KR20190000155A - 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. More specifically, the present invention provides a copolymer composition, a preparing method thereof, and a thermoplastic resin composition including the same. The copolymer composition contains: a first core-shell copolymer having a (meth)acrylic core which includes an alkyl (meth)acrylate monomer derived repetition unit, and a first shell which includes an aromatic vinyl monomer derived repetition unit and a vinyl cyanide monomer derived repetition unit; and a second core-shell copolymer having a conjugate diene core which includes a conjugate diene monomer derived repetition unit, and a second shell which includes an aromatic vinyl monomer derived repetition unit and a vinyl cyanide monomer derived repetition unit. An average particle size ratio between the (meth)acrylic core and the conjugate diene core is 1 : 1.66-1 : 7.6, and a weight ratio between the (meth)acrylic core and the conjugate diene core is 1 : 2-1 : 10. The present invention reduces content of an emulsifier when core is polymerized, shortens polymerization time and enhances coherence properties of latex, which is a copolymer composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a copolymer composition, a method for producing the same, and a thermoplastic resin composition containing the copolymer composition,

The present invention relates to a copolymer composition, and more particularly, to a copolymer composition contained in a thermoplastic resin composition and serving as an impact modifier, a method for producing the same, and a thermoplastic resin composition containing the same.

Acrylonitrile-butadiene-styrene (hereinafter abbreviated as ABS) is a representative resin having both functionality and versatility. It is a resin which is excellent in stiffness and chemical resistance of acrylonitrile, processability of butadiene and styrene, mechanical strength And aesthetic appearance, it has been widely used in automobile appliances, electric / electronic products and office equipment. Molded articles for use in these applications are generally produced through processes such as extrusion and injection molding.

On the other hand, the ABS resin is generally prepared by emulsion polymerization. When emulsion polymerization is carried out, the ABS copolymer is obtained in the form of a latex in which an ABS copolymer is dispersed in an aqueous solvent.

At this time, the emulsifier charged at the time of polymerization remains on the latex of the ABS copolymer, and the residual emulsifier has a problem of deteriorating the mechanical properties and appearance characteristics of the ABS resin.

Further, in order to carry out processes such as extrusion and injection molding using the obtained ABS copolymer latex, it is necessary to obtain the ABS copolymer latex in the form of dry powder by coagulating the ABS copolymer latex. The water content of the coagulated ABS copolymer There is a problem that the drying productivity is deteriorated. When the fine content of the fine particles is high, the fine particles after molding are projected on the surface of the molded article, and the appearance characteristics are deteriorated.

As a solution to this problem, in order to add the advantages of the butyl acrylate rubber to the ABS resin, many studies have been conducted to introduce a butadiene-butyl acrylate copolymer obtained by simultaneously polymerizing a butadiene monomer and a butyl acrylate monomer in the production of butadiene rubber However, due to the difference in degree of polymerization between the butadiene monomer and the butyl acrylate monomer, it is difficult to proceed to commercialization due to difficulty in producing the copolymer.

Therefore, it is important to simultaneously improve the mechanical properties and appearance properties of the ABS resin by reducing the amount of the emulsifier used, maintaining the mechanical properties of the ABS resin, improving the flocculation property after the production of the ABS copolymer latex, .

KR 1993-0019756 A

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above problems of the prior art, and it is an object of the present invention to provide a bimodal copolymer composition in which a shell is graft- It is an object of the present invention to provide a thermoplastic resin composition which is excellent in gloss and appearance while maintaining or improving mechanical properties at the same level by improving the cohesive property of the co-extruded composition latex and including the obtained copolymer composition.

According to one embodiment of the present invention for solving the above-mentioned problems, the present invention provides a method for producing an acrylic resin composition, which comprises (meth) acrylic core containing a repeating unit derived from an alkyl (meth) acrylate monomer, a repeating unit derived from an aromatic vinyl monomer, A first core-shell copolymer comprising a first shell comprising repeating units; And a second core-shell copolymer comprising a conjugated diene-based core comprising a conjugated diene monomer-derived repeating unit and a second shell comprising a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a vinyl cyan monomer, Acrylic core and the conjugated diene-based core is 1: 1.66 to 1: 7.6, and the weight ratio of the (meth) acrylic core and the conjugated diene-based core is 1: 2 to 1: 10. ≪ / RTI >

The present invention also relates to a process for producing a (meth) acryl-based core, comprising the steps of: (i) polymerizing an alkyl (meth) acrylate monomer to prepare a (meth) acrylic core; ii) polymerizing the conjugated diene monomer to prepare a conjugated diene-based core (S2); (meth) acrylate core prepared in the step (S1) and the conjugated diene-based core prepared in the step (S2) are introduced into one reactor, and the aromatic vinyl monomer and the vinyl cyan monomer are introduced into the reactor, (Meth) acrylic core prepared in the step (S1), and a step (S3) of graft polymerizing a first shell on the acrylic core and a second shell on the conjugated diene core, The ratio of the average particle diameter of the conjugated diene-based core prepared in the step (S2) is 1: 1.66 to 1: 7.6 and the ratio of the conjugated diene-based core prepared in the step (S1) Wherein the ratio of the weight of the core is 1: 2 to 1:10.

The present invention also provides a thermoplastic resin composition comprising a copolymer composition.

According to the present invention, when a bimodal copolymer composition in which a core is graft polymerized in each core and a method for producing the same are used, the content of the emulsifier is reduced during the core polymerization At the same time, it is possible to shorten the polymerization time and to improve the coagulation property of the latex of the copolymer composition.

Further, the thermoplastic resin composition containing the copolymer composition as an impact modifier has a higher gloss than a thermoplastic resin composition containing an ABS resin as an impact modifier, exhibiting mechanical properties, especially impact strength, The protrusion of the projection is small and the appearance characteristic is excellent.

