KR102241832B1 - Copolymer composition, method for preparing the same and thermoplastic resin composition comprising the same - Google Patents

Abstract

The present invention relates to a copolymer composition, and more particularly, a (meth)acrylic core comprising a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms, and a repeating unit derived from a methyl (meth)acrylate monomer, A first core-shell copolymer comprising a first shell comprising a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms and a repeating unit derived from a poly(alkylene glycol) di(meth)acrylate monomer; And a conjugated diene-based core comprising a repeating unit derived from a conjugated diene monomer, a repeating unit derived from a methyl (meth)acrylate monomer, a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms, and a poly(alkylene glycol) di A second core-shell copolymer comprising a second shell containing a repeating unit derived from a (meth)acrylate monomer, and the ratio of the average particle diameter of the (meth)acrylic core and the average particle diameter of the conjugated diene core is 1 : More than 0.138 to less than 1:1, and based on the total content of the copolymer composition, the content of the (meth)acrylic core is 20% to 50% by weight, and the content of the conjugated diene core is 25% to 45% by weight It is a weight %, and the content of the first shell and the second shell is 10% to 30% by weight to provide a copolymer composition, a method for producing the same, and a thermoplastic resin composition comprising the same.

Description

Copolymer composition, its manufacturing method, and thermoplastic resin composition comprising the same TECHNICAL FIELD [COPOLYMER COMPOSITION, METHOD FOR PREPARING THE SAME AND THERMOPLASTIC RESIN COMPOSITION COMPRISING THE SAME}

The present invention relates to a copolymer composition, and more particularly, to a copolymer composition that is included in the thermoplastic resin composition and serves as an impact modifier, a method for preparing the same, and a thermoplastic resin composition comprising the same.

Vinyl chloride-based polymers are polymers containing 50% by weight or more of repeating units derived from vinyl chloride monomers (VCM), and are inexpensive, easy to control hardness, and are applicable to most processing equipment. Is diverse. In addition, it is possible to provide a molded article excellent in physical and chemical properties, such as mechanical strength, weather resistance, chemical resistance, and the like, and is thus widely used in various fields.

These vinyl chloride-based polymers are prepared in different forms depending on the application. For example, a vinyl chloride-based polymer for straight processing such as an extrusion process, a calendar process, and an injection process is generally prepared by suspension polymerization, and a vinyl chloride-based polymer for paste processing such as dipping, spraying, and coating is prepared by emulsion polymerization.

On the other hand, the vinyl chloride-based resin is generally used as an impact modifier for reinforcing the impact strength when manufacturing a molded article, MBS (methyl methacrylate-butadiene-styrene) resin. In order to improve the impact strength, rubber in the MBS resin When the content of is increased, there is a problem in that surface properties are deteriorated due to protrusions or the like in the molded article. Therefore, research to improve the impact strength without deteriorating the surface properties of the molded article is continuously required.

KR 0180714 B1

The problem to be solved in the present invention is to improve the impact strength without deteriorating the surface properties of the molded article when molding a thermoplastic resin composition containing an impact modifier in order to solve the problems mentioned in the technology behind the background of the invention. It is to let you do.

That is, the present invention was conceived to solve the problems of the prior art, and a copolymer composition included as an impact modifier in a thermoplastic resin composition uses heterogeneous cores, and a shell is graft-polymerized on each core. And, by using a bimodal copolymer composition in which each shell contains a repeating unit derived from a hydrophilic monomer, it is intended to provide a copolymer composition that improves the impact strength without deteriorating the surface properties of the molded article. do.

According to an embodiment of the present invention for solving the above problems, the present invention is a (meth)acrylic core comprising a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms, and a methyl (meth)acrylate A first core comprising a repeating unit derived from a monomer, a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms, and a repeating unit derived from a poly(alkylene glycol) di(meth)acrylate monomer- Shell copolymer; And a conjugated diene-based core comprising a repeating unit derived from a conjugated diene monomer, a repeating unit derived from a methyl (meth)acrylate monomer, a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms, and a poly(alkylene glycol) di A second core-shell copolymer comprising a second shell containing a repeating unit derived from a (meth)acrylate monomer, and the ratio of the average particle diameter of the (meth)acrylic core and the average particle diameter of the conjugated diene core is 1 : More than 0.138 to less than 1:1, and based on the total content of the copolymer composition, the content of the (meth)acrylic core is 20% to 50% by weight, and the content of the conjugated diene core is 25% to 45% by weight It is a weight %, and the content of the first shell and the second shell is 10% to 30% by weight to provide a copolymer composition.

In addition, the present invention comprises the steps of i) polymerizing an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms to prepare a (meth)acrylic core (S10); ii) polymerizing the conjugated diene monomer to prepare a conjugated diene-based core (S20); iii) The (meth)acrylic core prepared in the (S10) step and the conjugated diene-based core prepared in the (S20) step were introduced into one reactor, and a methyl (meth)acrylate monomer, an alkyl having 2 to 8 carbon atoms (Meth)acrylate monomer and poly(alkylene glycol) di(meth)acrylate monomer were added to graft the first shell on the (meth)acrylic core, the second shell on the conjugated diene core, and at the same time Including the step of polymerization (S30), the ratio of the average particle diameter of the (meth)acrylic core prepared in step (S10) and the average particle diameter of the conjugated diene-based core prepared in step (S20) is greater than 1:0.138 to It provides a method for preparing a copolymer composition of less than 1:1.

In addition, the present invention provides a thermoplastic resin composition comprising the copolymer composition and a vinyl chloride resin.

According to the present invention, a bimodal copolymer composition containing a repeating unit derived from a hydrophilic monomer is used as a thermoplastic resin composition using a heterogeneous core, and graft polymerization of a shell on each core. When used as an impact modifier, there is an effect of improving the impact strength without deteriorating the surface properties of the molded article.

In addition, according to the present invention, cost competitiveness can be secured by replacing some of the conjugated diene-based monomers with severe price fluctuations among the raw materials recently applied to MBS with alkyl (meth)acrylate monomers, thereby providing excellent productivity.

