KR20120024231A - Mbs graft copolymer, method for preparing the same and pvc composition containing the same - Google Patents

Abstract

PURPOSE: A methylmethacrylate-butadiene-styrene graft copolymer is provided to improve cohesion property discussed at increasing the content of rubber, with maintaining the transparency of a PVC resin. CONSTITUTION: A methylmethacrylate-butadiene-styrene graft copolymer comprises 76-86 weight% of a conjugated diene based rubber core, and 15-35 weight% of a graft shell which surrounds the rubber core, and includes an alkyl (meth)acrylate monomer, and methacrylic acid. The amount of the methacrylic acid is 1-30 weight% on the basis of 100 weight% of the graft shell. The conjugated diene rubber core additionally comprises 5-35 weight% of an ethylenically unsaturated aromatic compound.

Description

Methyl methacrylate butadiene styrenic graft copolymer, preparation method thereof, and PPC composition comprising the same {MBS Graft Copolymer, Method For Preparing The Same And PVC Composition Containing The Same}

The present invention relates to a methyl methacrylate-butadiene-styrene graft copolymer, a method for preparing the same, and a PVC composition comprising the same, and more particularly, to an MBS copolymer having improved latex stability, and a method for preparing the same. The present invention relates to a polyvinyl chloride resin composition having improved cohesiveness and impact resistance while maintaining transparency of PVC and increasing rubber content.

Vinyl chloride resin (PVC) is a general-purpose resin widely used in various fields because of its excellent physical and chemical properties. However, the vinyl chloride resin has a narrow processing temperature range due to its processing temperature close to the pyrolysis temperature, and also has a high melt viscosity and low fluidity, so that it adheres to the surface of processing equipment to form carbides, which degrades the quality of the final product. There is a problem.

Therefore, in order to improve the processability of vinyl chloride resin, the monomer composition of the methyl methacrylate-butadiene-styrene graft copolymer, which is conventionally used as an impact modifier of vinyl chloride resin, the molecular weight, the structure, or the graft polymerization Attempts have been made to change the method.

The physical properties of such MBS graft copolymers are known to be affected by the content and polymerization method of each monomer to be grafted, the content and particle size of the rubber latex used as a substrate. In order to improve the impact strength, it is a general method to increase the content and particle size of the rubber latex used as the substrate, but when such rubber latex is used in PVC resin, light scattering effect is increased by increasing the particle size of the graft copolymer particles for impact modifier. As a result, the transparency of the PVC resin is reduced and the refractive index difference between the PVC resin and the graft copolymer particles for the impact modifier is large or when the deformation is weak, the bonding strength between the MBS graft copolymer and the PVC resin for the impact modifier is weak. If the void) is easily generated, the impact strength and the whitening characteristics are rather deteriorated.

In particular, when the use of rubber latex is limited, it is already known that the impact on the transparency and impact strength of the product is very large depending on the content and method of the grafted monomer.

As described above, methods for manufacturing the MBS-based impact modifiers to improve the impact resistance of vinyl chloride resin are disclosed in US Patent Nos. 3,761,455, 4,443,585, 5,204,406, 5,294,659, and 5,599,854. These methods produced MBS-based graft copolymers by emulsion polymerization divided into three stages to have a core-shell structure and a non-uniform structure.

In addition, in order to improve the impact strength, a method of controlling the particle size of the rubber phase before graft polymerization and increasing the rubber content and polymerizing the final average particle size during the graft copolymer polymerization is also disclosed. However, in the process of improving the impact resistance when using such a method, there may be a problem that the transparency and whitening resistance, the glass transition temperature decrease and the refractive index changes.

In general, the impact resistance is improved when the copolymer is prepared through rubber particles having a large particle size or rubber content increase in the emulsion polymerization range, but it is difficult to secure sufficiently satisfactory transparency and whitening properties in applications requiring high transparency.

Therefore, it is urgent to develop impact modifiers that can improve the cohesive properties and impact resistance which are a problem when rubber content is increased while maintaining the transparency of PVC resin during processing.

