KR20200051154A - 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 that is included in a thermoplastic resin composition to perform a role as an impact modifier, a method of manufacturing the same, and a thermoplastic resin composition comprising the same. In particular, the present invention is to provide a bimodal copolymer composition comprising a first core-shell copolymer and a second core-shell copolymer.

Description

Copolymer composition, method for manufacturing the same, and thermoplastic resin composition comprising the same {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 to perform the role of an impact modifier, a manufacturing method thereof, and a thermoplastic resin composition comprising the same.

Polycarbonate resin (PC), which is a thermoplastic resin, is widely used in the manufacture of molded products for electric and electronic products, including automobiles, because it has excellent impact resistance, electrical properties, and heat resistance.

However, the polycarbonate resin has the disadvantages of high melt viscosity, low impact resistance at low temperatures, and susceptibility to hydrolysis under high temperature and high humidity conditions. To compensate for these drawbacks, a methyl methacrylate-butadiene-styrene copolymer prepared by grafting monomers such as styrene and methyl methacrylate into rubber latex based on butadiene (hereinafter, ' MBS-based copolymers') has been proposed as a shock modifier to improve the impact resistance of polycarbonate resins. That is, a molded article is manufactured from a thermoplastic resin composition in which a polycarbonate resin and an MBS-based copolymer are mixed to improve the impact resistance of the molded article.

Methods for manufacturing the MBS-based impact modifier are disclosed in U.S. Patent Nos. 5,204,406 and 5,599,854. However, even if the MBS-based impact modifier obtained by the above method is used, there is a limit to increase the impact resistance of a molded article made of a thermoplastic resin composition under low temperature and moisture heat. In addition, there is a problem that the processability and thermal stability of the thermoplastic resin composition is lowered by the butadiene used in the manufacture of the MBS-based impact modifier.

U.S. Patent No. 5,204,406 U.S. Patent No. 5,599,854

The problem to be solved in the present invention, in order to solve the problems mentioned in the technology that is the background of the invention, is a copolymer composition that is included in the thermoplastic resin composition and serves as an impact modifier, when molding the thermoplastic resin composition, It is an object of the present invention to provide a copolymer composition capable of improving processability and thermal stability without lowering impact resistance.

In order to solve the above problems, the present invention provides a copolymer composition comprising a first core-shell copolymer and a second core-shell copolymer, wherein the first core-shell copolymer is an alkyl (meth) acrylate monomer. A first shell comprising a (meth) acrylic core comprising a repeating unit derived from, a repeating unit derived from a methyl (meth) acrylate monomer, a repeating unit derived from an alkyl (meth) acrylate monomer, and a repeating unit derived from an aromatic vinyl monomer, , The second core-shell copolymer is a conjugated diene-based core including 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, and an aromatic vinyl monomer It comprises a second shell containing a repeating unit derived, the average particle diameter of the (meth) acrylic core is 100 nm to 200 nm, the conjugated diene-based core The average particle diameter is 150 nm to 250 nm, with respect to the total content of the copolymer composition, the content of the (meth) acrylic core is 18 parts by weight to 50 parts by weight, and the content of the conjugated diene core is 28 parts by weight to 50 It provides a copolymer composition of 18 parts by weight to 32 parts by weight of the first shell and the second shell.

In addition, the present invention, i) polymerizing an alkyl (meth) acrylate monomer 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 step (S10) and the conjugated diene core prepared in step (S20) are introduced into a reactor, and methyl (meth) acrylate monomer, alkyl (meth) acrylate monomer, and Including an aromatic vinyl monomer, the first shell on the (meth) acrylic core, the second shell on the conjugated diene-based core, and simultaneously graft polymerization to prepare a copolymer composition (S30), and The average particle diameter of the (meth) acrylic core prepared in the step (S10) is 100 nm to 200 nm, and the average particle diameter of the conjugated diene core prepared in the step (S20) is 150 nm to 250 nm, and the (S30) The copolymer composition prepared in, relative to the total content of the copolymer composition, the content of the (meth) acrylic core is 18 parts by weight to 50 parts by weight, the content of the conjugated diene core is 28 parts by weight to 50 parts by weight , remind The first shell and the amount of the second shell provides 18 parts to 32 parts by weight, the manufacturing method of the copolymer composition.