Terms and words used in the description and claims of the present invention should not be construed as being limited to their usual or dictionary meanings, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

The copolymer composition according to the present invention comprises a (meth)acrylic core comprising a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms, a repeating unit derived from a methyl (meth)acrylate monomer, and an alkyl having 2 to 8 carbon atoms. A first core-shell copolymer comprising a first shell comprising a repeating unit derived from a (meth)acrylate monomer and a repeating unit derived from a poly(alkylene glycol) di(meth)acrylate monomer; And a conjugated diene-based core comprising a repeating unit derived from a conjugated diene monomer, a repeating unit derived from a methyl (meth)acrylate monomer, a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms, and a poly(alkylene glycol) di A second core-shell copolymer comprising a second shell containing a repeating unit derived from a (meth)acrylate monomer, and the ratio of the average particle diameter of the (meth)acrylic core and the average particle diameter of the conjugated diene core is 1 : More than 0.138 to less than 1:1, and based on the total content of the copolymer composition, the content of the (meth)acrylic core is 20% to 50% by weight, and the content of the conjugated diene core is 25% to 45% by weight % By weight, and the content of the first shell and the second shell may be 10% to 30% by weight of a copolymer composition.

That is, the copolymer composition according to the present invention includes a first core-shell copolymer and a second core in which heterogeneous cores of a (meth)acrylic core and a conjugated diene core are graft-polymerized into a first shell and a second shell, respectively. It may be a bimodal copolymer composition including a core-shell copolymer. As described above, the bimodal copolymer composition including the first core-shell copolymer and the second core-shell copolymer using heterogeneous cores can increase the rubber content contained in the impact modifier, It has excellent impact strength.

In this regard, in the case of preparing a bimodal copolymer composition of a small-diameter and large-diameter core using a conjugated diene-based core alone, such as a conventional MBS-based impact modifier, due to a single monomer component, small-diameter and large-diameter 2 Since the polymerization time of the core of the species may be prolonged, economic and commercial feasibility may not be secured in the manufacturing process. In addition, a large amount of emulsifier used to secure polymerization stability is required during polymerization, and when the rubber content is increased to improve the impact strength lowered from the small-diameter core, the dispersibility of MBS particles decreases, resulting in poor mechanical properties and surface properties. There may be a problem of deterioration, and it may be desirable to use a heterogeneous core according to the present invention.

In particular, in the case of using a (meth)acrylic core and a conjugated diene-based core according to the present invention, while securing mechanical properties from the conjugated diene-based core, cost competitiveness is secured from the (meth)acrylic core, and the surface characteristics of the molded article While preventing the reduction of the impact strength can be further improved, it may be preferable.

On the other hand, the ratio of the average particle diameter of the (meth)acrylic core and the average particle diameter of the conjugated diene core may be greater than 1:0.138 to less than 1:1, greater than 1:0.228 to less than 1:1, or 1:0.333 to 0.750 In addition, within this range, the thermoplastic resin composition including the copolymer composition as an impact modifier has excellent impact strength and surface properties.

In this regard, since the glass transition temperature of the (meth)acrylic core is higher than the glass transition temperature of the conjugated diene core, when the average particle diameter of the conjugated diene core is equal to or higher than the average particle diameter of the (meth)acrylic core, The impact strength of the thermoplastic resin composition decreases, and due to the large average particle diameter of the conjugated diene-based core, the polymerization time is lengthened and economic efficiency decreases, and the amount of emulsifier for securing latex stability during polymerization increases, resulting in the surface characteristics of the thermoplastic resin composition. It is degraded, and due to the small average particle diameter of the (meth)acrylic core, there may be a problem that mechanical properties such as impact strength are deteriorated.According to the present invention, the average particle diameter of the (meth)acrylic core and the average particle diameter of the conjugated diene core It may be desirable to adjust the ratio of.

In the present invention, the term'monomer' refers to all compounds for forming a polymer by participating in a polymerization reaction, and if a compound capable of forming a copolymer composition according to the present invention by participating in a polymerization reaction, the form of the compound is It is not limited whether it is a monomer which is a single compound, an oligomer which is an oligomer with few units, or a polymer which is a polymer with many units. That is, if a compound participates in the polymerization reaction for forming the copolymer composition according to the present invention, all of the monomers, oligomers, and polymers may be monomers.

In the present invention, the term'monomer-derived repeating unit' may refer to a component, structure, or substance itself derived from a monomer, and refers to a repeating unit formed in the polymer by participating in the polymerization reaction of the introduced monomer during polymerization of the polymer. It can be.

In the present invention, the term'core' may mean a rubber component or a rubber polymer component constituting the core or core layer of the core-shell type copolymer.

In the present invention, the term'shell' may mean a polymer component or a copolymer component that is graft-polymerized on a core of a core-shell type copolymer to form a shell or a shell layer.

In the present invention, the term'average particle diameter' refers to a weight average particle diameter (D50) measured according to an intensity Gaussian distribution by a dynamic laser light scattering method using Nicomp 380. I can.

According to an embodiment of the present invention, the (meth)acrylic core, the alkyl (meth)acrylate monomer having 2 to 8 carbon atoms constituting the repeating unit in the first shell and the second shell contains an alkyl group having 2 to 8 carbon atoms, respectively. It may be an alkyl (meth)acrylate monomer. In this case, the alkyl group having 2 to 8 carbon atoms may be meant to include both a linear alkyl group having 2 to 8 carbon atoms and a branched alkyl group having 3 to 8 carbon atoms. As a specific example, the alkyl (meth)acrylate monomer is ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate. ) Acrylate, octyl (meth)acrylate, or 2-ethylhexyl (meth)acrylate. Here, the alkyl (meth)acrylate monomer may mean an alkyl acrylate or an alkyl methacrylate.

In addition, according to an embodiment of the present invention, the conjugated diene monomer forming the repeating unit in the conjugated diene core is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1 ,3-octadiene, isoprene, 2-phenyl-1,3-butadiene, and 2-halo-1,3-butadiene (halo means a halogen atom) may be one or more selected from the group consisting of.

According to an embodiment of the present invention, the average particle diameter of the entire (meth)acrylic core and the conjugated diene core may be more than 175 nm to less than 245 nm, 180 nm to 235 nm, or 200 nm to 225 nm, Within the range, there is an effect of excellent impact strength and surface properties of the thermoplastic resin composition comprising the copolymer composition according to the present invention.

In particular, according to an embodiment of the present invention, the average particle diameter of the (meth)acrylic core may be greater than 180 nm to less than 360 nm, 200 nm to 350 nm, or 240 nm to 300 nm, within this range, There is an effect of excellent impact strength without deteriorating the surface properties of the thermoplastic resin composition including the copolymer composition.