The inventors of the present invention continue to solve the problems of the prior art as described above by using methacrylic acid as a comonomer in the alkyl (meth) acrylate monomer in the graft polymerization step content of rubber latex and crosslinker It is possible to control the glass transition temperature, the particle diameter, and in particular, it is easy to control the coagulation temperature when the rubber content is increased to confirm that the cohesive properties can be improved within the same conditions, and came to complete the present invention.

That is, an object of the present invention is to maintain the transparency of the PVC resin during processing, MBS-based copolymers, a method for producing the same and a vinyl chloride resin composition, which greatly improves the improvement of agglomeration properties and impact resistance, which is a problem when the rubber content is increased. I'm trying to provide.

In order to achieve the above object, the present invention

V) 65-85 wt% of the conjugated diene-based rubber core; And ii) 15 to 35% by weight of a graft shell formed around the rubber core and including an alkyl (meth) acrylate-based monomer and methacrylic acid, wherein the methacrylic acid is based on a total of 100% by weight of the graft shell. It provides an MBS graft copolymer, characterized in that contained in 1 to 30% by weight.

In addition,

Preparing a conjugated diene-based rubber core having an average particle diameter of 800 to 1300 mm 3;

Wrapping the conjugated diene-based rubber core and performing graft emulsion polymerization of the alkyl (meth) acrylate-based monomer and methacrylic acid to form a first shell; And

Surrounding the first shell and emulsion polymerizing an ethylenically unsaturated monomer to form a second shell having an average particle diameter of 1800 to 2300 mm 3; It provides a method for producing a MBS graft copolymer, characterized in that consisting of.

Further,

It provides a PVC composition excellent in cohesive properties and impact strength comprising 1 to 20% by weight of the MBS graft copolymer and 80 to 99% by weight of vinyl chloride resin.

Below. The present invention will be described in detail.

MBS-based graft copolymer of the present invention is iii) 65 to 85% by weight of the conjugated diene rubber core; And ii) 15 to 35% by weight of a graft shell formed by surrounding the rubber core and including an alkyl (meth) acrylate-based monomer and methacrylic acid, wherein the methacrylic acid ensures stability of latex during polymerization (polymerization). Without coagulation in the reaction) and after the final polymerization, the amount of coagulated matter is 800 ppm or less, and the final PSD characteristics are included in a good range of 1 to 30 wt% within a good range without significantly affecting final properties such as transparency and impact strength. It is done.

The conjugated diene rubber is preferably a rubber composed of one or more monomers selected from the group consisting of butadiene, isoprene, chloroisoprene, and the like, and preferably contains 5 to 35% by weight of an ethylenically unsaturated aromatic compound, more preferably about 25% by weight. It can be made by including more. The ethylenically unsaturated aromatic compound serves to adjust the refractive index, whitening resistance and impact strength of the SB-based rubber latex, the content and type thereof are changeable according to the desired physical properties.

The ethylenically unsaturated aromatic compound includes styrene, alphamethylstyrene, isopropenylnaphthalene, isopropenylnaphthalene, vinylnaphthalene, styrene in which at least one of each hydrogen of a benzene ring is substituted with an alkyl group of C ₁ to C ₃ , and a benzene ring. At least one of hydrogen may be one or more selected from the group consisting of styrene substituted with halogen.

The conjugated diene rubber may further include a crosslinkable vinyl monomer. The crosslinkable vinyl monomer is divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, aryl methacrylate And 1,3-butylene glycol diacrylate and the like.

The crosslinkable vinyl monomer is preferably included in 0.1 to 5% by weight or less based on the conjugated diene rubber, more preferably 0.1 to 2% by weight or less, wherein the crosslinkable monomer controls the crosslinking of the rubber latex. It plays a role. The conjugated diene rubber may be prepared through one or more reactions, but the composition of the monomers for each step is not particularly limited.

The graft shell is preferably composed of methacrylic acid and an alkyl (meth) acrylate-based monomer, and the ethylenically unsaturated aromatic compound may be formed by further including 60 wt% or less based on 100 wt% of the graft shell. In case of exceeding the above range, the prepared MBS graft copolymer has a problem in that compatibility with PVC resin is greatly decreased.