The terms and words used in the description of the present invention and in the claims should not be construed to be limited to ordinary or dictionary terms and the inventor should appropriately interpret the concepts of the terms appropriately The present invention should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The copolymer composition according to the present invention comprises a first shell comprising a (meth) acrylic core comprising a repeating unit derived from an alkyl (meth) acrylate monomer, a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a vinyl cyan monomer A first core-shell copolymer; And a second core-shell copolymer comprising a conjugated diene-based core comprising a conjugated diene monomer-derived repeating unit and a second shell comprising a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a vinyl cyan monomer, Acrylic core and the conjugated diene-based core is 1: 1.66 to 1: 7.6, and the weight ratio of the (meth) acrylic core and the conjugated diene-based core is 1: 2 to 1: 10 < / RTI >

That is, the copolymer composition according to the present invention comprises a first core-shell copolymer in which a core of a (meth) acrylic core and a conjugated diene-based core are graft-polymerized into a first shell and a second shell, respectively, Core-shell copolymer. ≪ / RTI > As described above, the bimodal copolymer composition comprising the first core-shell copolymer and the second core-shell copolymer using different kinds of cores is excellent in the cohesion of the copolymer composition latex due to emulsion polymerization, The characteristic has an excellent effect.

In this connection, in the case of producing a bimodal copolymer composition of a small-diameter and large-diameter core using a conjugated diene-based core alone, such as a conventional acrylonitrile-butadiene-styrene resin, The effect of improvement of the physical properties is insignificant and the polymerization time may be prolonged so that economical efficiency and commerciality can not be secured in the production process and mechanical properties and appearance characteristics may be deteriorated due to increase in the amount of emulsifier used during polymerization, According to the invention, it may be preferable to use different types of cores.

Particularly, when a (meth) acrylic core and a conjugated diene-based core are used in accordance with the present invention, a short polymerization time, a low amount of emulsifier used, and an effect of improving flocculation characteristics are obtained from the (meth) It is possible to secure the physical properties.

The ratio of the average particle diameter of the (meth) acrylic based core and the average particle diameter of the conjugated diene based core may be 1: 1.66 to 1: 7.6, 1: 2 to 1: 6, or 1: 2 to 1: Within this range, the copolymer composition latex exhibits excellent cohesive properties, and the thermoplastic resin composition containing the copolymer composition as an impact modifier has excellent mechanical properties and appearance characteristics.

In this connection, the ratio of the average particle diameter of the (meth) acrylic core and the average particle diameter of the conjugated diene-based core is set at an equivalent level (for example, 1: 1) In the case of producing at a ratio larger than the particle diameter, the coagulating property is lowered due to the large average particle diameter of the (meth) acrylic-based core, thereby deteriorating the appearance characteristics of the thermoplastic resin composition, and due to the small average particle diameter of the conjugated diene- It may be preferable to control the ratio of the average particle diameter of the (meth) acrylic core and the average particle diameter of the conjugated diene-based core according to the present invention.

The term " monomer-derived repeating unit " in the present invention refers to a component derived from a monomer, a structure thereof, or a substance itself, and when the polymer is polymerized, the introduced monomer means a repeating unit .

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, which is graft-polymerized on the core of the core-shell type copolymer to form a shell or a shell layer.

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

According to one embodiment of the present invention, the alkyl (meth) acrylate monomer may be an alkyl (meth) acrylate monomer containing an alkyl group having 2 to 8 carbon atoms. The alkyl group having 2 to 8 carbon atoms may be a linear alkyl group having 2 to 8 carbon atoms and a branched alkyl group having 3 to 8 carbon atoms. As specific examples, the alkyl (meth) acrylate monomer may be selected from the group consisting of ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, ) Acrylate, octyl (meth) acrylate, or 2-ethylhexyl (meth) acrylate. Here, the alkyl (meth) acrylate monomer may mean alkyl acrylate or alkyl methacrylate.

According to an embodiment of the present invention, the conjugated diene monomer may be 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 1,3-butadiene and 2-halo-1,3-butadiene (wherein halo means a halogen atom).

Also, according to one embodiment of the present invention, the aromatic vinyl monomer is at least one selected from the group consisting of styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, and 1-vinyl-5-hexyl naphthalene.

According to an embodiment of the present invention, the vinyl cyan monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

On the other hand, the aromatic vinyl monomer-derived recurring units and the vinyl cyan monomer-derived recurring units respectively contained in the first shell of the first core-shell copolymer and the second shell of the second core- , And in this case, there is an effect of excellent coagulation characteristics of the bimodal copolymer composition latex.

According to one embodiment of the present invention, the average particle size of the (meth) acrylic core may be 50 nm to 150 nm, 60 nm to 125 nm, or 70 nm to 125 nm, and within this range, Is excellent in the cohesive property of the thermoplastic resin composition, and thus the thermoplastic resin composition has excellent appearance characteristics.

According to an embodiment of the present invention, the average particle diameter of the conjugated diene-based core may be 250 nm to 380 nm, 250 nm to 360 nm, or 250 nm to 350 nm, and within this range, the thermoplastic resin composition And the mechanical properties such as the impact strength of the resin composition are excellent.

According to an embodiment of the present invention, the content of the (meth) acrylic core may be smaller than the content of the conjugated diene-based core in the total content of the copolymer composition. That is, except for the content of the first shell and the second shell of the first core-shell copolymer and the second core-shell copolymer, the content of the (meth) acrylic core is less than the content of the conjugated diene-based core In this case, the thermoplastic resin composition has excellent mechanical properties such as impact strength and the like. As a specific example, the weight ratio of the (meth) acrylic core and the conjugated diene core may be 1: 2 to 1:10, 1: 2.5 to 1: 9, or 1: 3 to 1: The thermoplastic resin composition has excellent appearance and mechanical properties.