In addition, the present invention, the copolymer composition; And it provides a thermoplastic resin composition comprising a polycarbonate resin.

According to the present invention, the copolymer composition is a bimodal copolymer composition comprising a first core-shell copolymer comprising a (meth) acrylic core and a second core-shell copolymer comprising a conjugated diene-based core. Accordingly, when the copolymer composition is used as an impact modifier in a thermoplastic resin composition, it is possible to obtain an effect of improving processability and heat stability without lowering the impact resistance (impact strength) of the molded article.

In addition, according to the present invention, a part of the conjugated diene-based monomer having high price fluctuation among the raw materials applied to the MBS-based copolymer is replaced with an alkyl (meth) acrylate monomer, so that cost competitiveness can be secured and productivity can be obtained. have.

Terms or words used in the description and claims of the present invention should not be construed as being limited to ordinary or lexical meanings, and the inventor appropriately explains the concept of terms in order to best explain his or her invention in the best way. Based on the principle of being able to be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

On the other hand, the term 'monomer' in the present invention refers to all compounds for forming a polymer by participating in a polymerization reaction, and if it is a compound capable of forming a copolymer composition according to the present invention by participating in a polymerization reaction, It is not limited whether it is a monomer having a single compound, an oligomer having a small amount of monomers, or a polymer having a lot of units. That is, if the compound participating in the polymerization reaction to form the copolymer composition according to the present invention, monomers, oligomers, polymers can all 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 upon polymerization of the copolymer, the monomer to be introduced participates in a polymerization reaction to form a repeating unit in the copolymer. It may mean.

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

In the present invention, the term 'shell' may be a graft polymerization to the core of the core-shell type copolymer, and may mean a polymer component or a copolymer component forming a shell or shell layer.

The term 'average particle diameter' in the present invention means a weight average particle diameter (D ₅₀ ) measured according to an intensity Gaussian distribution by a dynamic laser light scattering method using Nicomp 380. May be

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 includes a (meth) acrylic core including a repeating unit derived from an alkyl (meth) acrylate monomer, a repeating unit derived from a methyl (meth) acrylate monomer, and 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 conjugated diene-based core including 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, and a repeating unit derived from an aromatic vinyl monomer. It comprises a second shell-core copolymer comprising, the (meth) acrylic core has an average particle diameter of 100 nm to 200 nm, the average particle diameter of the conjugated diene-based core is 150 nm to 250 nm, the copolymer With respect to the total composition, the content of the (meth) acrylic core is 18 parts by weight to 50 parts by weight, the content of the conjugated diene core is 28 parts by weight to 50 parts by weight, and the first shell and the second shell The content of may be a copolymer composition of 18 parts by weight to 32 parts by weight.

That is, the copolymer composition according to the present invention is a (meth) acrylic core and a conjugated diene-based core of a heterogeneous (異種) is a first core-shell copolymer and a second graft polymerization of the first shell and the second shell, respectively. It may be a bimodal copolymer composition comprising a core-shell copolymer. As described above, the copolymer composition of the present invention comprising a first core-shell copolymer and a second core-shell copolymer using heterogeneous cores has an impact of a thermoplastic resin composition as the rubber content is relatively high. When applied as a reinforcing agent, it is possible to increase the impact resistance (impact strength) of a molded article made of a thermoplastic resin composition.

In this regard, copolymer particles having a small-diameter and large-diameter core using a conjugated diene-based core alone, such as a conventional MBS-based copolymer, may increase the polymerization time of the core due to a single monomer component, thereby making it economical in the manufacturing process And commerciality may not be secured. In addition, a large amount of the 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 the copolymer particles decreases, resulting in mechanical properties and surface. There may be a problem that the characteristics are deteriorated. Therefore, it may be preferable to use a first core-shell copolymer and a second core-shell copolymer having heterogeneous cores as in the present invention.