In addition, according to an embodiment of the present invention, the average particle diameter of the conjugated diene-based core may be greater than 50 nm to less than 240 nm, 80 nm to 200 nm, or 100 nm to 180 nm, and within this range, thermoplastic The resin composition has excellent impact strength.

On the other hand, according to an embodiment of the present invention, with respect to the total content of the copolymer composition, the content of the (meth)acrylic core is from 20% by weight to 50% by weight, from 30% by weight to 50% by weight, or from 40% by weight It may be 50% by weight, and within this range, the impact strength and surface properties of the thermoplastic resin composition are excellent.

In addition, according to an embodiment of the present invention, with respect to the total content of the copolymer composition, the content of the conjugated diene-based core is 25% to 45% by weight, 25% to 40% by weight, or 30% to 40% by weight. It may be a weight%, and within this range, there is an effect of excellent mechanical properties such as impact strength of the thermoplastic resin composition.

In addition, according to an embodiment of the present invention, with respect to the total content of the copolymer composition, the content of the first shell and the second shell is 10% to 30% by weight, 15% to 30% by weight, or 15 It may be in the range of% to 25% by weight, and the mechanical properties and surface properties of the thermoplastic resin composition are excellent.

Meanwhile, according to an embodiment of the present invention, the (meth)acrylic core may include a repeating unit derived from a crosslinkable monomer. As described above, when the (meth)acrylic core includes a repeating unit derived from a crosslinkable monomer, on the (meth)acrylic core including a repeating unit derived from an alkyl (meth)acrylate monomer, graphs of the first shell and the second shell The polymer composition is easily carried out, thereby improving the cohesive properties of the copolymer composition latex and the appearance properties of the copolymer composition. The crosslinkable monomers are specific examples, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, allyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol (Meth)acrylic crosslinkable monomers such as tetra(meth)acrylate and the like; It may be at least one selected from vinyl-based crosslinkable monomers such as divinylbenzene, divinylnaphthalene and diallylphthalate. When the (meth)acrylic core contains a crosslinkable monomer, the (meth)acrylic core is a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms based on the total content of the (meth)acrylic core. 98 wt% to 99.9 wt%, or 98.5 wt% to 99.5 wt%; And 0.1 wt% to 2 wt%, or 0.5 wt% to 1.5 wt% of a repeating unit derived from a crosslinkable monomer.

In addition, according to an embodiment of the present invention, the conjugated diene-based core may further include a repeating unit derived from an aromatic vinyl monomer. The aromatic vinyl monomers are styrene, ?-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene and 1-vinyl It may be one or more selected from the group consisting of -5-hexylnaphthalene, and when the conjugated diene-based core further includes a repeating unit derived from an aromatic vinyl monomer, the content of the repeating unit derived from the aromatic vinyl monomer is, the conjugated diene-based core Based on the total content, it may be 10% by weight to 40% by weight, 15% by weight to 30% by weight, or 18% by weight to 25% by weight, within this range, there is an effect excellent in surface properties and colorability.

In addition, according to an embodiment of the present invention, the repeating unit derived from the poly(alkylene glycol) di(meth)acrylate monomer contained in the first shell and the second shell is derived from a polymeric monomer for performing a hydrophilic function. As a repeating unit, when forming the first shell and the second shell of the copolymer composition, the graft efficiency is increased to improve processability, and furthermore, a high rubber content due to the (meth)acrylic core and the conjugated diene core in the copolymer composition It may be to play a role of preventing deterioration of surface properties such as protrusions and improving adhesion resistance.

According to an embodiment of the present invention, the poly(alkylene glycol) di(meth)acrylate monomer may have 3 to 12, 4 to 10, or 4 to 8 number of repeating units derived from alkylene glycol, It is easy to participate in the polymerization reaction of the first shell and the second shell within the range, and has excellent hydrophilicity, thereby preventing deterioration of surface properties such as protrusions from a high rubber content, and improving adhesive resistance. In another example, the alkylene of the poly(alkylene glycol) di(meth)acrylate monomer may be an alkylene having 1 to 10, 2 to 8, or 2 to 5 carbon atoms, and as a specific example, the poly(alkylene glycol) ) Di(meth)acrylate monomers include poly(ethylene glycol) diacrylate, poly(ethylene glycol) dimethacrylate, poly(propylene glycol) diacrylate and poly( Propylene glycol) may be one or more selected from the group consisting of dimethacrylate.

In addition, according to an embodiment of the present invention, the first shell and the second shell may further include a repeating unit derived from an aromatic vinyl monomer. The aromatic vinyl monomers are styrene, ?-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene and 1-vinyl It may be one or more selected from the group consisting of -5-hexylnaphthalene, and when the first and second shells further include repeating units derived from aromatic vinyl monomers, the content of repeating units derived from aromatic vinyl monomers is Based on the total content of the 1 shell and the second shell, it may be 1% to 20% by weight, 5% to 15% by weight, or 10% to 15% by weight, and within this range, surface properties and colorability are It is excellent and has an excellent effect of latex stability during polymerization.

The method for preparing a copolymer composition according to the present invention comprises the steps of i) polymerizing an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms to prepare a (meth)acrylic core (S10); ii) polymerizing the conjugated diene monomer to prepare a conjugated diene-based core (S20); iii) The (meth)acrylic core prepared in the (S10) step and the conjugated diene-based core prepared in the (S20) step were introduced into one reactor, and a methyl (meth)acrylate monomer, an alkyl having 2 to 8 carbon atoms (Meth)acrylate monomer and poly(alkylene glycol) di(meth)acrylate monomer were added to graft the first shell on the (meth)acrylic core, the second shell on the conjugated diene core, and at the same time Including the step of polymerization (S30), the ratio of the average particle diameter of the (meth)acrylic core prepared in step (S10) and the average particle diameter of the conjugated diene-based core prepared in step (S20) is greater than 1:0.138 to It may be less than 1:1.

The step (S10) is a step for preparing a (meth)acrylic core, and in the presence of an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms, a peroxide-based, redox, or azo-based initiator is used. It can be prepared by radical polymerization, and as the polymerization method, emulsion polymerization, bulk polymerization, solution polymerization, or suspension polymerization method can be used, from the viewpoint of controlling the average particle diameter of the (meth)acrylic core according to the present invention. , Using a redox initiator, it can be carried out by an emulsion polymerization method.