According to an embodiment of the present invention, the content of the (meth) acrylic core is 5 wt% to 20 wt%, 5 wt% to 15 wt%, or 7 wt% to 15 wt% %. Within this range, the thermoplastic resin composition has an effect of preventing deterioration of the mechanical properties of the thermoplastic resin composition and exhibiting excellent appearance and aggregation characteristics.

According to an embodiment of the present invention, the content of the conjugated diene-based core is 40 wt% to 60 wt%, 40 wt% to 55 wt%, or 45 wt% to 53 wt% By weight, and the mechanical properties such as impact strength and the like of the thermoplastic resin composition are excellent within this range.

According to an embodiment of the present invention, the content of the first shell and the second shell may be 30 wt% to 50 wt%, or 35 wt% to 45 wt%, based on the entire content of the copolymer composition In this range, the copolymer composition latex exhibits excellent cohesive properties and excellent mechanical properties and appearance characteristics of the thermoplastic resin composition. As a specific example, the content of the repeating unit derived from an aromatic vinyl monomer contained in the first shell and the second shell is 20% by weight to 40% by weight, or 25% by weight to 35% by weight, And the content of the repeating unit derived from a vinyl cyan monomer contained in the first shell and the second shell is 5 wt% to 15 wt%, or 10 wt% to 15 wt% based on the entire content of the copolymer composition %. As a more specific example, the content of the aromatic vinyl monomer-derived repeating units and the content ratio of the vinyl cyan monomer-derived repeating units (content of repeating units derived from aromatic vinyl monomers: content of repeating units derived from vinyl cyan monomers) 4: 1, or from 2.33: 1 to 3: 1. Within this range, the copolymer composition latex exhibits excellent coagulation characteristics, and the mechanical and cosmetic properties of the thermoplastic resin composition This is an excellent effect.

Meanwhile, according to one embodiment of the present invention, the (meth) acrylic core may contain a repeating unit derived from a crosslinkable monomer. As described above, when the (meth) acrylic-based core contains a repeating unit derived from a crosslinkable monomer, a (meth) acrylic-based core containing a repeating unit derived from an alkyl (meth) Polymerization is easily carried out, so that the coagulation property of the copolymer composition latex and the appearance characteristics of the copolymer composition are improved. Specific examples of the crosslinkable monomer include 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; Vinyl-based cross-linkable monomers such as divinyl benzene, divinyl naphthalene and diallyl phthalate, and the like. (Meth) acrylate based on the total content of the (meth) acryl-based core in the case where the (meth) acrylic-based core contains a crosslinkable monomer, the repeating unit derived from alkyl (meth) Wt%, or 98.5 wt% to 99.5 wt%; And 0.1 to 2% by weight, or 0.5 to 1.5% by weight of a repeating unit derived from a crosslinkable monomer.

Meanwhile, according to one embodiment of the present invention, the copolymer composition may be obtained in the form of a dry powder through a process such as coagulation, aging, dehydration and drying from the latex of the copolymer composition, The water content of the composition latex after coagulation of the composition latex may be less than 30% by weight, 29% by weight or 27% by weight based on the total amount of the coagulated copolymer composition latex, Whereby the use amount of the flocculant can be reduced, thereby improving the appearance characteristics. Also, the fine content of fine particles after the coagulation of the copolymer composition latex may be less than 10% by weight, 8% by weight or 7% by weight based on the total amount of the coagulated copolymer composition latex, Within this range, there is an effect of improving the regular product yield and the process environment. Here, the total content of the coagulated copolymer composition latex may mean the entire content including the content of the copolymer composition (solid content), the water content, the fine content, and the residual content such as the flocculant and the like, fine) may mean fine particles having an average particle diameter of 75 mu m or less.

The process for producing a copolymer composition according to the present invention comprises the steps of: (i) polymerizing an alkyl (meth) acrylate monomer to prepare a (meth) acrylic core; ii) polymerizing the conjugated diene monomer to prepare a conjugated diene-based core (S2); (meth) acrylate core prepared in the step (S1) and the conjugated diene-based core prepared in the step (S2) are introduced into one reactor, and the aromatic vinyl monomer and the vinyl cyan monomer are introduced into the reactor, (Meth) acrylic core prepared in the step (S1), and a step (S3) of graft polymerizing a first shell on the acrylic core and a second shell on the conjugated diene core, The ratio of the average particle diameter of the conjugated diene-based core prepared in the step (S2) is 1: 1.66 to 1: 7.6 and the ratio of the conjugated diene-based core prepared in the step (S1) The ratio of the weight of the core may be 1: 2 to 1:10.

The step (S1) is a step for producing a (meth) acrylic core by radical polymerization using a peroxide type, redox, or azo type initiator in the presence of an alkyl (meth) acrylate monomer As the polymerization method, emulsion polymerization, bulk polymerization, solution polymerization or suspension polymerization may be used. In order to control the average particle diameter of the (meth) acrylic-based core according to the present invention, a redox initiator And can be carried out by an emulsion polymerization method.

According to one embodiment of the present invention, the redox initiator which can be used in step (S1) is selected from the group consisting of t-butyl hydroperoxide, diisopropylbenzene hydroperoxide and cumene hydroperoxide And in this case, it is effective to provide a stable polymerization environment.

According to an embodiment of the present invention, the emulsifier used in the emulsion polymerization of step (S1) may be selected from the group consisting of alkylaryl sulfonates, alkaline methyl alkyl sulfates, fatty acid soaps, oleic acid alkali salts, rosin acid alkali salts, , Sodium diethylhexyl phosphate, phosphonated polyoxyethylene alcohol, and phosphonated polyoxyethylene phenol. In this case, it is effective to provide a stable polymerization environment. The emulsifier may be added in an amount of, for example, 2 parts by weight or less, 1.5 parts by weight or 0.3 parts by weight to 1 part by weight based on 100 parts by weight of the whole monomer charged in the step (S1) , It is possible to maintain the polymerization stability of the latex in addition to the improvement of the appearance characteristics and may be preferable in terms of controlling the average particle size of the (meth) acrylic core.

