KR100508153B1 - Impact Modifier Having Multi-Layer Structure and Thermoplastic Resin Composition Containing the Same - Google Patents

Abstract

The present invention relates to an impact modifier having a multilayer structure and a thermoplastic resin composition comprising the same, comprising: a first seed layer made of silicone rubber; A second seed layer made of a copolymer obtained by grafting at least one monomer selected from the group consisting of aromatic monomers and non-aromatic monomers to the polymer of the first seed layer; A core layer made of a copolymer obtained by grafting an acrylate monomer to the polymer of the second seed layer; And a shell layer made of a copolymer obtained by grafting at least one monomer selected from the group consisting of alkyl acrylate monomers and aromatic vinyl monomers to the polymer of the core layer. Thermoplastic resin containing a multi-layered impact modifier comprising an excellent impact strength, colorability and chemical resistance.

Description

Impact Modifier Having Multi-Layer Structure and Thermoplastic Resin Composition Containing the Same}

The present invention relates to an impact modifier of a multilayer structure and a thermoplastic resin composition comprising the same. More specifically, a multilayer structure manufactured by grafting (second seed layer) an aromatic monomer or a non-aromatic monomer onto a silicone rubber (first seed layer) and then grafting an acrylic rubber (core layer, shell layer) thereon. It relates to a thermoplastic resin composition including an impact modifier, excellent in impact strength, colorability and chemical resistance.

Conventional impact modifiers include MBS and acrylic impact modifiers. However, due to the high industrial development, there is a demand for an impact enhancer having superior chemical resistance, gloss, weather resistance, processability, and low temperature impact strength than conventional MBS or acrylic impact modifiers. Accordingly, silicone-based impact modifiers having excellent impact strength and gloss at room temperature and cryogenic temperature have been developed.

Japanese Patent Laid-Open No. Hei 8-283524 discloses that an impact modifier obtained by graft copolymerization of a vinyl polymerizable functional group of methacryl to a silicone polymer has improved impact resistance and pigment coloring property.

Japanese Patent Laid-Open No. 9-157484 discloses that an impact modifier prepared by grafting a copolymer of an aromatic alkenyl compound and a vinyl cyanide compound on a core of polyorganosiloxane and polyalkyl acrylate improves impact resistance, pigment colorability, and moldability. It is posted.

Japanese Patent Laid-Open No. 2001-220487 discloses that an impact modifier made of a blend of silicone and butadiene rubber improves molding gloss, cryogenic impact strength and weather resistance, and improves pigment coloring.

In addition, Korean Patent No. 2000-0076255 discloses an impact modifier prepared by controlling a particle size of a particle by grafting a silicone to an acrylic rubber prepolymerized in a polymerization step of a silicone rubber.

However, the existing impact modifiers are difficult to maintain the physical properties such as impact strength, colorability, chemical resistance, etc. at the same time, it was difficult to graf the silicone rubber directly to the acrylic rubber.

In order to achieve the above object, an object of the present invention is to provide an impact modifier made of a composite of a silicone rubber and an acrylic rubber.

In addition, an object of the present invention is to provide a thermoplastic resin composition excellent in impact strength, colorability and chemical resistance by using an impact modifier composed of a composite of silicone rubber and acrylic rubber.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention is a first seed layer (seed layer) made of a silicone-based rubber; A second seed layer made of a copolymer obtained by grafting at least one monomer selected from the group consisting of aromatic monomers and non-aromatic monomers to the polymer of the first seed layer; A core layer made of a copolymer obtained by grafting an acrylate monomer to the polymer of the second seed layer; And a shell layer made of a copolymer obtained by grafting at least one monomer selected from the group consisting of alkyl acrylate monomers and aromatic vinyl monomers to the polymer of the core layer. It provides an impact modifier of a multi-layer structure, characterized in that made.

The first seed layer may be 5 to 50% by weight based on the impact modifier.

The silicone rubber constituting the first seed layer may be prepared from a raw material consisting of dimethyl siloxane, a siloxane having a vinyl group, and a siloxane crosslinking agent.