Since the graft shell requires an increase in refractive index in order for the manufactured MBS-based graft copolymer to be used for a transparent use, the graft shell is further added to the graft polymerization step including the methacrylic acid and the alkyl (meth) acrylate monomer. It may be prepared by including a graft polymerization step comprising an ethylenically unsaturated aromatic compound. In this case, the added content of the ethylenically unsaturated aromatic compound may be such that the refractive index of the MBS-based copolymer to be prepared is the same level as that of the PVC resin.

Accordingly, the graft shell may include a first graft layer made of the methacrylic acid and an alkyl (meth) acrylate monomer and a second graft layer made of an ethylene unsaturated aromatic compound.

The alkyl (meth) acrylate monomers are methyl methacrylate, n-butyl methacrylate, lauryl methacrylate, stearyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate It is preferable that it is at least one selected from the group consisting of. The use amount is preferably 40 to 45% by weight based on 100% by weight of the graft shell, in this case there is an effect of improving the amount of coagulation, impact strength and whitening resistance.

The MBS graft copolymer is 65 to 85% by weight of the butadiene rubber core, 1 to 30% by weight, preferably 5 to 15% by weight of the methacrylic acid, the alkyl (meth) acrylate monomer or The total weight of the alkyl (meth) acrylate-based monomer and the ethylenically unsaturated aromatic compound is preferably 40% by weight or less. The MBS-based graft copolymer prepared within this range prevents condensation of methacrylic acid from occurring. Gel formation can be prevented and transparency can be maintained. When the content exceeds 40% by weight, the prepared MBC graft copolymer is not preferable because it causes a problem of incompatibility with the PVC resin.

That is, when the MBS graft copolymer prepared according to the present invention is used as an impact modifier, it is excellent in improving the adhesion resistance and impact strength of the PVC composition.

In addition, the MBS-based graft copolymer production method of the present invention comprises the first step of producing a conjugated diene rubber core having an average particle diameter of 800 to 1300 mm 3; Wrapping the conjugated diene rubber core and graft-emulsifying the alkyl (meth) acrylate-based monomer and methacrylic acid to form a first shell; And a third step of covering the first shell and emulsifying the ethylenically unsaturated monomer to form a second shell having an average particle diameter of 1800 to 2300 mm 3, more preferably 1900 to 2100 mm 3; .

By using methacrylic acid monomer as a comonomer, it is possible to improve the coagulation temperature and increase coagulation by increasing the glass transition temperature (Tg) of the shell part, without using the conventional microaggregation method using an electrolyte such as acid or salt. The coagulation enlargement becomes possible and a new microaggregation method can be proposed.

In other words, when MBS-based graft copolymer is used as an impact modifier of PVC resin, the aggregation temperature decreases when rubber content is increased in the graft polymer due to an increase in graft efficiency and an increase in glass transition temperature (Tg) of the graft polymer. In this invention, the methacryl-based copolymer has the characteristics of transparency and processability according to the difference in refractive index, because it can contribute to the formation of stability and more precise shell structure on the surface of the polymer latex according to the carboxylic acid group of methacrylic acid. It is possible to improve the impact strength and the flocculation temperature without damaging.

At this time, it is preferable to use anionic, amphoteric and nonionic surfactants that exhibit good stability to acids or bases as the surfactant when forming the first graft layer, and among them, polyoxyethylene sorbitan fatty acid ester series (Polyoxyethylene sorbitan). Among the fatty acid esters, polysorbate 80, polystyrene glycol dodecyl ether and alkyldiphenyl disulfonate show good stability, especially alkyldiphenyl disulfonate. The use of is more preferred, as demonstrated in the examples below when considering industrial applications. The amount of the alkyldiphenyl disulfonate used is preferably 0.1 to 1.0% by weight, and according to the polymerization conditions, it is preferable to use a minimum content that is easy to mix during polymerization, and more preferably 0.2 to 0.5% by weight.

In addition, the first graft layer is more preferably corrected to pH 9 to 10 by further including potassium hydroxide solution for the purpose of solving the pH degradation that may occur in the process of using the methacrylic acid monomer as a comonomer. Do.

In addition, the method for producing the MBS-based copolymer is to prepare a second graft shell by making the graft shell as a first graft shell as necessary, and injecting a styrene monomer into the first graft shell and graft polymerization. The method may further include a step, in which case the MBS-based graft copolymer prepared may have suitable physical properties to be used as a transparent impact modifier.