According to an embodiment of the present invention, the redox initiator that can be used in step (S10) is, for example, one selected from the group consisting of t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, and cumene hydroperoxide. It may be more than that, and in this case, there is an effect of providing a stable polymerization environment.

In addition, according to an embodiment of the present invention, the emulsifier used in the emulsion polymerization of step (S10) is an alkylaryl sulfonate, an alkali methyl alkyl sulfate, a soap of a fatty acid, an alkali salt of oleic acid, an alkali salt of rosin acid, an alkali salt of lauryl acid. , Sodium diethylhexyl phosphate, phosphonate polyoxyethylene alcohol, phosphonate polyoxyethylene phenol, and the like may be one or more selected from the group consisting of, and in this case, there is an effect of providing a stable polymerization environment. The emulsifier is, for example, 2 parts by weight or less, 1.5 parts by weight or less, or 0.3 parts by weight to 1 part by weight based on 100 parts by weight of the total monomer content introduced in step (S10). It may be preferable in terms of preventing, in addition to improving appearance properties, maintaining polymerization stability of the latex, and controlling the average particle diameter of the (meth)acrylic core.

On the other hand, as in the above step (S10), when preparing a (meth)acrylic core by emulsion polymerization of an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms, a conjugated diene core having an average particle diameter of the same or equivalent level Compared to the case of emulsion polymerization of the conjugated diene monomer for production, the polymerization of rubber, that is, the production of the core is possible with only the use of a smaller amount of emulsifier, and the content of the residual emulsifier in the finally obtained polymer or copolymer is small, so impact strength, etc. There is an effect of preventing deterioration of mechanical properties and improving appearance properties.

As another example, the (S10) step may be carried out including a crosslinkable monomer.

The step (S20) is a step for preparing a conjugated diene-based core, and may be carried out as a separate step, not as a continuous step from the step (S10), and in the presence of a conjugated diene monomer, peroxide-based, redox (redox), or can be prepared by radical polymerization using an azo-based initiator, and as the polymerization method, emulsion polymerization, bulk polymerization, solution polymerization or suspension polymerization method may be used. According to the present invention, a conjugated diene-based core From the viewpoint of controlling the average particle diameter of, it can be carried out by an emulsion polymerization method using a redox initiator.

According to an embodiment of the present invention, the redox initiator that can be used in step (S20) is, for example, one selected from the group consisting of t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, and cumene hydroperoxide. It may be more than one, and the peroxide-based initiator may be one or more selected from the group consisting of potassium persulfate and sodium persulfate, for example, and in this case, there is an effect of providing a stable polymerization environment.

In addition, according to an embodiment of the present invention, the emulsifier used in the emulsion polymerization of step (S20) is an alkylaryl sulfonate, an alkali methyl alkyl sulfate, a soap of a fatty acid, an alkali salt of oleic acid, an alkali salt of rosin acid, an alkali salt of lauryl acid. , Sodium diethylhexyl phosphate, phosphonate polyoxyethylene alcohol, phosphonate polyoxyethylene phenol, and the like may be one or more selected from the group consisting of, and in this case, there is an effect of providing a stable polymerization environment. The emulsifier is added in an amount of 2.5 parts by weight or less, 2.0 parts by weight or less, or 0.3 parts by weight to 1.5 parts by weight based on 100 parts by weight of the total monomer content introduced in step (S20). It may be desirable in

The (S30) step is a step for simultaneously graft polymerization of the (meth)acrylic core prepared in the (S10) step and the conjugated diene-based core prepared in the (S20) step, prepared in the (S10) step. By introducing the (meth)acrylic core and the conjugated diene-based core prepared in step (S20) into one reactor and performing graft polymerization, a monomer of the same component is used on the (meth)acrylic-based core and the conjugated diene-based core. There is an effect of forming a first shell and a second shell including repeating units derived from monomers of the same component in each core through graft polymerization. The step (S30) includes a (meth)acrylic core, a conjugated diene core, a methyl (meth)acrylate monomer, an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms, and a poly(alkylene glycol) di(meth)acrylate. In the presence of a monomer, it can be prepared by radical polymerization using a peroxide-based, redox, or azo-based initiator, and as a polymerization method, an emulsion polymerization, bulk polymerization, solution polymerization or suspension polymerization method is used. However, from the viewpoint of forming a shell on each of the different types of cores according to the present invention, it may be carried out by an emulsion polymerization method using a redox initiator.

According to an embodiment of the present invention, the redox initiator that can be used in step (S30) is one selected from the group consisting of t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, and cumene hydroperoxide. It may be more than that, and in this case, there is an effect of providing a stable polymerization environment.

In addition, according to an embodiment of the present invention, the emulsifier used in the emulsion polymerization in step (S30) is an alkylaryl sulfonate, an alkali methyl alkyl sulfate, a soap of a fatty acid, an alkali salt of oleic acid, an alkali salt of rosin acid, an alkali salt of lauryl acid. , Sodium diethylhexyl phosphate, phosphonate polyoxyethylene alcohol, phosphonate polyoxyethylene phenol, and the like may be one or more selected from the group consisting of, and in this case, there is an effect of providing a stable polymerization environment. The emulsifier is preferably added in an amount of 3 parts by weight or less, 2.5 parts by weight or less, or 1.3 parts by weight or less based on 100 parts by weight of the total monomer content introduced in step (S30) in terms of maintaining the polymerization stability of the latex. can do.

According to an embodiment of the present invention, the method for preparing the copolymer composition may include agglomeration, aging, dehydration and drying to obtain the latex of the copolymer composition obtained by emulsion polymerization in powder form. . The copolymer composition powder obtained through the above step may serve as an impact modifier in the thermoplastic resin composition.

According to an embodiment of the present invention, the agglomeration step may be performed by adding one or more flocculants selected from the group consisting of magnesium sulfate, calcium chloride, aluminum sulfate, sulfuric acid, phosphoric acid and hydrochloric acid to the copolymer composition latex. The agglomeration step may be carried out, for example, at 30° C. to 90, or 45° C. to 75, and in this case, powder particles having an average particle diameter of 75 to 1,400 μm may be obtained. After the coagulation step, when performing the aging step, the aging step may be carried out at 75 °C to 95 °C, or 80 °C to 90 °C, and in this case, residual monomers not participating in the polymerization may be removed by volatilization. , There is an effect of preventing cracking of powder particles and reducing moisture content. The dehydration and drying step may be performed by using a hot air drying method after removing the moisture from the coagulated and/or aged copolymer composition latex with a dehydrator and separating it into solids, and in this case, shortening the drying time through dehydration, There is an effect of removing residual monomers that have not participated in polymerization through hot air drying.