The dimethyl siloxane may be selected from one or more selected from the group consisting of nuxamethylcyclotrisiloxane, octomethylcyclotetrasiloxane, and dodecamethylcyclonuxasiloxane.

The siloxane having a vinyl group may be selected from the group consisting of triethoxy vinylsilane, 3- (trimethoxysilyl) propyl acrylate and 3- (trimethoxysilyl) propyl methacrylate.

The siloxane crosslinking agent may be methyltriethoxysilane.

The second seed layer may be 2 to 20% by weight of the entire impact modifier.

The aromatic monomer constituting the polymer of the second seed layer may be styrene or alphamethyl styrene, and the non-aromatic monomer may be methyl methacrylate, ethyl methacrylate or 2-ethylnucleosil methacrylate.

The polymer of the second seed layer may include at least one monomer selected from the group consisting of aromatic monomers and non-aromatic monomers in the polymer of the first seed layer; And allyl methacrylate and 3- (trimethoxysilyl) propylmethacrylate; one or more crosslinkable monomers selected from the group consisting of; It may be a copolymer grafted.

The second seed layer may be a polymer having a particle diameter of 150 to 250nm.

The polymer of the core layer may be from 10 to 90% by weight of the impact modifier.

The polymer of the core layer may be a polymer obtained by emulsifying the acrylate-based monomer and the crosslinking agent with water and an emulsifier, and slowly dropping the polymer into the second seed layer polymer, or by dividing several times.

The acrylate monomer is C ₂ ~ C ₈ alkyl acrylate selected from the group consisting of ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and octyl acrylate It is a monomer, and the crosslinking agent may be selected from the group consisting of allyl methacrylate and trimethylolpropane triacrylate.

The polymer of the shell layer may be 10 to 90% by weight of the total impact modifier.

The alkyl acrylate monomer constituting the polymer of the shell layer may be methyl methacrylate or a derivative of methyl methacrylate.

The aromatic vinyl monomer constituting the polymer of the shell layer may be an aromatic nitrile monomer.

The polymer of the shell layer is an alkyl acrylate monomer to the polymer of the core layer; And at least one monomer selected from the group consisting of aromatic vinyl monomers; It may be a copolymer grafted in the presence of at least one crosslinking agent selected from the group consisting of allyl methacrylate, trimethylolpropane triacrylate and divinylbenzene.

The impact modifier may be a polymer having a particle diameter of 200 to 300nm.

The polymer of the first seed, the second seed, the core and the shell layer is prepared by using 0.1 to 10% by weight of one or more emulsifiers selected from the group consisting of sodium dodecyl sulfate, dioctylsodium sulfosuccinate, and fatty acid salts. Can be prepared.

In addition, the present invention provides a thermoplastic resin composition, comprising the impact modifier as described above.

Hereinafter, the present invention will be described in detail.

The present invention intends to use a composite of a silicone rubber and an acrylic rubber as an impact modifier for producing a thermoplastic resin composition having excellent impact strength, colorability, and chemical resistance, but it is difficult to directly graf the acrylic rubber to the silicone rubber. The rubber is characterized by grafting an aromatic monomer such as styrene, a non-aromatic monomer such as methyl methacrylate or a mixture thereof, and then grafting the acrylic rubber thereon.

That is, the impact modifier of the multilayer structure according to the present invention comprises a first seed layer made of a silicone rubber; A second seed layer made of a copolymer obtained by grafting at least one monomer selected from the group consisting of aromatic monomers and non-aromatic monomers to the polymer of the first seed layer; A core layer made of a copolymer obtained by grafting an acrylate monomer to the polymer of the second seed layer; And a shell layer comprising a copolymer obtained by grafting at least one monomer selected from the group consisting of an alkyl acrylate monomer and an aromatic vinyl monomer to the polymer of the core layer. It is made, including.

As described above, the impact modifier of the present invention is prepared by sequentially polymerizing the first seed layer, the second seed layer, the core layer, and the shell layer. The polymer conversion ratio of each layer is maximized, and the particle size of the finally polymerized latex is 200. It is preferable to set it as -300 nm, and to make latex solid content rate into 30 to 35%. The characteristics of each layer will be described in detail below.