The graft polymerization is not particularly limited, but may be emulsion polymerization, and the reaction conditions, the reaction medium, the emulsifier, the initiator, and the like may be selected and controlled within a conventional range, and may include two or more polymerization steps.

The vinyl chloride resin (PVC) composition having excellent cohesive properties and impact strength of the present invention is characterized by comprising 1 to 20% by weight of the MBS graft copolymer and 80 to 99% by weight of vinyl chloride resin. The PVC resin composition may include additives such as antioxidants, heat stabilizers, plasticizers, colorants and lubricants known in the art, if necessary.

In summary, according to the prior art in which only styrene and methacrylic acid are copolymerized through bulk or solution polymerization, gel formation by condensation reaction of methacrylic acid cannot be prevented without an operation by a special addition device. And even when the methacrylic acid is used as the co-monomer in the alkyl (meth) acrylate-based monomers only by the above-described content control, the condensation reaction of methacrylic acid does not occur, it is possible to prevent gel formation and maintain transparency.

As described above, according to the present invention, MBS-based copolymer having improved latex stability, a method for preparing the same, and vinyl chloride having excellent cohesiveness and impact resistance, which are a problem when rubber content is increased while maintaining transparency of PVC. There is an effect of providing a resin composition.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely illustrative of the present invention and various changes and modifications within the scope and spirit of the present invention will be apparent to those skilled in the art. It is natural that modifications and variations fall within the scope of the appended claims.

Example  One

< Conjugated diene system  Rubber Latex Manufacturing>

The weight percentages of the following compounds are based on 100% by weight of the total monomers used for the preparation of conjugated diene rubber latex, and parts by weight are based on 100 parts by weight of the total monomers.

150 parts by weight of ion-exchanged water in a 120 L high-pressure polymerization vessel equipped with a stirrer, 0.5 parts by weight of buffer solution as an additive, 2.0 parts by weight of potassium oleate, 0.0047 parts by weight of ethylenediamine tetrasodium acetate, 0.003 parts by weight of ferrous sulfate, sodium form 0.02 parts by weight of aldehyde sulfoxy acid and 0.1 parts by weight of diisopropylbenzene hydroperoxide were initially charged.

75 wt% butadiene, 24 wt% styrene and 1 wt% divinylbenzene were polymerized at 50 ° C. for 18 hours to obtain a conjugated diene rubber latex, where the final polymerization conversion rate was 98% and the average particle diameter was 110%. nm.

< MBS system Graft  Preparation of Copolymer Latex>

The weight percentages of the following compounds are based on 100% by weight of the total amount of the conjugated diene-based rubber latex and the newly added monomers used for the preparation of MBS-based graft copolymer, the weight parts of the conjugated diene-based rubber latex and The total amount of the newly added monomer is shown based on 100 parts by weight.

74 wt% of the obtained conjugated diene-based rubber latex was added to a sealed reactor based on solid content, and thereafter, nitrogen was charged and 0.0094 parts by weight of ethylenediamine tetrasodium acetate, 0.006 parts by weight of ferrous sulfate, and sodium formaldehyde. after input sulfoxides acid 0.04 parts by weight of methyl methacrylate, 9.35% by weight, and methacrylic acid 1.65% by weight, alkyl diphenyl dimethyl sulfonate (alkyl diphenyl disulfonate: Dowfax) 0.3 parts by weight of ion-exchanged water 15 parts by weight, and 0.05 parts by weight of t-butylhydroperoxide and potassium hydroxide solution (content necessary for pH 9-10 correction) were thoroughly stirred and mixed, and then added for 10 minutes.

Then, the polymerization was carried out at 60 DEG C for 3 hours, followed by 15 weight% of styrene , 0.0094 weight part of ethylenediamine tetrasodium acetate, 0.006 weight part of ferrous sulfate, 0.04 weight part of sodium formaldehyde sulfoxylate, and 0.16 weight of potassium oleate. Part, 16 parts by weight of ion-exchanged water and 0.05 part by weight of t-butyl hydroperoxide were added, followed by polymerization at 60 ° C. for 2 hours to prepare MBS graft copolymer latex.