The thermoplastic resin composition according to the present invention may include the copolymer composition and a vinyl chloride resin. The thermoplastic resin composition may include, for example, the copolymer composition as an impact modifier. The thermoplastic resin composition may be a thermoplastic resin composition for manufacturing a molded article through molding, and in this case, a base resin of a thermoplastic resin composition comprising the copolymer composition as an impact modifier, that is, of a thermoplastic resin composition. The underlying thermoplastic resin may be a vinyl chloride resin.

According to an embodiment of the present invention, the vinyl chloride resin may not be particularly limited as long as it is a vinyl chloride resin that can be used for molding. On the other hand, the thermoplastic resin composition, based on the total content of the thermoplastic resin composition, 80% to 99% by weight of the vinyl chloride resin, 90% to 99% by weight, or 95% to 99% by weight, the copolymer The composition may be included in an amount of 1% to 20% by weight, 1% to 10% by weight, or 1% to 5% by weight, and within this range, the processability, impact strength, and surface properties of the thermoplastic resin composition are excellent. There is.

The thermoplastic resin composition according to the present invention, in addition to the vinyl chloride resin and the copolymer composition, if necessary, a foaming agent, a stabilizer, a processing aid, a heat stabilizer, a lubricant, a pigment, a dye, and an oxidation agent within a range that does not degrade its physical properties. It may further include additives such as inhibitors.

On the other hand, according to an embodiment of the present invention, the thermoplastic resin composition, while rotating the circular saw blade, applied to the saw blade at a speed of 15 mm / second, the specimen is measured at a 50% cracking rpm, the rotational impact strength exceeds 1020 rpm, 1040 rpm or more, or 1040 rpm to 1230 rpm, and the number of protrusions on the surface of which the number of migelates present in the specimen is measured may be 10 or less, or 5 or less.

Hereinafter, the present invention will be described in more detail by examples. However, the following examples are intended to illustrate the present invention, and that various changes and modifications can be made within the scope of the present invention and the scope of the technical idea are obvious to those skilled in the art, and the scope of the present invention is not limited thereto.

Example

Example 1

<Manufacture of Butyl Acrylate Core>

Based on 100 parts by weight of the butyl acrylate monomer content in the nitrogen-substituted polymerization reactor, butyl acrylate 11.88 parts by weight, allyl methacrylate 0.12 parts by weight, fatty acid soap as an emulsifier 0.02 parts by weight, t-butyl hydroperoxide as a polymerization initiator 0.1 Parts by weight, 0.004 parts by weight of iron sulfide as an activator, 0.08 parts by weight of ethylene diamine acetate, 0.1 parts by weight of sodium formaldehyde sulfoxylate, and 42 parts by weight of ion-exchanged water were collectively added and reacted at 45 to 55 for 0.5 hours. Then, 87.12 parts by weight of butyl acrylate, 0.88 parts by weight of allyl methacrylate, 1.64 parts by weight of fatty acid soap as an emulsifier, 0.34 parts by weight of t-butyl hydroperoxide as a polymerization initiator, 0.014 parts by weight of iron sulfide as an activator, ethylene Diamine acetate 0.27 parts by weight, sodium formaldehyde sulfoxylate 0.35 parts by weight, and ion-exchanged water 68 parts by weight are continuously added and reacted at 45 to 55 for 1.5 hours, and the average particle diameter of the butyl acrylate rubber is 300 nm. Was prepared.

<Manufacture of Butadiene Core>

In a nitrogen-substituted polymerization reactor (autoclave) based on 100 parts by weight of 1,3-butadiene monomer, 150 parts by weight of ion-exchanged water, 100 parts by weight of 1,3-butadiene as a monomer, 2.0 parts by weight of fatty acid soap as an emulsifier, as an electrolyte. 0.4 parts by weight of sodium sulfate, 0.1 parts by weight of diisopropylbenzene hydroperoxide as a polymerization initiator, 0.05 parts by weight of ethylenediamine tetrasodium acetate as an activator, 0.005 parts by weight of ferrous sulfate, 0.05 parts by weight of sodium formaldehyde sulfoxy acid in batch It was added and reacted at 45 to 55° C. to prepare a butadiene rubber latex having an average particle diameter of 100 nm of the butadiene rubber.

<Preparation of copolymer composition>

In a nitrogen-substituted polymerization reactor, based on 100 parts by weight of the total monomer content, 40 parts by weight of the butyl acrylate rubber latex obtained above (based on the solid content) and 40 parts by weight of the butadiene rubber latex (based on the solid content) were collectively added, and then the reactor temperature was adjusted. Maintained at 45 to 55, 10 parts by weight of ion-exchanged water, 17.8 parts by weight of methyl methacrylate, 2 parts by weight of butyl acrylate, and 0.2 parts by weight of poly(ethylene glycol) diacrylate having 6 repeating units derived from ethylene glycol, 0.12 parts by weight of fatty acid soap as an emulsifier, 0.1 parts by weight of t-butyl hydroperoxide as a polymerization initiator, 0.004 parts by weight of iron sulfide as an activator, 0.08 parts by weight of ethylene diamine acetate and 0.1 parts by weight of sodium formaldehyde sulfoxylate for 1.5 hours During a graft polymerization reaction was continuously added at 45 to 55 to obtain a copolymer composition latex. The composition of the copolymer composition is shown in Table 1 below.

<Copolymer composition powder production>

After adding 0.5 parts by weight of an antioxidant (IR245) emulsion having an average particle diameter of 0.9 µm to the obtained latex copolymer composition and stirring, agglomeration at an aggregation temperature of 40° C. in the presence of 0.4 parts by weight of an aqueous sulfuric acid solution (concentration 5% by weight) as a coagulant Made it. The agglomerated copolymer composition latex was aged until reaching 85° C., dehydrated, and then dried at a drying temperature of 65° C. until the moisture content reached less than 1% by weight to obtain a copolymer composition powder.

Example 2

In Example 1, when preparing the copolymer composition, except that 50 parts by weight of butyl acrylate rubber latex (based on solid content) and 30 parts by weight of butadiene rubber latex (based on solid content) was added to Example 1 and It was carried out in the same way.