In particular, in the case of using the (meth) acrylic core and the conjugated diene-based core as in the present invention, mechanical properties are secured from the conjugated diene-based core and cost competitiveness is secured from the (meth) acrylic core, while workability and thermal stability are secured. This is improved, while improving the impact resistance of the thermoplastic resin composition containing it, it is possible to further improve the processability and thermal stability.

Moreover, the present invention has an average particle diameter of the (meth) acrylic core in the range of 100 nm to 200 nm, an average particle diameter of the conjugated diene core in the range of 150 nm to 250 nm, and impacts the copolymer composition comprising the same It has an excellent effect of increasing the impact resistance, processability and thermal stability of the thermoplastic resin composition used as a reinforcing agent.

Specifically, according to an embodiment of the present invention, the average particle diameter of the (meth) acrylic core is in the range of 120 nm to 180 nm, or 150 nm to 180 nm, and the average particle diameter of the conjugated diene core is 180 nm to 230 nm Or 180 nm to 200 nm. As the average particle diameter of the (meth) acrylic core and the average particle diameter of the conjugated diene core are within the above ranges, impact resistance, processability, and thermal stability of the thermoplastic resin composition using the copolymer composition containing it as an impact modifier can be increased. .

In particular, when the average particle diameter of the (meth) acrylic core is less than or equal to the average particle diameter of the conjugated diene core, the inter-particle distance between the first core-shell copolymer particles and the second core-shell copolymer particles When it is possible to reduce, when using a copolymer composition containing the same as the impact modifier in the thermoplastic resin composition, it is possible to increase not only the impact resistance, but also the coloring and glossiness.

According to an embodiment of the present invention, the ratio (a: b) of the average particle diameter of the (meth) acrylic core and the average particle diameter of the conjugated diene-based core (b) is 1: 0.75 to 1: 2.5, 1: 1 to 1: 2, or 1: 1 to 1: 1.95. As the ratio (a: b) of the average particle diameter is within the above range, impact resistance, processability, and thermal stability of the thermoplastic resin composition using the copolymer composition containing it as an impact modifier may be increased.

According to an embodiment of the present invention, the total average particle diameter of the (meth) acrylic core and the conjugated diene core may be 175 nm to 220 nm, 180 nm to 220 nm, or 180 nm to 215 nm. As the average particle diameter of the (meth) acrylic core and the conjugated diene-based core is within the above range, impact resistance, processability, and thermal stability of the thermoplastic resin composition using the copolymer composition including the same as an impact modifier may be increased.

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 18 parts by weight to 50 parts by weight, and the content of the conjugated diene core is 28 parts by weight to 50 parts by weight Part, the total content of the first shell and the second shell may be 18 parts by weight to 32 parts by weight. As the (meth) acrylic core, the conjugated diene core, the first shell and the second shell are included in the copolymer composition within the content range, the copolymer composition containing the same is used as an impact modifier in the thermoplastic resin composition. Impact resistance, workability and thermal stability can be improved.

Specifically, 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 20 parts by weight to 50 parts by weight, and the content of the conjugated diene core is 30 parts by weight to 50 parts by weight, the content of the first shell and the second shell may be 20 parts by weight to 30 parts by weight. As the (meth) acrylic core, the conjugated diene core, the first shell and the second shell are included in the copolymer composition within the content range, the copolymer composition containing the same is applied to the thermoplastic resin composition as an impact modifier. Impact resistance, workability and thermal stability can be improved.

According to one embodiment of the present invention, the (meth) acrylic core, the first shell and the alkyl (meth) acrylate monomers forming the repeating unit in the second shell are each alkyl having 2 to 8 carbon atoms. It may be a meth) acrylate monomer. In this case, the alkyl group having 2 to 8 carbon atoms may mean a linear alkyl group having 2 to 8 carbon atoms and a branched alkyl group having 3 to 8 carbon atoms. Specifically, the alkyl (meth) acrylate monomer is ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) It may be one or more selected from the group consisting of acrylate, octyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. More specifically, the alkyl (meth) acrylate monomer may be an alkyl acrylate (eg, butyl acrylate), or an alkyl methacrylate.