The first seed layer is a layer made of silicone rubber and preferably occupies 5 to 50% by weight of the impact modifier.

The silicone rubber is made from a raw material consisting of dimethyl siloxane, a siloxane having a vinyl group, and a siloxane crosslinking agent. Dimethyl siloxane can be used singly or in combination of nucleated methylcyclotrisiloxane, octomethylcyclotetrasiloxane, dodecamethylcyclonuclesiloxane, and the like, and more preferably, octomethylcyclotetrasiloxane is used. The siloxane having a vinyl group may be used alone or in combination of triethoxy vinylsilane, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, and the like. It is preferable to use it in 10 weight%. In addition, although the siloxane crosslinking agent can use methyl triethoxysilane, it is preferable to use 1-20 weight% of dimethyl siloxane.

In addition, the silicone rubber is emulsified dimethyl siloxane, siloxane having a vinyl group, and siloxane crosslinking agent in water and emulsifier, and then emulsified the size of the emulsified monomer using a homogenizer having a high speed rotational force of 10,000rpm, and emulsified monomer 80 It is prepared by adding to a high temperature aqueous solution of ℃ or higher and then polymerized for at least 5 hours to obtain a latex, the latex obtained is cooled slowly and left for at least 24 hours and then neutralized with an alkaline solution. In the production of the silicone rubber, a catalyst and an emulsifier may be added. As the catalyst, dodecylbenzenesulfonic acid, which is an aliphatic substituted benzene sulfonic acid, is preferable, and as an emulsifier, sodium dodecylbenzenesulfonic acid substituted with sodium dodecylbenzenesulfonic acid, etc. Can be used. Sodium carbonate may be used to neutralize the acidic latex to pH 7-8 after completion of the polymerization.

In order to connect the silicone rubber, which is the first seed layer, and the acrylic rubber of the core layer, a second seed layer is formed between the first seed layer and the core layer. The second seed layer is a layer formed by copolymerizing at least one grafting monomer selected from the group consisting of aromatic monomers and non-aromatic monomers in the first seed layer, and preferably occupies 2 to 20% by weight of the impact modifier.

Among the grafting monomers constituting the polymer of the second seed layer, aromatic monomers include styrene, alphamethyl styrene, and the like. Non-aromatic monomers include methyl methacrylate methyl methacrylate, ethyl methacrylate, and 2-ethyl nucleosil metal. Acrylates and the like.

The polymer of the second seed layer may be prepared by adding crosslinkable monomers such as allyl methacrylate and 3- (trimethoxysilyl) propyl methacrylate alone or in addition to the grafting monomer. As the crosslinkable monomer, allyl methacrylate, 3- (trimethoxysilyl) propyl methacrylate, or the like is preferably used in an amount of 0 to 5% by weight based on the grafting monomer.

The polymer of the second seed layer is prepared by emulsifying the grafting monomer and the crosslinkable monomer with water and an emulsifier, followed by dropwise addition to the prepolymerized silicone rubber over 2 hours, and simultaneously grafting copolymerization with an initiator. The emulsifier is preferably used in an amount of 1 to 5% by weight based on monomers alone or in combination with sodium dodecyl sulfate, dioctyl sodium sulfosuccinate, fatty acid salts and the like. The initiator is preferably a persulfate pyrolysis initiator, and is used with a reaction temperature of 70 ° C or higher.

The second seed layer may be a polymer having a particle diameter of 150 to 250 nm.

The core layer is a layer made of a copolymer obtained by grafting an acrylate-based monomer to the polymer of the second seed layer, and preferably occupies 10 to 90% by weight of the impact modifier. More preferably, it is 65 to 80 weight%.

The core layer is polymerized by emulsifying the acrylate monomer and the crosslinking agent with water and an emulsifier, and then slowly dropping the polymer into the second seed layer polymer or by dividing the solution several times.

Examples of the acrylate monomers alone or two C ₂ ~ C ₈ alkyl acrylates such as ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, 2-ethylnuclear acrylate, octyl acrylate It is preferable to mix and use the above. More preferably, in consideration of reactivity and physical properties, butyl acrylate, 2-ethylnuclear acrylate, octyl acrylate are used alone or in combination of two or more thereof.