Example 3

In Example 1, when preparing a butyl acrylate core, 19.8 parts by weight of butyl acrylate, 0.2 parts by weight of allyl methacrylate, 0.07 parts by weight of fatty acid soap as an emulsifier, 0.3 parts by weight of t-butyl hydroperoxide as a polymerization initiator, activation As an activator, 0.012 parts by weight of iron sulfide, 0.24 parts by weight of ethylene diamine acetate, 0.3 parts by weight of sodium formaldehyde sulfoxylate, and 117 parts by weight of ion-exchanged water were collectively added and reacted at 45 to 55 for 0.5 hours, and then butyl acrylic Rate 79.2 parts by weight, allyl methacrylate 0.8 parts by weight, 1 part by weight of fatty acid soap as an emulsifier, 0.3 parts by weight of t-butyl hydroperoxide as a polymerization initiator, 0.012 parts by weight of iron sulfide as an activator, 0.24 parts by weight of ethylene diamine acetate Parts, 0.3 parts by weight of sodium formaldehyde sulfoxylate and 40 parts by weight of ion-exchanged water were continuously added and reacted at 45 to 55 for 1 hour to prepare a butyl acrylate rubber latex having an average particle diameter of 240 nm of the butyl acrylate rubber, When preparing the butadiene core, it was carried out in the same manner as in Example 1, except that 0.75 parts by weight of sodium sulfate was added as an electrolyte to prepare a butadiene rubber latex having an average particle diameter of 180 nm.

Example 4

In Example 1, when preparing the copolymer composition, 40 parts by weight of butyl acrylate rubber latex (based on solid content) and 35 parts by weight of butadiene rubber latex (based on solid content) were added, and 12 parts by weight of ion-exchanged water, methyl It was carried out in the same manner as in Example 1, except that 19.3 parts by weight of methacrylate, 2.5 parts by weight of butyl acrylate, and 3 parts by weight of styrene were added.

Example 5

In Example 1, when preparing the butadiene core, it was carried out in the same manner as in Example 1, except that 79 parts by weight of 1,3-butadiene monomer and 21 parts by weight of styrene monomer were added.

Example 6

In Example 1, when preparing the copolymer composition, the above except that poly(propylene glycol) dimethacrylate having 7 repeating units derived from propylene glycol was added in an amount of 0.2 parts by weight instead of poly(ethylene glycol) diacrylate. It was carried out in the same manner as in Example 1.

Comparative Example 1

In Example 1, when preparing a butyl acrylate core, 29.7 parts by weight of butyl acrylate, 0.3 parts by weight of allyl methacrylate, 0.07 parts by weight of fatty acid soap as an emulsifier, 0.3 parts by weight of t-butyl hydroperoxide as a polymerization initiator, activation As an activator, 0.012 parts by weight of iron sulfide, 0.24 parts by weight of ethylene diamine acetate, 0.3 parts by weight of sodium formaldehyde sulfoxylate, and 134 parts by weight of ion-exchanged water were collectively added and reacted at 45 to 55 for 0.5 hours, and then butyl acrylic Rate 69.3 parts by weight, allyl methacrylate 0.7 parts by weight, 1 part by weight of fatty acid soap as an emulsifier, 0.3 parts by weight of t-butyl hydroperoxide as a polymerization initiator, 0.012 parts by weight of iron sulfide as an activator, 0.24 parts by weight of ethylene diamine acetate Parts, 0.3 parts by weight of sodium formaldehyde sulfoxylate and 30 parts by weight of ion-exchanged water were continuously added and reacted at 45 to 55 for 1 hour to prepare a butyl acrylate rubber latex having an average particle diameter of 200 nm of the butyl acrylate rubber, The butadiene core was not prepared and was carried out in the same manner as in Example 1, except that 80 parts by weight (based on solid content) of butyl acrylate rubber latex was added when preparing the copolymer composition.

Comparative Example 2

In Example 1, when the butyl acrylate core was not prepared, when the butadiene core was prepared, 0.85 parts by weight of sodium sulfate was added, and when the copolymer composition was prepared, 80 parts by weight (based on solid content) of the butadiene rubber latex was added. Except, it was carried out in the same manner as in Example 1.

Comparative Example 3

In Example 1, when preparing the copolymer composition, 55 parts by weight of butyl acrylate rubber latex (based on solid content) and 20 parts by weight of butadiene rubber latex (based on solid content) were added, and ion-exchanged water 12 parts by weight, methyl meta It was carried out in the same manner as in Example 1, except that 22.3 parts by weight of acrylate and 2.5 parts by weight of butyl acrylate were added.

Comparative Example 4

In Example 1, when preparing the copolymer composition, except that 30 parts by weight of butyl acrylate rubber latex (based on solid content) and 50 parts by weight of butadiene rubber latex (based on solid content) was added to Example 1 and It was carried out in the same way.

Comparative Example 5

In Example 1, when preparing a butyl acrylate core, 6.3 parts by weight of butyl acrylate, 0.07 parts by weight of allyl methacrylate, 0.01 parts by weight of fatty acid soap as an emulsifier, 0.1 parts by weight of t-butyl hydroperoxide as a polymerization initiator, activation As an activator, 0.004 parts by weight of iron sulfide, 0.08 parts by weight of ethylene diamine acetate, 0.1 parts by weight of sodium formaldehyde sulfoxylate, and 20 parts by weight of ion-exchanged water were collectively added and reacted at 45 to 55 for 0.5 hours, and then butyl acrylic 92.7 parts by weight of rate, 0.93 parts by weight of allyl methacrylate, 1.69 parts by weight of fatty acid soap as an emulsifier, 0.34 parts by weight of t-butyl hydroperoxide as a polymerization initiator, 0.014 parts by weight of iron sulfide as an activator, 0.27 parts by weight of ethylene diamine acetate Parts, 0.35 parts by weight of sodium formaldehyde sulfoxylate and 75 parts by weight of ion-exchanged water were continuously added and reacted at 45 to 55 for 1.5 hours to prepare a butyl acrylate core having an average particle diameter of 360 nm of the butyl acrylate rubber, and butadiene When preparing the core, it was carried out in the same manner as in Example 1, except that sodium sulfate was not added as an electrolyte to prepare a butadiene rubber latex having an average particle diameter of 50 nm of the butadiene rubber.