< MBS system Graft  Preparation of Copolymer Powder>

0.5 parts by weight of an antioxidant (Irganox-245) was added to 100 parts by weight of the prepared latex MBS graft copolymer (liquid phase), followed by agitation by adding an aqueous sulfuric acid solution while stirring, and then separating the copolymer and water at 70 ° C. Dehydration and drying gave MBS graft copolymer powder.

< PVC  Production of Resin Composition Sheet>

Sheet production of the PVC resin composition was carried out by producing a PVC resin masterbatch in order to facilitate processing. The specific PVC resin master batch is 100 parts by weight of PVC resin, 1.5 parts by weight of thermal stabilizer (Sn stearate), 1.0 part by weight of internal lubricant (calcium stearate), 0.5 part by weight of external lubricant (paraffin wax), processing aid (LG Chemical, PA) -910) 0.5 part by weight and 0.3 part by weight of pigment were prepared by sufficiently mixing at a temperature of 130 ° C. using a high speed stirrer and cooling.

8 parts by weight of the MBS-based graft copolymer powder was added to the prepared PVC resin masterbatch, and a sheet having a thickness of 0.5 mm for impact strength measurement was prepared using a roll at 195 ° C.

Example  2

Except for using methyl methacrylate in 9.9% by weight, and 1.1% by weight of methacrylic acid in Example 1 was carried out in the same manner as in Example 1.

Example  3

100 wt% butadiene is used in the preparation of the conjugated diene-based core in Example 1, styrene and divinylbenzene are not used, methyl methacrylate is 10.45 wt%, and methacrylic acid is 0.55 wt% in the graft polymerization. The same procedure as in Example 1 was carried out except that% was used.

Comparative example  One

Except for using methyl methacrylate in 11% by weight in Example 1, and not using methacrylic acid was carried out in the same manner as in Example 1.

Comparative example  2

Except for using methyl methacrylate as 7.7% by weight and methacrylic acid as 3.3% by weight in Example 1 and at the same time 10% by weight of styrene in the <manufacture of MBS graft copolymer latex> step It carried out in the same manner as in Example 1.

Comparative example  3

In Example 1 in a 5.5% by weight of methyl methacrylate, and methacrylic acid is 5.5, except that weight percent was carried out as Example 1.

Comparative example  4

In Example 1, methyl methacrylate is used at 15% by weight, methacrylic acid is not used, and at the same time, styrene is used at 12.75% by weight in the <manufacture of MBS graft copolymer latex> step. It was carried out in the same manner as in Example 1 except for using 2.25% by weight.

Comparative example  5

PVC sheet was prepared only by the PVC resin masterbatch of Example 1.

Comparative example  6

Example 3 was carried out in the same manner as in Example 3, except that methyl methacrylate was used at 26% by weight and methacrylic acid was not used.

[ Test Example ]

The properties of the PVC composition sheets prepared in Examples 1 to 3 and Comparative Examples 1 to 6 were measured by the following method, and the results are shown in Table 1 below.

* Particle size measurement: The particle size of the graft polymer was measured by dynamic laser light scattering method using Nicomp 380.

* Refractive index evaluation: Refractive index was measured at 25 degreeC using Abbe Refractometer.

* Evaluation of transparency: The sheets prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were prepared in a specimen of 3 mm thickness for measuring transparency of ASTM D1003 standard using a heat press at 130 ° C. and transparency using a Haze Meter. Haze values were measured. The transparency of the thermoplastic PVC resin composition preferably has a Haze value of 5.0 or less.

* Impact strength: by cutting the sheets prepared in Examples 1 to 3 and Comparative Examples 1 to 5 to produce a 10 cm x 16 cm specimen having a thickness of 0.5 mm and aged for 2 hours at 25 ℃ rotating a circular saw blade 15mm The rpm at which the specimen broke 50% when applied to the saw blade at a rate of / sec was measured. The higher the impact strength is, the better and preferably 1000 rpm or more.

* The amount of coagulum after polymerization: The content of the coagulum can be measured by drying the coagulum generated after graft polymerization with a sieve, and the amount of coagulum is preferably 1000 ppm or less, and the smaller the amount of coagulum, the better.