On the other hand, in the case of (meth) acryl-based cores prepared by emulsion polymerization of an alkyl (meth) acrylate monomer as in the step (S1), in order to prepare a conjugated diene-based core having an average particle diameter of the same or equivalent level, Compared with the case where the monomers are emulsion-polymerized, the polymerization of the rubber, that is, the production of the core can be carried out only with the use of a smaller amount of the emulsifier, and the residual emulsifier content in the final polymer or copolymer obtained is small and the mechanical properties And the appearance characteristics are improved.

As another example, the step (S1) may be carried out by including a crosslinkable monomer.

The step (S2) is a step for producing a conjugated diene-based core, which can be carried out in an individual step, not in a continuous step with the step (S1), and in the presence of a conjugated diene monomer, (redox) or an azo-based initiator. As the polymerization method, emulsion polymerization, bulk polymerization, solution polymerization or suspension polymerization can be used. According to the present invention, the conjugated diene-based core May be carried out by an emulsion polymerization method using a redox initiator from the viewpoint of adjusting the average particle diameter of the resin.

According to one embodiment of the present invention, the redox initiator that can be used in step (S2) is, for example, one kind selected from the group consisting of t-butyl hydroperoxide, diisopropylbenzene hydroperoxide and cumene hydroperoxide And the peroxide initiator may be at least one selected from the group consisting of potassium persulfate and sodium persulfate. In this case, it is effective to provide a stable polymerization environment.

According to an embodiment of the present invention, the emulsifier used in the emulsion polymerization of the step (S2) may be an alkyl aryl sulfonate, an alkali metal alkyl sulfate, a soap of a fatty acid, an alkali metal salt of an oleic acid, an alkali metal salt of a rosin acid, , Sodium diethylhexyl phosphate, phosphonated polyoxyethylene alcohol, and phosphonated polyoxyethylene phenol. In this case, it is effective to provide a stable polymerization environment. The emulsifier may be added in an amount of 2 parts by weight or less, 1.5 parts by weight or 0.3 parts by weight to 1 part by weight based on 100 parts by weight of the whole monomer charged in the step (S2) Lt; / RTI >

The step (S3) is a step for simultaneously graft-polymerizing the (meth) acrylic core prepared in the step (S1) and the conjugated diene-based core prepared in the step (S2) (Meth) acrylic-based core and the conjugated diene-based core prepared in the step (S2) were put into one reactor and graft polymerization was carried out to obtain a copolymer of the monomer of the same component on the (meth) acrylic- It is possible to form a first shell and a second shell each containing a monomer-derived repeating unit of the same component in each core through graft polymerization. The step (S3) may be carried out by radical polymerization using a peroxide-based, redox-based or azo-based initiator in the presence of a (meth) acrylic core, a conjugated diene-based core, an aromatic vinyl monomer and a vinyl cyan monomer As the polymerization method, emulsion polymerization, bulk polymerization, solution polymerization or suspension polymerization can be used. From the viewpoint of forming a shell in each of different types of cores according to the present invention, a redox initiator And can be carried out by an emulsion polymerization method.

According to one embodiment of the present invention, the redox initiator that may be used in step (S3) is one or more selected from the group consisting of t-butyl hydroperoxide, diisopropylbenzene hydroperoxide and cumene hydroperoxide And in this case, it is effective to provide a stable polymerization environment.

According to an embodiment of the present invention, the emulsifier used in the emulsion polymerization of step (S3) may be selected from the group consisting of alkylaryl sulfonates, alkaline methyl alkyl sulfates, fatty acid soaps, oleic acid alkali salts, rosin acid alkali salts, , Sodium diethylhexyl phosphate, phosphonated polyoxyethylene alcohol, and phosphonated polyoxyethylene phenol. In this case, it is effective to provide 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 to be added in the step (S3), from the viewpoint of maintaining the polymerization stability of the latex can do.

According to one embodiment of the present invention, the method for producing the copolymer composition may include a step of coagulating, aging, dehydrating and drying the copolymer composition latex obtained by emulsion polymerization in the form of a powder . The copolymer composition powder obtained through the above step can serve as an impact modifier in the thermoplastic resin composition.

According to one embodiment of the present invention, the flocculation step may be carried out by adding at least one flocculant 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 flocculation step may be carried out, for example, at 50 ° C to 90 ° C, or 55 ° C to 75 ° C, in which case powder particles having an average particle size of 75 μm to 1,400 μm can be obtained. When the aging step is carried out after the agglomeration step, the aging step may be carried out at 80 to 98 ° C, or 85 to 95 ° C, in which case residual monomers not participating in polymerization can be removed by volatilization , Cracking of the powder particles is prevented, and the water content is reduced. The dewatering and drying step can be carried out by using a hot air drying method after separating the coagulated and / or aged copolymer composition latex into solid components by removing moisture with a dehydrator. In this case, drying time is shortened through dehydration, The residual monomers not participating in the polymerization can be removed through hot air drying.

The thermoplastic resin composition according to the present invention may include the above copolymer composition. 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 producing a molded product through extrusion, injection molding or the like. In this case, the base resin of the thermoplastic resin composition containing the copolymer composition as an impact modifier, that is, The thermoplastic resin serving as a base of the thermoplastic resin composition may be a styrene-based copolymer. The styrenic copolymer may be a copolymer comprising an aromatic vinyl monomer-derived repeating unit and a vinyl cyan monomer-derived repeating unit.