Comparative Example 6

In Example 1, when preparing a butyl acrylate core, 34.65 parts by weight of butyl acrylate, 0.35 parts by weight of allyl methacrylate, 0.08 parts by weight of fatty acid soap as an emulsifier, 0.3 parts by weight of t-butyl hydroperoxide as a polymerization initiator, activation As an activator, 0.012 parts by weight of iron sulfide, 0.24 parts by weight of ethylene diamine acetate, 0.3 parts by weight of sodium formaldehyde sulfoxylate, and 145 parts by weight of ion-exchanged water were collectively added and reacted at 45 to 55 for 0.5 hours, and then butyl acrylic Rate 64.35 parts by weight, allyl methacrylate 0.65 parts by weight, 1 part by weight of fatty acid soap as an emulsifier, 0.3 parts by weight of t-butyl hydroperoxide as a polymerization initiator, 0.012 parts by weight of iron sulfide as an activator, 0.24 parts by weight of ethylene diamine acetate Parts, 0.3 parts by weight of sodium formaldehyde sulfoxylate and 25 parts by weight of ion-exchanged water were continuously added and reacted at 45 to 55 for 1 hour to prepare a butyl acrylate rubber latex having an average particle diameter of 180 nm of the butyl acrylate rubber, When preparing the butadiene core, it was carried out in the same manner as in Example 1, except that 1.1 parts by weight of sodium sulfate was added as an electrolyte to prepare a butadiene rubber latex having an average particle diameter of 240 nm.

Comparative Example 7

In Example 1, when preparing the copolymer composition, it was carried out in the same manner as in Example 1, except that 18 parts by weight of methyl methacrylate was added and poly(ethylene glycol) diacrylate was not added.

Experimental example

Experimental Example 1

The average particle diameter of each core prepared in Examples 1 to 6 and Comparative Examples 1 to 7 was measured by the following method, and the composition of each copolymer composition together with the results are shown in Tables 1 and 2 below.

* Average particle diameter (D50, nm): After preparing a sample obtained by diluting the manufactured rubber latex to 200 ppm or less, using Nicomp 380 at room temperature (23° C.), by dynamic laser light scattering. The average particle diameter (D50) of the rubber particles dispersed in the rubber latex was measured according to the intensity Gaussian distribution.

division Example One 2 3 4 5 6 (Meth)acrylic core BA ¹⁾ content
(Part by weight) 39.6 49.5 39.6 39.6 39.6 39.6 AMA ²⁾ content
(Part by weight) 0.4 0.5 0.4 0.4 0.4 0.4 Average particle diameter
(nm) 300 300 240 300 300 300 Conjugated Diene Core BD ³⁾ content
(Part by weight) 40 30 40 35 31.5 40 SM ⁴⁾ content
(Part by weight) - - - - 8.5 - Average particle diameter
(nm) 100 100 180 100 100 100 Core average particle diameter (nm) 200 225 210 205 200 200 First shell and second shell ⁵⁾ content of MMA
(Part by weight) 17.8 17.8 17.8 19.3 17.8 17.8 BA ¹⁾ content
(Part by weight) 2 2 2 2.5 2 2 SM ⁴⁾ content
(Part by weight) - - - 3 - - PEGDA ⁶⁾ content
(Part by weight) 0.2 0.2 0.2 0.2 0.2 - PPGDA ⁷⁾ content
(Part by weight) - - - - - 0.2 1) BA: butyl acrylate
2) AMA: allyl methacrylate
3) BD: 1,3-butadiene
4) SM: styrene
5) MMA: methyl methacrylate
6) PEGDA: poly(ethylene glycol) diacrylate with 6 repeating units derived from ethylene glycol
7) PPGDA: poly(propylene glycol) dimethacrylate with 7 repeating units derived from propylene glycol

division Comparative example One 2 3 4 5 6 7 (Meth)acrylic core BA ¹⁾ content
(Part by weight) 79.2 - 54.5 29.7 39.6 39.6 39.6 AMA ²⁾ content
(Part by weight) 0.8 - 0.5 0.3 0.4 0.4 0.4 Average particle diameter
(nm) 200 - 300 300 360 180 300 Conjugated Diene Core BD ³⁾ content
(Part by weight) - 80 20 50 40 40 40 SM ⁴⁾ content
(Part by weight) - - - - - - - Average particle diameter
(nm) - 200 100 100 50 240 100 Core average particle diameter (nm) 200 200 245 175 205 210 200 First shell and second shell ⁵⁾ content of MMA
(Part by weight) 17.8 17.8 22.3 17.8 17.8 17.8 18 BA ¹⁾ content
(Part by weight) 2 2 2.5 2 2 2 2 SM ⁴⁾ content
(Part by weight) - - - - - - - PEGDA ⁶⁾ content
(Part by weight) 0.2 0.2 0.2 0.2 0.2 0.2 - 1) BA: butyl acrylate
2) AMA: allyl methacrylate
3) BD: 1,3-butadiene
4) SM: styrene
5) MMA: methyl methacrylate
6) PEGDA: poly(ethylene glycol) diacrylate with 6 repeating units derived from ethylene glycol

Experimental Example 2

The rotational impact strength and the number of protrusions on the surface of the thermoplastic resin composition including the copolymer compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 7 were measured by the following method, and are shown in Tables 3 and 4.

* Sex rotation impact strength (rpm): 100 parts by weight of vinyl chloride resin (LG Chemical, LS100), 1.5 parts by weight of heat stabilizer (Sn stearate), 1.0 parts by weight of internal lubricant (calcium stearate), 0.3 parts by weight of external lubricant (paraffin wax) Parts by weight, 0.5 parts by weight of processing aid (LG Chemical, PA-910), and 0.3 parts by weight of pigment were sufficiently mixed at a temperature of 130 using a high-speed stirrer and then cooled to prepare a vinyl chloride resin masterbatch. 6 parts by weight of each of the copolymer composition powders prepared in Examples 1 to 6 and Comparative Examples 1 to 7 were added to 94 parts by weight of the prepared vinyl chloride resin masterbatch, and 0.5 mm thick using a roll of 195 A sheet of was prepared, and the prepared sheet was cut to prepare a specimen having a thickness of 0.5 mm and an area of 10 cm X 14 cm, aged at 25 for 2 hours, and then rotated the circular saw blade and applied to the saw blade at a speed of 15 mm/sec. As a method of measuring the% cracking rpm, the impact strength of rotating rotation was measured.