The crosslinking agent is preferably used in an amount of 0 to 5% by weight based on allyl methacrylate and trimethylolpropane triacrylate alone or in combination with the acrylate monomer. More preferably, it is used at 0.1 to 1.5% by weight, which does not impair the impact and graft efficiency of the rubber.

The emulsifier may be used in an amount of 1 to 5% by weight of the acrylate monomer alone or in combination with sodium dodecyl sulfate, dioctyl sodium sulfosuccinate, fatty acid salts.

As the initiator, a hydroperoxide-based redox initiator may be used.

The shell layer is a layer made of a copolymer obtained by grafting at least one monomer selected from the group consisting of alkyl acrylate monomers and aromatic vinyl monomers to the polymer of the core layer, preferably occupying 10 to 90% by weight of the impact modifier. Do. More preferably, it is 10-40 weight%.

The monomer forming the shell layer is one or more monomers selected from the group consisting of alkyl acrylate monomers and aromatic vinyl monomers, and monomers used to prepare a hard polymer having a high glass transition temperature are preferable. As the alkyl acrylate monomer, methyl methacrylate, a derivative of methyl methacrylate, and the like are preferable. As said aromatic vinyl monomer, an aromatic nitrile monomer etc. are preferable. In addition, a crosslinking agent may be used to prepare the polymer of the shell layer, with allyl methacrylate, trimethylolpropane triacrylate, divinylbenzene and the like being preferred.

In addition, the polymer of the first seed, the second seed, the core, and the shell layer may use 0.1 to 10% by weight of an emulsifier such as sodium dodecyl sulfate, dioctyl sodium sulfosuccinate and fatty acid salt.

The latex prepared in the order of the first seed, the agent seed, the core and the shell layer may be obtained in powder form for application to the thermoplastic resin. That is, the prepared latex is diluted with ion-exchanged water so as to have a content of 10 to 15% by weight of solids, and then aggregated by adding an acid or basic solution, and the aged mixed solution is heated to 90 ° C. or higher, and cooled. After washing, filtration, and drying, an impact modifier in powder form is obtained.

In addition, the present invention is a polycarbonate (PC), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyamide-based (PA) , Thermoplastics such as polyethylene (PE), polypropylene (PP), polymethyl methacrylate (PMMA), PC / ABS, PC / PBT, PA / PP, PVC / PMMA

The thermoplastic resin composition is prepared by extrusion molding or injection molding at a temperature of 250 to 320 ° C. by adding 1 to 20 parts by weight of an impact modifier having a multilayer structure to 100 parts by weight of a thermoplastic resin.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

Examples 1 to 10: Preparation of a thermoplastic resin using an impact modifier having a multilayer structure of the first seed-second seed-core-shell layer

Example 1

First step: first seed polymerization

235 g of ion-exchanged water, 1 g of dodecylbenzenesulfonic acid (70% by weight solution), 5 g of sodium dodecylbenzenesulfonic acid (9.5% by weight solution), 68 g of octamethylcyclotetrasiloxane, 3.5 g of triethoxymethylsilane and trimethoxysilyl propyl After emulsifying 6.5 g of methacrylate in a container, the emulsion monomer was granulated for 30 seconds using a homogenizer having a high speed of 10,000 rpm. The emulsified monomer was introduced into a reactor in a nitrogen atmosphere, heated to a temperature of 85 ° C., and reacted for 5 hours. After the reaction, the mixture was cooled to room temperature, left for 24 hours, and the latex of the first seed was polymerized by neutralizing the pH to 7.5 with sodium carbonate (2 wt% solution). The particle size of the polymerized latex was 175 nm and the conversion was 81%.

Second Step: Second Seed Polymerization

Ion exchange water 25g, sodium lauryl sulfate (42 wt% solution) 20g, methyl methacrylate 19g, and 0.5g of allyl methacrylate was emulsified in a container. The emulsified monomer was added dropwise to the first seed latex contained in a reactor at a temperature of 75 ° C. and a nitrogen atmosphere for 2 hours, and 15 g of sodium persulfate (1% by weight solution) was added to the reaction to react the latex of the first seed. The polymerization was completed. The particle size of the polymerized latex was 179 nm and the conversion was 95%.