The styrenic copolymer may contain, for example, from 10% by weight to 90% by weight, from 30% by weight to 80% by weight, or from 50% by weight to 80% by weight, based on the entire styrenic copolymer, of an aromatic vinyl monomer- And may contain 10 to 90% by weight, 20 to 70% by weight, or 20 to 50% by weight of repeating units derived from a vinyl cyan monomer. In this case, the mechanical properties of the thermoplastic resin composition There is an effect of excellent physical properties.

According to one embodiment of the present invention, aromatic vinyl monomers usable in the styrenic copolymer include styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4- Cyclohexylstyrene, 4- (p-methylphenyl) styrene and 1-vinyl-5-hexyl naphthalene.

According to an embodiment of the present invention, the vinyl cyan monomer that can be used for the styrenic copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

According to an embodiment of the present invention, the thermoplastic resin composition may include the copolymer composition and the styrenic copolymer. For example, the thermoplastic resin composition may contain 10 wt% to 90 wt%, 10 wt% To 70% by weight, or from 10% by weight to 50% by weight, and the styrenic copolymer is contained in an amount of 10% by weight to 90% by weight, 30% by weight to 90% by weight, or 50% by weight to 90% Within this range, excellent mechanical properties such as impact strength and excellent workability can be obtained.

The thermoplastic resin composition may optionally contain additives such as a heat stabilizer, a light stabilizer, an antioxidant, an antistatic agent, an antimicrobial agent and a lubricant within a range not lowering the physical properties.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood, however, that the following examples are illustrative of the present invention and that various changes and modifications can be made within the scope and spirit of the present invention, which are obvious to those of ordinary skill in the art and do not limit the scope of the present invention.

Example

Example 1

<Preparation of butyl acrylate core>

9.9 parts by weight of butyl acrylate, 0.1 part by weight of allyl methacrylate, 0.08 part by weight of a fatty acid soap as an emulsifier, and 0.1 part by weight of t-butyl hydroperoxide as a polymerization initiator, based on 100 parts by weight of the total monomers, , 0.008 part by weight of iron sulfide as an activator, 0.15 part by weight of ethylenediamine acetic acid salt, 0.2 part by weight of sodium formaldehyde sulfoxylate and 50 parts by weight of ion-exchanged water were added and reacted at 45 ° C to 55 ° C for 1 hour To prepare a butyl acrylate rubber latex having an average particle diameter of 100 nm of butyl acrylate rubber.

<Preparation of butadiene core>

35 parts by weight of ion-exchanged water, 37.5 parts by weight of 1,3-butadiene as an monomer, 1 part by weight of a fatty acid soap as an emulsifier, 0.6 part by weight of sodium sulfate as an electrolyte, and 3 parts by weight of a molecular weight regulator 0.15 part by weight of dodecylmercaptan (TDDM) and 0.2 part by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as an initiator were charged and reacted until the polymerization conversion was 30% to 40% at a reaction temperature of 70 ° C., 12.5 parts by weight of 3-butadiene and 0.2 parts by weight of a fatty acid soap were added, and the reaction was terminated at a polymerization conversion of 95% to prepare a butadiene rubber latex having an average particle size of 300 nm of butadiene rubber. At this time, the time required for the polymerization was 23 hours.

&Lt; Preparation of copolymer composition >

10 parts by weight (based on solid content) of butylacrylate rubber latex obtained above, 50 parts by weight (based on solid content) of butadiene rubber latex, 29 parts by weight of styrene, and 100 parts by weight of acryloyl peroxide And 11 parts by weight of nitrile were added in one portion, and then the temperature of the reactor was kept at 45 to 55 DEG C, 0.1 part by weight of t-butyl hydroperoxide as a polymerization initiator, 0.008 part by weight of iron sulfide as an activator, 0.15 part by weight of ethylenediamine acetic acid And 0.2 part by weight of sodium formaldehyde sulfoxylate were added all at once and graft polymerization was carried out at 45 ° C to 55 ° C for 2 hours to obtain a copolymer composition latex. The composition of the copolymer composition is shown in Table 1 below.

<Preparation of Copolymer Composition Powder>

0.5 part by weight of an antioxidant (winstay-L / IR1076 = 0.8 / 0.2) having an average particle size of 0.9 m was added to the copolymer composition latex obtained above and stirred. Then, an aqueous magnesium sulfate solution (concentration 5% by weight) Lt; RTI ID = 0.0 &gt; 75 C. &lt; / RTI &gt; At this time, the water content and the fine content are shown in Table 3 below.

The coagulated copolymer composition latex was aged until it reached 90 DEG C, dehydrated and dried at a drying temperature of 65 DEG C until the water content reached less than 1 wt% to obtain a copolymer composition powder.

Example 2

In Example 1, butyl acrylate was added in an amount of 6.9 parts by weight, allyl methacrylate 0.1 part by weight, and fatty acid soap 0.06 part by weight to prepare a butyl acrylate core. In the preparation of the butadiene core, 1 , 39.75 parts by weight of 3-butadiene at the beginning of polymerization, 13.25 parts by weight of a polymerization conversion of 30% to 40% at the start of polymerization, 1 part by weight of fatty acid soap at the start of polymerization, 0.3% Except that 7 parts by weight of butyl acrylate rubber latex (based on solid content) and 53 parts by weight of butadiene rubber latex (based on solid content) were added during the preparation of the copolymer composition. The same procedure was followed.

Example 3

In the preparation of the butyl acrylate core, 14.8 parts by weight of butyl acrylate, 0.2 parts by weight of allyl methacrylate and 0.12 part by weight of fatty acid soap were added to prepare a butyl acrylate core in Example 1, , 33.75 parts by weight of 3-butadiene at the time of initiating the polymerization, 11.25 parts by weight at a polymerization conversion of 30% to 40%, and 0.9 parts by weight of the fatty acid soap at the beginning of polymerization, 0.2% Except that 15 parts by weight of butyl acrylate rubber latex (based on solid content) and 45 parts by weight of butadiene rubber latex (based on solid content) were added during the preparation of the copolymer composition. The same procedure was followed.

