vinylcyan compounds; And d) methyl methacrylate MBS graft copolymer composition comprising a. a) iv) 50 to 95 parts by weight of the conjugated diene compound; And an inner layer having a swelling degree of up to 7 containing 10 to 90 parts by weight of the monomer including 5 to 50 parts by weight of ethylenically unsaturated monomer, and 0.1 to 5 parts by weight of the graft crosslinking agent; And    50 to 95 parts by weight of the conjugated diene compound; And an outer layer having an swelling degree of at least 14 containing 10 to 90 parts by weight of the remaining monomers including 5 to 50 parts by weight of ethylenically unsaturated monomers.   Ii) aromatic vinyl compounds;   Iii) a vinylcyan compound; And   Iii) methyl methacrylate   MBS graft copolymer comprising a; And b) vinyl chloride resin Vinyl chloride-based resin comprising a.