* Final PSD: The final obtained powder is filtered through a specific standard test sieve (C8.20032 Sieve, KS / ASTM mesh, No.20, ISO mesh 850 μm). The particle size distribution was confirmed by calculating the weight wt%.

* Average particle diameter: The average particle diameter of the graft polymer was measured by the dynamic laser light scattering method using Nicomp 380.

* Glass transition temperature: The Tg of the polymer was calculated using the Fox equation to calculate, for example, the Tg of the copolymers of monomers M1 and M2 (TGFox, Bull. Am. Physics Soc., Volumn 1 , Issue No. 3, page 123 (1956)):

1 / Tg (calculated value) = w (M1) / Tg (M1) = w (M2) / Tg (M2)

Where Tg (calculated value) is the glass transition temperature calculated for the copolymer, w (M1) is the weight fraction of monomer M1 in the copolymer, w (M2) is the weight fraction of monomer M2 in the copolymer, and Tg ( M1) is the glass transition temperature of the homopolymer of M1, Tg (M2) is the glass transition temperature of the homopolymer of M2, and all temperatures are represented by K.) The glass transition temperature of the homopolymer is, for example, literature ( Polymer handbook, edited by J. Brandrup and EH Immergut, Interscience publishers).

division Example Comparative example One 2 3 One 2 3 4 5 6 Sex Rubber
polymerization BD 75 75 100 75 75 75 75 - 100 SM 24 24 0 24 24 24 24 - 0 DVB One One 0 One One One One - 0 Rubber Average Particle Size ^* 1100 Graft
polymerization Rubber 74 74 74 74 74 74 74 - 74 First graft layer MMA 9.35 9.9 10.45 11 7.7 5.5 15 - 26 MAA 1.65 1.1 0.55 - 3.3 5.5 - - - Second graft layer SM 15 15 0 15 10 15 12.75 - 0 MMA - - - - - - 21.25 - - Graft Polymer Average Particle Size ^** 2100 2000 1900 1300 2200 2300 1900 - 1400 PVC processing MBS 8 8 8 8 8 8 8 - 8 Amount of coagulated product after polymerization (ppm) <500 <450 <400 <300 <1000 <1500 <800 - <790 Holy rotation impact strength (rpm) 1100 1000 950 600 930 800 950 <200 650 Shell glass transition temperature (℃) 105 103 102 101 108 113 101 - 102 Haze 4.0 4.1 3.9 3.9 4.3 4.4 4.5 3.7 4.8 Final PSD (Coarse (# 24) / Fine (# 200)) (Aggregation Temperature -38 ℃) 10/2 12/3 14/3 30/4 28/2 30/5 26/5 - 38/8

Abbreviations in the tables are as follows: BD: butadiene, SM: styrene monomer, DVB: divinylbenzene, MMA: methacrylate monomer, MAA: methacrylic acid monomer.

As shown in Table 1, the PVC composition (Examples 1 to 3) comprising the MBS graft copolymer of the present invention as an impact modifier has excellent impact strength, transparency, and final PSD, and the amount of coagulated product after polymerization is also excellent. It was 500 ppm or less.

On the other hand, in Comparative Example 2, 3 and the second graft layer step of the excessive methacrylic acid content, Comparative Example 5 using methacrylic acid as a copolymer, the amount of coagulation after polymerization is more than 800ppm, the impact strength and the final PSD is carried out It was confirmed that it is worse than Examples 1-3.

On the other hand, Comparative Example 1 is a case in which the methacrylic acid is not added in the first graft layer step, but the impact strength and transparency are not bad, but the agglomeration hypertrophy effect of methacrylic acid does not occur, so that the average particle diameter of the graft polymer is completed at 1300 kPa. Transparency in which the average particle diameter of the graft polymer is proportional shows relatively good results, but the impact strength is remarkably decreased. In addition, the result of increasing the content of coarse powder in the polymerization final PSD was confirmed.

Furthermore, in Comparative Example 6, only the first graft layer was formed and the second graft layer was not formed, the transparency and impact strength showed similar results as in Comparative Example 1, and the final PSD was significantly widened. In addition, the PVC composition (Comparative Example 5) without using the impact modifier was confirmed that the impact strength is significantly reduced.