Example 4

In Example 1, butyl acrylate was added in an amount of 4.95 parts by weight, allyl methacrylate 0.05 part by weight, and fatty acid soap 0.04 part by weight to prepare butyl acrylate core. In the preparation of butadiene core, 1 , 41.25 parts by weight of 3-butadiene at the start of polymerization, 13.75 parts by weight of a polymerization conversion of 30% to 40% at the start of polymerization, 1.1 parts by weight of fatty acid soap at the start of polymerization, 0.3% Except that 5 parts by weight of butyl acrylate rubber latex (based on solid content) and 55 parts by weight of butadiene rubber latex (based on solid content) were added during the preparation of the copolymer composition. The same procedure was followed.

Example 5

In Example 1, 19.8 parts by weight of butyl acrylate, 0.2 parts by weight of allyl methacrylate and 0.16 part by weight of fatty acid soap were added during the production of butyl acrylate core to prepare a butyl acrylate core. In producing the butadiene core, 1 , 30 parts by weight of 3-butadiene at the start of polymerization, 10 parts by weight of a polymerization conversion of 30% to 40%, 10 parts by weight of the fatty acid soap, 0.8 parts by weight at the start of polymerization, 0.2% Except that 20 parts by weight of butyl acrylate rubber latex (based on solid content) and 40 parts by weight of butadiene rubber latex (based on solid content) were added during the preparation of the copolymer composition. The same procedure was followed.

Example 6

In Example 1, 0.2 weight parts of fatty acid soap was added to prepare a butyl acrylate core to prepare a butyl acrylate rubber latex having an average particle diameter of 50 nm. To prepare a butadiene core, 1 weight part of sodium sulfate was added as an electrolyte , And 1.2 parts by weight of a fatty acid soap at the time of initiating polymerization and 0.3 part by weight of a polymerization conversion rate of 30% to 40% were added to prepare a butadiene rubber latex having an average particle diameter of 380 nm. Respectively.

Example 7

The butyl acrylate rubber latex having an average particle diameter of 150 nm was prepared by adding 0.032 parts by weight of a fatty acid soap in the preparation of the butyl acrylate core in Example 1 and 0.5 part by weight of sodium sulfate as an electrolyte in the production of butadiene core Was added to prepare a butadiene rubber latex having an average particle diameter of 250 nm.

Comparative Example 1

In Example 1, 45 parts by weight of 1,3-butadiene at the start of polymerization and 15 parts by weight of a polymerization conversion rate of 30% to 40% at the time of preparing the butadiene core were prepared without preparing the butyl acrylate core, 1.2 parts by weight of soap at the initiation of polymerization and 0.3 part by weight of a polymerization conversion of 30% to 40% were added to prepare a butadiene core. To prepare a copolymer composition, butadiene rubber latex 60 (Based on solid basis) was added to the reaction mixture. The composition of the copolymer composition is shown in Table 2 below.

Comparative Example 2

In Example 1, butyl acrylate was added in an amount of 24.7 parts by weight, allyl methacrylate 0.3 part by weight, and fatty acid soap 0.2 part by weight to prepare a butyl acrylate core. To prepare a butadiene core, 1 part of 1 , 26.25 parts by weight of 3-butadiene at the start of polymerization, 8.75 parts by weight of a polymerization conversion of 30% to 40% at the start of polymerization, 0.7 parts by weight of fatty acid soap at the start of polymerization, 0.2% Except that 25 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 during the preparation of the copolymer composition. The same procedure was followed.

Comparative Example 3

In Example 1, 9.9 parts by weight of butyl acrylate, 0.1 part by weight of allyl methacrylate and 0.05 part by weight of total fatty acid soap were added during the production of the butyl acrylate core, And a monomer ratio in the second stage of 1: 9 were polymerized to prepare butyl acrylate rubber latex having an average particle diameter of 250 nm of butyl acrylate rubber. To prepare butadiene core, 50 parts by weight of 1,3-butadiene was added Except that 10 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) were added during the preparation of the copolymer composition, Respectively.

Comparative Example 4

1.98 parts by weight of butyl acrylate, 0.02 part by weight of allyl methacrylate and 0.02 part by weight of a fatty acid soap were added to the butylacrylate core to prepare a butyl acrylate core in Example 1, , 43.5 parts by weight of 3-butadiene at the start of the polymerization, 14.5 parts by weight of the polymerization conversion of 30% to 40% at the start of the polymerization, 1.1 parts by weight of the fatty acid soap at the beginning of polymerization, 0.3% Except that 2 parts by weight of butyl acrylate rubber latex (based on solid content) and 58 parts by weight of butadiene rubber latex (based on solid content) were added during the preparation of the copolymer composition. The same procedure was followed.

Comparative Example 5

In Example 1, butyl acrylate was added in an amount of 29.7 parts by weight, allyl methacrylate 0.3 part by weight and fatty acid soap 0.24 part by weight to prepare butyl acrylate core. In the preparation of butadiene core, 1 , 22.5 parts by weight of 3-butadiene at the start of polymerization, 7.5 parts by weight of a polymerization conversion of 30% to 40% at the start of polymerization, 0.6 parts by weight of fatty acid soap at the start of polymerization, 0.1% Except that 30 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) were added during the preparation of the copolymer composition. The same procedure was followed.

Comparative Example 6

In Example 1, 0.35 parts by weight of a fatty acid soap was added to prepare a butyl acrylate core to prepare a butyl acrylate rubber latex having an average particle diameter of 30 nm. In preparing the butadiene core, 1.2 parts by weight of sodium sulfate as an electrolyte 1.5 parts by weight of a fatty acid soap at the initiation of polymerization and 0.5 part by weight of a polymerization conversion of 30% to 40% were added to prepare a butadiene rubber latex having an average particle size of 450 nm. But the polymerization stability of the butadiene rubber latex was very low, and a large amount of solid matter was generated, and the butadiene rubber latex was not obtained.