Step 3: core polymerization

30 g of ion-exchanged water, 5 g of fatty acid salt (8 wt% solution), 34.85 g of butyl acrylate and 0.15 g of allyl methacrylate as a crosslinking agent were placed in a container to emulsify. The emulsified monomer is added to the seed latex in a reactor at a temperature of 60 ° C. and a nitrogen atmosphere at an interval of three times for 1 hour. Before mixing the monomer, 1 g of a mixed solution of FES (Ferrous Sulfate Heptahydrate, FeH ₁₄ O ₁₁ S) and EDTA is added. After the addition of the monomer, 10 minutes after the monomer addition, 2 g of SFS (Sodium Formaldehyde Sulfoxylate, CH ₃ NaO ₃ S, 3 wt% solution) and 0.5 g of t-butylhydroperoxide, an initiator, were added to react to polymerize the core latex. The particle size of the polymerized latex was 215 nm and the conversion was 98%.

Step 4: Shell Polymerization

In the shell polymerization, a method of dividing the monomer to be used twice was selected. Methyl methacrylate 9.95 and 0.05 g of crosslinking agent allyl methacrylate were added to a core latex in a reactor at a temperature of 75 ° C. and a nitrogen atmosphere. Then, 1 g of fatty acid salt was added and 0.5 g of sodium persulfate as an initiator was added. The reaction was carried out for 30 minutes. After 30 minutes, the same amount of monomer and emulsifier were added to the reactor and then an initiator was added. In order to increase the conversion rate, a small amount of initiator was further added, followed by reaction for 1 hour to prepare a final latex. The particle size of the final latex was 230 nm and the conversion was 99%.

Step 5: preparing a thermoplastic resin

To 100 parts by weight of polycarbonate resin (LG Dow's PC200-1) was mixed with 3 parts by weight of the impact modifier prepared in the first to fourth steps, 0.5 parts by weight of the processing additive and 0.02 parts by weight of the pigment for colorability test were added. Using a twinscrew extruder manufactured by Leistritz at 200 rpm at a speed of improvement of 60 kg / hr at 250-320 ° C. and an EC100 Φ 30 injection machine manufactured by ENGEL at a temperature of 250-320 ° C. By injection, a specimen was prepared to evaluate impact strength, colorability and chemical resistance.

The particle size of the polymer was measured using a laser light scattering device (NICOMP), and the amount of latex solids was weighed by placing the latex in a container and then placed in a drying oven for more than 12 hours at 80 ℃. The amount of solids was calculated and the conversion was calculated.

[Examples 2 to 8]

The same procedure as in Example 1 was carried out except that the amount of the monomer was adjusted such that the first seed, the second seed, the core, and the shell were composed of the weight ratio as shown in Table 1 in the entirety of the impact modifier. Carbonate resin specimens were prepared.

Example 9

A polycarbonate resin specimen was prepared in the same manner as in Example 1 except that styrene was used as a monomer for preparing the second seed.

In this case, the particle size of the second seed in the prepared impact modifier, the particle size of the final latex was 232nm, the conversion rate was 98%.

Example 10

 In the fourth shell polymerization step, 25.46 g of styrene, 8.49 g of acrylonitrile, 0.7 g of divinylbenzene, and 0.35 g of allyl methacrylate were emulsified in 18 g of ion-exchanged water and 5 g of fatty acid salt, followed by 70 ° C. containing a core polymer. Polycarbonate was carried out in the same manner as in Example 1 except that the monomer was emulsified in a nitrogen atmosphere reactor over 1 hour, and at the same time, a shell was prepared by adding 2 g of t-butyl hydroperoxide and 10 g of SFS and polymerizing the same. Resin specimens were prepared.

The particle size of the final latex produced was 228nm, the conversion was 98%.