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

According to an embodiment of the present invention, the methyl (meth) acrylate monomer constituting the repeating unit in the first shell and the second shell may be a commonly known methyl (meth) acrylate monomer.

According to an embodiment of the present invention, the aromatic vinyl monomer constituting the repeating unit in the first shell and the second shell is styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1 -Vinyl naphthalene, 4-cyclohexyl styrene, 4- (p-methylphenyl) styrene, and 1-vinyl-5-hexyl naphthalene. Specifically, the aromatic vinyl monomer may be styrene.

According to an embodiment of the present invention, the (meth) acrylic core may further include a repeating unit derived from a crosslinkable monomer. When the (meth) acrylic core further comprises a repeating unit derived from a crosslinkable monomer, on the (meth) acrylic core comprising an repeating unit derived from an alkyl (meth) acrylate monomer, the graft of the first shell and the second shell Polymerization is easily carried out, and there is an effect of improving the aggregation characteristics and appearance characteristics of the copolymer composition. The crosslinkable monomer constituting the repeating unit in the (meth) acrylic core is specifically ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, allyl (meth) acrylate, trimethylolpropane tri (Meth) acrylic crosslinkable monomers such as (meth) acrylate and pentaerythritol tetra (meth) acrylate; And vinyl-based crosslinkable monomers such as divinylbenzene, divinylnaphthalene and diallylphthalate. More specifically, the crosslinkable monomer may be allyl (meth) acrylate.

When the (meth) acrylic core includes the repeating unit derived from the crosslinkable monomer, the (meth) acrylic core, based on the total content of the (meth) acrylic core, the repeating unit derived from an alkyl (meth) acrylate monomer 98 Weight percent to 99.9 weight percent, or 98.5 weight percent to 99.5 weight percent; And a repeating unit derived from a crosslinkable monomer, 0.1% to 2% by weight, or 0.5% to 1.5% by weight.

On the other hand, the manufacturing method of the copolymer composition according to the present invention, i) polymerizing an alkyl (meth) acrylate monomer 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 step (S10) and the conjugated diene core prepared in step (S20) are introduced into a reactor, and methyl (meth) acrylate monomer, alkyl (meth) acrylate monomer, and Including an aromatic vinyl monomer, the first shell on the (meth) acrylic core, the second shell on the conjugated diene-based core, and simultaneously graft polymerization to prepare a copolymer composition (S30), and The average particle diameter of the (meth) acrylic core prepared in the step (S10) is 100 nm to 200 nm, and the average particle diameter of the conjugated diene core prepared in the step (S20) is 150 nm to 250 nm, and the (S30) The copolymer composition prepared in, relative to the total content of the copolymer composition, the content of the (meth) acrylic core is 18 parts by weight to 50 parts by weight, the content of the conjugated diene core is 28 parts by weight to 50 parts by weight , remind The first shell and the amount of the second shell may be an 18 to 32 parts by weight.

The (S10) step is a step for preparing a (meth) acrylic core, and may be made of radical polymerization using a peroxide-based, redox, or azo-based initiator in the presence of an alkyl (meth) acrylate monomer. have. Examples of the polymerization method include emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, and the like. In order to control the average particle diameter of the (meth) acrylic core as in the present invention, it is preferable to perform emulsion polymerization using a redox initiator. Do.

According to an embodiment of the present invention, the redox initiator that can be used in step (S10) is specifically selected from the group consisting of t-butylhydroperoxide, diisopropylbenzenehydroperoxide and cumenehydroperoxide 1 It may be a species or more, and using them can provide a stable polymerization environment.