Comparative Example 7

In Example 1, 0.04 parts by weight of fatty acid soap was added during the production of the butyl acrylate core, and the polymerization was carried out in two stages to polymerize 1:16 of the monomers in the first and second stages to obtain butyl acrylate Except that butyl acrylate rubber latex having an average particle diameter of 300 nm was prepared and 0.4 part by weight of sodium sulfate was added to prepare a butyl acrylate rubber latex having an average particle diameter of 200 nm when preparing the butadiene core. The procedure of Example 1 was repeated.

Experimental Example

Experimental Example 1

The average particle diameters of the respective cores prepared in Examples 1 to 7 and Comparative Examples 1 to 7 were measured by the following methods. The compositions of the respective copolymer compositions are shown in Tables 1 and 2 below.

* Average particle diameter (D50, nm): A sample prepared by diluting the prepared rubber latex to 200 ppm or less was prepared and analyzed by dynamic laser light scattering method using Nicomp 380 at room temperature (23 캜) The average particle size (D50) of the rubber particles dispersed in the rubber latex was measured according to an intensity Gaussian distribution.

division Example One 2 3 4 5 6 7 (Meth) acrylic core BA ¹⁾ Content (parts by weight) 9.9 6.9 14.8 4.95 19.8 9.9 9.9 AMA ^{2 )} Content (parts by weight) 0.1 0.1 0.2 0.05 0.2 0.1 0.1 Average particle diameter (nm) 100 100 100 100 100 50 150 Conjugated diene-based core BD ³⁾ Content (parts by weight) 50 53 45 55 40 50 50 Average particle diameter (nm) 300 300 300 300 300 380 250 The first shell and the second shell SM ⁴⁾ Content (parts by weight) 29 29 29 29 29 29 29 AN ⁵⁾ Content (parts by weight) 11 11 11 11 11 11 11 1) BA: butyl acrylate
2) AMA: allyl methacrylate
3) BD: 1,3-butadiene
4) SM: styrene
5) AN: acrylonitrile

division Comparative Example One 2 3 4 5 6 7 (Meth) acrylic core BA ¹⁾ Content (parts by weight) - 24.7 9.9 1.98 29.7 9.9 9.9 AMA ^{2 )} Content (parts by weight) - 0.3 0.1 0.02 0.3 0.1 1.1 Average particle diameter (nm) - 100 250 100 100 30 300 Conjugated diene-based core BD ³⁾ Content (parts by weight) 60 35 50 58 30 50 50 Average particle diameter (nm) 300 300 300 300 300 - ⁶⁾ 200 The first shell and the second shell SM ⁴⁾ Content (parts by weight) 29 29 29 29 29 - ⁶⁾ 29 AN ⁵⁾ Content (parts by weight) 11 11 11 11 11 - ⁶⁾ 11 1) BA: butyl acrylate
2) AMA: allyl methacrylate
3) BD: 1,3-butadiene
4) SM: styrene
5) AN: acrylonitrile
6) -: The average particle size of the conjugated diene-based core was 450 nm. However, when the conjugated diene-based core was produced, a large amount of solid matter was generated,

Experimental Example 2

In order to evaluate the coagulation characteristics of the copolymer composition latexes in Examples 1 to 7 and Comparative Examples 1 to 7, the water content and fine content of the coagulated copolymer composition latex were measured by the following method, &Lt; tb &gt; &lt; TABLE &gt;

* Water content (% by weight): When the weight of the sample is no longer changed (residual moisture content is 0.5% by weight or less) using water meter (METTLER / TOLEDO HR83-P) Weight change was measured.

Pine Content (% by Weight): The powder of the copolymer composition obtained by drying was subjected to vibration shaking in a particle size measuring device using a standard netting, classified by size, and fine particles of 75 탆 or less Fine, fine) was measured.

division Example One 2 3 4 5 6 7 Coagulation characteristics of coagulated copolymer composition Moisture content
(weight%) 25 27 22 29.5 19 28 26 Pine content
(weight%) 5 7 2 8 3 6 5

division Comparative Example One 2 3 4 5 6 7 Coagulation characteristics of coagulated copolymer composition Moisture content
(weight%) 30 21 31 31 16 - ¹⁾ 30 Pine content
(weight%) 10 3 12 11 2 - ¹⁾ 11

1) -: The average particle diameter of the conjugated diene-based core was 450 nm, but when the conjugated diene-based core was produced, a large amount of solid matter was generated,

As shown in Tables 3 and 4, it was confirmed that the water content and the fine content in the coagulated copolymer composition were reduced in Examples 1 to 7 containing a certain amount of butylacrylate core having an average particle diameter of 150 nm or less . On the other hand, in the case of Comparative Examples 1 and 4 which did not use the butyl acrylate core or exceeded the content ratio of the core defined in the present invention, the water content and the pine content were both high. Also, it was confirmed that both the water content and the pine content were higher in Comparative Examples 3 and 7, which were similar to the same season, when the average mouth ratio between the butyl acrylate core and the butadiene core was 200 nm or more. In addition, as in Comparative Example 6, when the particle size of the butadiene core was very large, the polymerization stability deteriorated and the copolymer composition itself could not be obtained.

Experimental Example 3

25 parts by weight of the copolymer composition powder prepared in Examples 1 to 7 and Comparative Examples 1 to 7 and 100 parts by weight of the styrene-acrylonitrile copolymer (LG And 75 parts by weight of Grade SAN 92HR manufactured by Kagaku Kogyo Seiyaku Co., Ltd.), and the mixture was melted and kneaded at 200 ° C to 210 ° C using a twin-screw extruder to prepare a resin composition in the form of pellets. The composition was injected to prepare specimens according to the following standard methods of measuring the impact strength and surface gloss, and physical properties thereof were measured by the following methods and shown in Tables 5 and 6.