Comparative Example 1 Preparation of Thermoplastic Resin Using Impact Reinforcement Consist of Seed Only

Comparative Example 1

The impact modifier is composed of only the first seed layer and the second seed layer in the same manner as in Example 1, except that the weight ratio is as shown in Table 1, and the core polymerization step and the shell polymerization step are omitted. After preparing the impact modifier, a polycarbonate resin specimen was prepared using the same.

Comparative Example 2: Preparation of thermoplastic resin using impact modifier without second seed layer

Comparative Example 2

The structure of the first seed layer-core layer-shell layer was prepared in the same manner as in Example 1 except that the impact modifier was composed of a weight ratio as shown in Table 1 below, and the second seed polymerization step was omitted. After preparing an impact modifier having a polycarbonate resin specimen was prepared using the same.

Comparative Example 3: Preparation of thermoplastic resin using silicone-based acrylic impact modifier

Comparative Example 3

The impact modifier having the structure of the core-shell layer in the same manner as in Example 1 except that the first and the second seed polymerization step is omitted, and the weight ratio as shown in Table 1 in the overall impact modifier. After preparing the prepared polycarbonate resin specimen using the same.

Test Example: Evaluation of Hardness, Colorability and Chemical Resistance of Thermoplastics

Impact strength is Izod (Izod) impact strength by the method of ASTM D-256 and after measuring 1/8 inch specimens at room temperature and -40 ℃, respectively, the results are shown in Table 1 below.

Chemical resistance is injected by 2mm thick and 100mm diameter circular disk specimens, then dries 2-3 drops of thinner in the center of the specimen surface and dries it, and frees the fall weight of 15 pounds from DART drop impact tester at 150cm height. The degree of cracking of the circular specimen at the time of dropping was measured. 5 points for the degree of breakage, 4 points for the cracks caused by the bending, 3 points for the cracks of the support while bending, 2 points for the holes formed during the bending, and 1 point for the broken points, and the results are shown in the following table. 1 is shown.

The colorability measured CIELab color values through color tester for the specimens processed by the colorant at the time of injection molding. ΔE = (ΔL) representing the difference in color value based on the specimen with the best coloration (the specimen most similar to the color of the colorant). ² + Δa ² + Δb ² ) ^1/2 value to distinguish the degree of coloring. 5 points for ΔE values of 2 or less, 4 points for ΔE values of 2 to 4, 3 points for ΔE values of 4 to 6, 2 points for ΔE values of 6 to 8, and ΔE values of 8 In case of exceeding one point, the result is shown in Table 1 below.

As can be seen in Table 1, after grafting (second seed layer) to an aromatic monomer or a non-aromatic monomer on the silicone rubber (first seed layer), and grafting acrylic rubber (core layer, shell layer) thereon The thermoplastic resins of Examples 1 to 10 prepared by using the impact modifier of the multilayer structure prepared by the step of polymerizing Comparative Example 1, the second seed layer prepared by using the impact modifier made of only a seed layer (silicone-based rubber) Omitted, compared with the thermoplastic resin of Comparative Example 2 prepared using the impact modifier prepared by grafting the acrylic rubber directly to the silicone rubber and Comparative Example 3 made of only the acrylic rubber without the silicone rubber, the impact strength, colorability and chemical resistance It can be seen that excellent.

As described above, the impact modifier of the multilayer structure according to the present invention and the thermoplastic resin composition comprising the same are grafted (second seed layer) to an aromatic monomer or a non-aromatic monomer on a silicone rubber (first seed layer), It is a useful invention which has the effect of excellent impact strength, coloring property, and chemical resistance, including the impact modifier of the multilayer structure manufactured by grafting acrylic rubber (core layer, shell layer) on it.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such variations and modifications fall within the scope of the appended claims. It is also natural.