According to an embodiment of the present invention, the emulsifier used in the emulsion polymerization of step (S10) is specifically alkylaryl sulfonate, alkali methyl alkyl sulfate, soap of fatty acid, alkali salt of oleic acid, alkali salt of rosin acid, lauryl acid It may be at least one selected from the group consisting of alkali salts, sodium diethylhexyl phosphate, phosphonated polyoxyethylene alcohol, and phosphonated polyoxyethylene phenol, and using them can 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 less, or 0.3 parts by weight to 1 part by weight based on the total amount of monomers introduced in the step (S10). As the emulsifier is added in the above range, it is possible to improve the mechanical properties and appearance properties of the thermoplastic resin composition, maintain the polymerization stability of the latex, and efficiently control the average particle diameter of the (meth) acrylic core.

When the (meth) acrylic core is prepared by emulsion polymerization of the alkyl (meth) acrylate monomer as described above, compared with the case of the emulsion polymerization of the conjugated diene monomer for producing a conjugated diene core having an average particle diameter of the same or equivalent level, Even if a smaller amount of emulsifier is used, it is possible to polymerize the rubber, that is, to manufacture a core, and the residual emulsifier content in the finally obtained polymer or copolymer is small, preventing deterioration of mechanical properties such as impact strength and improving appearance characteristics. I can do it.

On the other hand, the (S10) step may be carried out by introducing a crosslinkable monomer.

The (S20) step is a step for producing a conjugated diene-based core, and may be carried out as an individual step, not a step that is continuous with the (S10) step. This (S20) step may be made of radical polymerization using a peroxide-based, redox, or azo-based initiator in the presence of a conjugated diene monomer. Examples of the polymerization method include emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, and the like. In order to control the average particle diameter of the conjugated diene-based core as in the present invention, it is preferable to perform emulsion polymerization using a redox initiator. .

According to an embodiment of the present invention, the redox initiator that can be used in step (S20) is specifically selected from the group consisting of t-butylhydroperoxide, diisopropylbenzenehydroperoxide and cumenehydroperoxide 1 It may be a species or more, and using them can provide a stable polymerization environment.

According to an embodiment of the present invention, the emulsifier used in the emulsion polymerization of step (S20) is specifically, alkylaryl sulfonate, alkali methyl alkyl sulfate, soap of fatty acid, alkali salt of oleic acid, alkali salt of rosin acid, lauryl It may be at least one selected from the group consisting of acid alkali salts, sodium diethylhexyl phosphate, phosphonated polyoxyethylene alcohol, and phosphonated polyoxyethylene phenol, and when using them, a stable polymerization environment can be provided. The emulsifier may be 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 the total amount of monomers introduced in the step (S20). As the emulsifier is added in the above range, polymerization stability of the conjugated diene-based core can be enhanced.

The (S30) step is a step for simultaneously graft polymerizing the (meth) acrylic-based core prepared in the (S10) step and the conjugated diene-based core prepared in the (S20) step, prepared in the (S10) step The (meth) acrylic core and the conjugated diene-based core prepared in the step (S20) are introduced into one reactor and subjected to graft polymerization, so that each core includes a first shell comprising a monomer-derived repeating unit of the same component and A second shell can be formed. The (S30) step is in the presence of a (meth) acrylic core, a conjugated diene core, a methyl (meth) acrylate monomer, an alkyl (meth) acrylate monomer and an aromatic vinyl monomer, peroxide-based, redox, Or radical polymerization using an azo-based initiator. Examples of the polymerization method include emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, and the like. In order to form a shell on each of the heterogeneous cores as in the present invention, it is necessary to perform emulsion polymerization using a redox initiator. desirable.

According to an embodiment of the present invention, the redox initiator that can be used in step (S30) is specifically selected from the group consisting of t-butyl hydroperoxide, diisopropylbenzenehydroperoxide, and cumene hydroperoxide. It may be the above, and when using them, it is possible to provide a stable polymerization environment.