* Number of protrusions on the surface (pcs): When preparing a vinyl chloride resin masterbatch for measuring the impact strength of the rolling, 50 parts by weight of dioctyl phthalate (DOP) as a plasticizer is added to 100 parts by weight of the masterbatch, 10 parts by weight of the copolymer composition powder prepared in Examples 1 to 6 and Comparative Examples 1 to 7 were added, and a sheet prepared by using a 190 roll was cut to obtain a specimen having a thickness of 0.5 mm and an area of 10 cm X 10 cm. The total number of protrusions was measured as a method of measuring the number of microgeloids present in the specimen.

division Example One 2 3 4 5 6 Thermoplastic resin composition Sex rotation impact strength (rpm) 1,110 1,160 1,230 1,070 1,040 1,100 Protrusion (dog) <5 <5 <5 <5 <5 <5

division Comparative example One 2 3 4 5 6 7 Thermoplastic resin composition Sex rotation impact strength (rpm) 780 1,020 920 850 960 1,210 1,000 Protrusion (dog) <5 >100 <5 28 15 14 22

As shown in Tables 3 and 4, when using the copolymer composition of the present invention as an impact modifier in the thermoplastic resin composition, it was confirmed that the rotational impact strength was 1,040 rpm or more and 5 or less protrusions on the surface.

On the other hand, in the case of Comparative Example 1 in which the butadiene core was not used and only the butyl acrylate core was used as an impact modifier, the impact strength was very poor, and the butyl acrylate core was not used, and only the butadiene core was used. In the case of Comparative Example 2 in which the used MBS resin was used as an impact modifier, it was confirmed that the surface properties were rapidly deteriorated to 100 or more protrusions on the surface.

In addition, in the case of Comparative Examples 3 and 4 that deviated from the content of each core according to the present invention, when the butyl acrylate core was excessive, the impact resistance of the butadiene core was not sufficiently exhibited, and the impact strength was lowered, and when the butadiene core was excessive, It was confirmed that both the impact strength and the surface properties were deteriorated.

In addition, in the case of Comparative Examples 5 and 6, which deviated from the ratio of the average particle diameter between the cores according to the present invention, the surface characteristics were deteriorated, and in particular, the average particle diameter of the butyl acrylate core was very large, and the average particle diameter of the butadiene core was very small. It was confirmed that the strength had decreased.

In addition, in the case of Comparative Example 7 in which the repeating unit derived from the poly(alkylene glycol) di(meth)acrylate monomer according to the present invention was not included in the first shell and the second shell, it was confirmed that the impact strength and surface characteristics were decreased. Could.

From the above results, the present inventors used a heterogeneous core according to the present invention, a shell is graft-polymerized on each core, and each shell is a bimodal (bimodal) containing repeating units derived from a hydrophilic monomer. When using the) type copolymer composition as an impact modifier in the thermoplastic resin composition, it was confirmed that the impact strength can be improved without deteriorating the surface properties of the molded article compared to the case of using the conventional MBS resin as an impact modifier.

Claims (9)

Repeating from a (meth)acrylic core containing a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms, a repeating unit derived from a methyl (meth)acrylate monomer, and a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms A first core-shell copolymer comprising a first shell including a repeating unit derived from a unit and a poly(alkylene glycol) di(meth)acrylate monomer; And
Conjugated diene core consisting of repeating units derived from conjugated diene monomers, repeating units derived from methyl (meth)acrylate monomers, repeating units derived from alkyl (meth)acrylate monomers having 2 to 8 carbon atoms, and poly(alkylene glycol) di(meth) ) Comprising a second core-shell copolymer comprising a second shell comprising a repeating unit derived from an acrylate monomer,
The (meth)acrylic core includes 98% to 99.9% by weight of repeating units derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms and 0.1% to 2% by weight of repeating units derived from a crosslinkable monomer,
The ratio of the average particle diameter of the (meth)acrylic core and the average particle diameter of the conjugated diene core is greater than 1:0.138 to less than 1:1,
Based on the total content of the copolymer composition, the content of the (meth)acrylic core is 30% by weight to 50% by weight, the content of the conjugated diene core is 25% by weight to 45% by weight, and the first shell and the The content of the second shell is 10% to 30% by weight of the copolymer composition. The method of claim 1,
The average particle diameter of the entire (meth)acrylic core and the conjugated diene core is greater than 175 nm and less than 245 nm. The method of claim 1,
The average particle diameter of the (meth)acrylic core is greater than 180 nm to less than 360 nm, and the average particle diameter of the conjugated diene core is greater than 50 nm to less than 240 nm. The method of claim 1,
The (meth)acrylic core is a copolymer composition comprising a repeating unit derived from a crosslinkable monomer. delete The method of claim 4,
The crosslinkable monomers are ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, allyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate. ) A copolymer composition that is one or more selected from the group consisting of acrylate, divinylbenzene, divinylnaphthalene, and diallylphthalate. The method of claim 1,
The poly(alkylene glycol) di(meth)acrylate monomer is a copolymer composition having 3 to 12 repeating units derived from alkylene glycol. i) preparing a (meth)acrylic core by polymerizing an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms (S10);
ii) polymerizing the conjugated diene monomer to prepare a conjugated diene-based core composed of repeating units derived from the conjugated diene monomer (S20);
iii) The (meth)acrylic core prepared in the (S10) step and the conjugated diene-based core prepared in the (S20) step were introduced into one reactor, and a methyl (meth)acrylate monomer, an alkyl having 2 to 8 carbon atoms (Meth)acrylate monomer and poly(alkylene glycol) di(meth)acrylate monomer were added to graft the first shell on the (meth)acrylic core, the second shell on the conjugated diene core, and at the same time Including the step of polymerization (S30),
The (meth)acrylic core includes 98% to 99.9% by weight of repeating units derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms and 0.1% to 2% by weight of repeating units derived from a crosslinkable monomer,
The ratio of the average particle diameter of the (meth)acrylic core prepared in step (S10) and the average particle diameter of the conjugated diene-based core prepared in step (S20) is greater than 1:0.138 to less than 1:1,
In the copolymer composition polymerized in (S30), the content of the (meth)acrylic core is 30% by weight to 50% by weight, and the content of the conjugated diene core is 25% by weight, based on the total content of the copolymer composition. 45% by weight, and the content of the first shell and the second shell is 10% by weight to 30% by weight of the copolymer composition manufacturing method. A thermoplastic resin composition comprising the copolymer composition of any one of claims 1 to 4 and 6 to 7 and a vinyl chloride resin.