Claims (20)

A first seed layer made of silicon-based rubber; A second seed layer made of a copolymer obtained by grafting at least one monomer selected from the group consisting of aromatic monomers and non-aromatic monomers to the polymer of the first seed layer; A core layer made of a copolymer obtained by grafting an acrylate monomer to the polymer of the second seed layer; And A shell layer made of a copolymer obtained by grafting at least one monomer selected from the group consisting of alkyl acrylate monomers and aromatic vinyl monomers to the polymer of the core layer; Impact modifier of the multi-layer structure, characterized in that made. The method of claim 1, Impact modifier of the multi-layer structure, characterized in that the first seed layer is 5 to 50% by weight of the total impact modifier. The method of claim 1, The impact modifier of the multilayer structure, characterized in that the silicone rubber constituting the first seed layer is made from a raw material consisting of dimethyl siloxane, a siloxane having a vinyl group, and a siloxane-based crosslinking agent. The method of claim 3, Multi-layered impact modifier, characterized in that the dimethyl siloxane is selected from the group consisting of nuxamethylcyclotrisiloxane, octomethylcyclotetrasiloxane and dodecamethylcyclonuxasiloxane. The method of claim 3, The siloxane having a vinyl group is at least one selected from the group consisting of triethoxy vinylsilane, 3- (trimethoxysilyl) propyl acrylate and 3- (trimethoxysilyl) propyl methacrylate. Impact modifier. The method of claim 3, Multi-layered impact modifier, characterized in that the siloxane-based crosslinking agent is methyltriethoxysilane. The method of claim 1, Impact modifier of the multi-layer structure, characterized in that the second seed layer is 2 to 20% by weight of the total impact modifier. The method of claim 1, The impact modifier of the multilayer structure characterized in that the aromatic monomer constituting the polymer of the second seed layer is styrene or alphamethyl styrene, and the non-aromatic monomer is methyl methacrylate, ethyl methacrylate or 2-ethylnucleosil methacrylate. The method of claim 1, At least one monomer selected from the group consisting of an aromatic monomer and a non-aromatic monomer in the polymer of the first seed layer; And allyl methacrylate and 3- (trimethoxysilyl) propylmethacrylate; one or more crosslinkable monomers selected from the group consisting of; Impact modifier of the multilayer structure characterized in that the copolymer is grafted. The method of claim 1, Multi-layered impact modifier, characterized in that the second seed layer is a polymer having a particle diameter of 150 to 250nm. The method of claim 1, Impact modifier of the multi-layer structure, characterized in that the polymer of the core layer is 10 to 90% by weight of the total impact modifier. The method of claim 1, The polymer of the core layer is an impact modifier of a multi-layered structure, characterized in that the polymer is emulsified acrylate monomer and crosslinking agent with water and emulsifier and slowly dropwise added to the second seed layer polymer, or divided into several times. The method of claim 12, C ₂ ~ C ₈ alkyl acrylate wherein the acrylate monomer is at least one selected from the group consisting of ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and octyl acrylate And a crosslinking agent is at least one selected from the group consisting of allyl methacrylate and trimethylolpropane triacrylate. The method of claim 1, Impact modifier of the multi-layer structure, characterized in that the polymer of the shell layer is 10 to 90% by weight in the total impact modifier. The method of claim 1, Multi-layered impact modifier, characterized in that the alkyl acrylate monomer constituting the polymer of the shell layer is methyl methacrylate or a derivative of methyl methacrylate. The method of claim 1, The impact modifier of the multilayer structure characterized in that the aromatic vinyl monomer constituting the polymer of the shell layer is an aromatic nitrile monomer. The method of claim 1, The polymer of the shell layer is an alkyl acrylate monomer to the polymer of the core layer; And at least one monomer selected from the group consisting of aromatic vinyl monomers; The impact modifier of a multilayer structure characterized in that the copolymer is grafted in the presence of at least one crosslinking agent selected from the group consisting of allyl methacrylate, trimethylolpropane triacrylate and divinylbenzene. The method of claim 1, The impact modifier of the multi-layer structure, characterized in that the polymer having a particle size of 200 to 300nm. The method of claim 1, The polymer of the first seed, the second seed, the core and the shell layer is prepared by using 0.1 to 10% by weight of one or more emulsifiers selected from the group consisting of sodium dodecyl sulfate, dioctylsodium sulfosuccinate, and fatty acid salts. Impact modifier of the multi-layer structure, characterized in that the manufacturing. 20. A thermoplastic resin composition comprising an impact modifier according to claim 1.