According to an embodiment of the present invention, the emulsifier used in the emulsion polymerization in the step (S30) is alkylaryl sulfonate, alkali methyl alkyl sulfate, soap of fatty acid, alkali salt of oleic acid, alkali salt of rosin acid, alkali salt of lauric acid, It may be at least one selected from the group consisting of sodium diethylhexyl phosphate, phosphonated polyoxyethylene alcohol, and phosphonated polyoxyethylene phenol, and using them can provide a stable polymerization environment. The emulsifier may be added in an amount of 1.5 parts by weight or less, 1 part by weight or less, or 0.5 part by weight or less based on the total amount of monomers introduced in the step (S30). As the emulsifier is added in the above range, polymerization stability of the latex can be increased.

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

According to an embodiment of the present invention, the coagulation step may be carried out by introducing one or more coagulants selected from the group consisting of magnesium sulfate, calcium chloride, aluminum sulfate, sulfuric acid, phosphoric acid and hydrochloric acid to the copolymer composition latex. This agglomeration step can be carried out, for example, at 30 ° C to 90 ° C, or at 45 ° C to 75 ° C, in which case powder particles having an average particle diameter of 75 to 1,400 μm can be obtained.

According to an embodiment of the present invention, the aging step may be carried out by heat-treating the powder particles obtained in the aggregation step to 75 ℃ to 99 ℃, or 80 ℃ to 95 ℃. As a result of this aging step, residual monomers not participating in polymerization may be removed, cracks of powder particles may be prevented, and an effect of reducing water content may be obtained.

According to an embodiment of the present invention, the dehydration and drying step is performed by using a hot air drying method after separating the solids through a process of removing moisture by introducing the aggregated and / or aged copolymer composition powder particles into a dehydrator. Can be. The drying time may be shortened as the dehydration and drying steps are performed, and an effect of removing residual monomers not participating in polymerization may be obtained through hot air drying.

The thermoplastic resin composition according to the present invention may include the copolymer composition and a polycarbonate resin. The thermoplastic resin composition according to the present invention may include the copolymer composition as an impact modifier. The thermoplastic resin composition may be a thermoplastic resin composition for manufacturing a molded article through molding, wherein the base resin of the thermoplastic resin composition comprising the copolymer composition as an impact modifier, that is, the base of the thermoplastic resin composition The thermoplastic resin to be may be a polycarbonate resin. Specifically, the polycarbonate resin may not be particularly limited as long as it is a polycarbonate resin that can be used for molding.

According to an embodiment of the present invention, the thermoplastic resin composition, based on the total content of the thermoplastic resin composition, 80 parts by weight to 99 parts by weight of the polycarbonate resin, 90 parts by weight to 99 parts by weight, or 95 parts by weight to In 99 parts by weight, the copolymer composition may include 1 part by weight to 20 parts by weight, 1 part by weight to 10 parts by weight, or 1 part by weight to 5 parts by weight. As the copolymer composition and the polycarbonate resin are included within the above range, impact resistance, processability, and thermal stability of the thermoplastic resin composition may be increased.

According to one embodiment of the present invention, the thermoplastic resin composition is added to the additives such as blowing agents, stabilizers, processing aids, heat stabilizers, lubricants, pigments, dyes, or antioxidants within a range that does not degrade its physical properties, if necessary. It may further include.

Hereinafter, the present invention will be described in more detail by examples. However, the following examples are intended to illustrate the present invention, and it is apparent to those skilled in the art that various changes and modifications can be made within the scope and technical scope of the present invention, 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 butyl acrylate monomer content in the nitrogen-substituted polymerization reactor, 17.32 parts by weight of butyl acrylate, 0.18 parts by weight of allyl methacrylate, 0.1 parts by weight of fatty acid soap as emulsifier, and t-butyl hydroperoxide as polymerization initiator 0.1 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 183 parts by weight of ion-exchanged water are batched at 45 ° C to 55 ° C for 1 hour. After reaction, 81.68 parts by weight of butyl acrylate, 0.82 parts by weight of allyl methacrylate, 1.5 parts by weight of fatty acid soap as an emulsifier, 0.34 parts by weight of t-butyl hydroperoxide as a polymerization initiator, and 0.014 parts by weight of iron sulfide as an activator , 0.27 parts by weight of ethylene diamine acetate, 0.35 parts by weight of sodium formaldehyde sulfoxylate and 50 parts by weight of ion-exchanged water 45 To from 55 ℃ reacted continuously added for 1.5 hours to prepare the average particle size of 180 nm of a butyl acrylate rubber latex.