* Impact strength (Notched Izod Impact Strength, kgf · cm / cm): Impact strength was measured according to the standard measurement method ASTM D256 using 1/4 "(6.35 mm) thick specimens with notch .

* Surface gloss (45 [deg.]): Standard measurement at 45 [deg.] Angle using a specimen. Surface gloss was measured according to ASTM D528.

* Projections: Using a 1-axis extrusion kneader (Lab tech) with a sheet thickness of 10 μm and measuring projections within an area of 1 m ² using the projection measurement program of OCS, Germany Respectively. Among them, protrusions of 100 탆 or less were ignored, and the total number of protrusions of 101 탆 or more was measured.

division Example One 2 3 4 5 6 7 Thermoplastic resin composition Impact strength
(kgfcm / cm) 23.3 23.5 23.0 24.1 22.8 23.6 23.7 Surface gloss
(45 [deg.]) 95 94 97 93 97 95 96 Protrusion (dog) 9 15 5 16 4 15 10

division Comparative Example One 2 3 4 5 6 7 Thermoplastic resin composition Impact strength
(kgfcm / cm) 23.2 20.1 22.9 23.0 19.2 - ¹⁾ 21.3 Surface gloss
(45 [deg.]) 90 98 92 90 98 - ¹⁾ 92 Protrusion (dog) 25 3 8 22 3 - ¹⁾ 16

1) -: The average particle diameter of the conjugated diene-based core was 450 nm, but when the conjugated diene-based core was produced, a large amount of solid matter was generated,

As shown in Tables 5 and 6, when the copolymer composition of the present invention was used as an impact modifier in a thermoplastic resin composition, a comparative example using an ABS copolymer using only a butadiene core as an impact modifier without using a butyl acrylate core 1 and a comparatively low content of butyl acrylate core, the surface gloss was high, the number of projections was remarkably reduced, and the appearance characteristics were remarkably excellent there was. On the other hand, in the case of Comparative Example 2 and Comparative Example 5 using a copolymer composition which does not satisfy the weight ratio defined in the present invention as an impact modifier even if different types of cores were used, the cohesive characteristics of the copolymer composition were improved Table 4), the appearance characteristics of the thermoplastic resin composition were improved, but the content of the butadiene core was not sufficient, and the impact strength was markedly lowered, indicating that the impact resistance was very poor. In Comparative Examples 3 and 7 using a copolymer composition which does not satisfy the average particle size ratio defined in the present invention as an impact modifier even when different kinds of cores were used, the impact strength was lowered and the appearance characteristics And the improvement of the quality of life.

From the above results, the inventors of the present invention have found that when a bimodal type copolymer composition is produced by using a different kind of core according to the present invention and by limiting the weight ratio and average particle size ratio between cores to a specific range, And the use of the copolymer composition as an impact modifier in a thermoplastic resin composition makes it possible to maintain or improve the impact strength at the same level as compared with the case where the existing ABS copolymer is used as an impact modifier, And the number of protrusions protruding on the surface is reduced, thereby confirming that the appearance characteristics can be remarkably improved.

Claims (9)

A first core-shell copolymer comprising a (meth) acrylic core comprising a repeating unit derived from an alkyl (meth) acrylate monomer, and a first shell comprising a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a vinyl cyan monomer; And
A second core-shell copolymer comprising a conjugated diene-based core comprising a conjugated diene monomer-derived repeat unit and a second shell comprising an aromatic vinyl monomer-derived repeat unit and a vinyl cyan monomer-derived repeat unit,
The ratio of the average particle diameter of the (meth) acrylic core and the average particle diameter of the conjugated dienic core is 1: 1.66 to 1: 7.6,
Wherein the weight ratio of the (meth) acrylic based core and the conjugated diene based core is 1: 2 to 1:10. The method according to claim 1,
Wherein the (meth) acrylic core has an average particle diameter of 50 nm to 150 nm. The method according to claim 1,
Wherein the conjugated diene-based core has an average particle diameter of 250 nm to 380 nm. The method according to claim 1,
The content of the (meth) acrylic core is 5 wt% to 20 wt%
The content of the conjugated diene-based core is 40 wt% to 60 wt%
And the content of the first shell and the second shell is 30 wt% to 50 wt%. The method according to claim 1,
Wherein the (meth) acrylic-based core comprises a repeating unit derived from a crosslinkable monomer. 6. The method of claim 5,
Wherein the (meth) acrylic core comprises 98% by weight to 99.9% by weight of repeating units derived from an alkyl (meth) acrylate monomer and 0.1% to 2% by weight of repeating units derived from a crosslinkable monomer. 6. The method of claim 5,
The crosslinkable monomer may be at least one selected from the group consisting of ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, allyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra ) Acrylate, divinylbenzene, divinylnaphthalene, and diallyl phthalate. (i) polymerizing an alkyl (meth) acrylate monomer to produce a (meth) acrylic core;
ii) polymerizing the conjugated diene monomer to prepare a conjugated diene-based core (S2);
(meth) acrylate core prepared in the step (S1) and the conjugated diene-based core prepared in the step (S2) are introduced into one reactor, and the aromatic vinyl monomer and the vinyl cyan monomer are introduced into the reactor, (S3) a first shell on an acrylic core and a second shell on a conjugated diene-based core,
The ratio of the average particle diameter of the (meth) acrylic based core prepared in the step (S1) and the average particle diameter of the conjugated diene based core prepared in the step (S2) is 1: 1.66 to 1: 7.6,
Wherein the ratio of the weight of the (meth) acrylic core produced in the step (S1) to the weight of the conjugated diene core produced in the step (S2) is 1: 2 to 1:10. A thermoplastic resin composition comprising the copolymer composition of any one of claims 1 to 7.