Claims (18)

V) 65-85 wt% of the conjugated diene-based rubber core; And ii) 15 to 35% by weight of a graft shell formed around the rubber core and including an alkyl (meth) acrylate-based monomer and methacrylic acid, wherein the methacrylic acid is based on a total of 100% by weight of the graft shell. Characterized in that it comprises 1 to 30% by weight
MBS graft copolymer. The method of claim 1,
The methacrylic acid is characterized in that 5 to 15% by weight based on 100% by weight of the graft shell
MBS-based graft copolymer. The method of claim 1,
The conjugated diene rubber, characterized in that the ethylenically unsaturated aromatic compound further comprises 5 to 35% by weight based on 100% by weight of the graft shell
MBS graft copolymer. The method of claim 1,
The conjugated diene rubber, characterized in that the cross-linking vinyl monomer further comprises 0.1 to 5.0% by weight relative to the total 100% by weight of the conjugated diene rubber.
MBS graft copolymer. The method of claim 1,
The alkyl (meth) acrylate monomers are methyl methacrylate, n-butyl methacrylate, lauryl methacrylate, stearyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acryl At least one selected from the group consisting of the rate
MBS graft copolymer. The method of claim 1,
The graft shell, characterized in that the cross-linkable vinyl monomer further comprises 0.1 to 1.0% by weight based on 100% by weight of the graft shell total
MBS graft copolymer. The method of claim 1,
The graft shell comprises a first graft layer made of an alkyl (meth) acrylate monomer and methacrylic acid; and a second graft layer made of an ethylene unsaturated aromatic compound.
MBS graft copolymer. The method of claim 7, wherein
The first graft layer is characterized in that the alkyl diphenyl disulfonate, or polyoxyethylene sorbitan fatty acid esters (0.1 to 1.0% by weight) is used.
MBS graft copolymer. The method of claim 7, wherein
The first graft layer further comprises a potassium hydroxide solution, characterized in that adjusted to pH 9 to 10
MBS graft copolymer. The method of claim 7, wherein
The ethylenically unsaturated aromatic compound is grafted at least one selected from the group consisting of styrene, alphamethylstyrene, isopropenyl naphthalene, vinylnaphthalene, styrene substituted with C ₁ to C ₃ alkyl group, and styrene substituted with halogen. Based on 100% by weight of shell Characterized in that it comprises less than 60% by weight
MBS graft copolymer. The method of claim 1,
The conjugated diene rubber core is 65 to 85% by weight, the methacrylic acid is 5 to 15% by weight, the alkyl (meth) acrylate monomer is characterized in that 40 to 45% by weight
MBS graft copolymer. The method of claim 1,
The average particle diameter of the conjugated diene rubber core is characterized in that 800 to 1300 mm 3
MBS-based graft copolymer. The method of claim 1,
The average particle diameter of the graft shell is characterized in that 1800 to 2300 mm 3
MBS-based graft copolymer. The method of claim 1,
The MBS-based graft copolymer is characterized in that the use of impact modifiers for vinyl chloride resin
MBS graft copolymer. Preparing a conjugated diene-based rubber core having an average particle diameter of 800 to 1300 mm 3;
Wrapping the conjugated diene-based rubber core and performing graft emulsion polymerization of the alkyl (meth) acrylate-based monomer and methacrylic acid to form a first shell; And
Surrounding the first shell and emulsion polymerizing an ethylenically unsaturated monomer to form a second shell having an average particle diameter of 1800 to 2300 mm 3; Consists of
Method for producing MBS graft copolymer. The method of claim 15,
In forming the first shell, at least one selected from alkyldiphenyl disulfonate or polyoxyethylene sorbitan fatty acid esters is used as a surfactant for emulsion polymerization.
Method for producing MBS graft copolymer. The method of claim 15,
The first shell is characterized in that it is adjusted to pH 9 to 10
Method for producing MBS graft copolymer. 15 to 20% by weight of the MBS graft copolymer of any one of claims 1 to 14 and 80 to 99% by weight of vinyl chloride resin
Polyvinyl chloride resin composition excellent in cohesive properties and impact strength.