<Manufacture of butadiene core>

Based on 100 parts by weight of 1,3-butadiene monomer in a nitrogen-substituted polymerization reactor (autoclave), 150 parts by weight of ion-exchanged water, 100 parts by weight of 1,3-butadiene, 2.0 parts by weight of fatty acid soap as an emulsifier, and sodium alcohol as electrolyte 0.9 parts by weight of pate, 0.17 parts by weight of diisopropylbenzene hydroperoxide as a polymerization initiator, 0.1 parts by weight of ethylenediamine tetrasodium acetate as an activator, 0.01 parts by weight of ferrous sulfate, and 0.125 parts by weight of sodium formaldehyde sulfoxylate By reacting at 60 ℃ to 70 ℃ to prepare a butadiene rubber latex having an average particle diameter of 180 nm.

<Copolymer composition preparation>

30 parts by weight of butyl acrylate rubber latex (based on solid content) obtained above, and 50 parts by weight of butadiene rubber latex obtained above (based on solid content) are added to the nitrogen-substituted polymerization reactor based on 100 parts by weight of the total monomer content. After maintaining the reactor temperature at 45 ℃ to 55 ℃, 10 parts by weight of ion-exchanged water, 15 parts by weight of methyl methacrylate, 3 parts by weight of butyl acrylate and 2 parts by weight of styrene, 0.1 parts by weight of fatty acid soap as an emulsifier, polymerization start 0.05 parts by weight of zero t-butyl hydroperoxide, 0.002 parts by weight of iron sulfide as an activator, 0.04 parts by weight of ethylene diamine acetate and 0.05 parts by weight of sodium formaldehyde sulfoxylate were continuously added at 45 ° C to 55 ° C for 1.5 hours. The copolymer composition latex was obtained by graft polymerization reaction.

<Copolymer composition powder production>

To the obtained copolymer composition latex, 2.5 parts by weight of an antioxidant (IR1076) emulsion having an average particle diameter of 0.9 µm was added and stirred, and then aggregated at a temperature of 55 ° C. in the presence of 0.3 parts by weight of a sulfuric acid aqueous solution (concentration 5% by weight) as a flocculant. Ordered. The aggregated copolymer composition latex was aged until reaching 90 ° 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, butadiene core preparation, butadiene rubber latex having an average particle diameter of 230 nm was carried out in the same manner as in Example 1, except that 1.8 parts by weight of fatty acid soap and 1.2 parts by weight of sodium sulfate were added. Was prepared.

Next, when preparing the copolymer composition, butyl acrylate rubber latex as 50 parts by weight (based on solids), butadiene rubber latex (average particle diameter: 230 nm) obtained above was added as 30 parts by weight (based on solids) Then, it was carried out in the same manner as in Example 1.

Example 3

In Example 1, butadiene core preparation, butadiene rubber latex having an average particle diameter of 230 nm was carried out in the same manner as in Example 1, except that 1.8 parts by weight of fatty acid soap and 1.2 parts by weight of sodium sulfate were added. Was prepared.

Next, in preparing the copolymer composition, butyl acrylate rubber latex was used in 20 parts by weight (based on solid content), butadiene rubber latex (average particle diameter: 230 nm) obtained above was 50 parts by weight (based on solid content), ion-exchanged water Was carried out in the same manner as in Example 1, except that 15 parts by weight, methyl methacrylate as 23 parts by weight, butyl acrylate as 4 parts by weight, styrene as 3 parts by weight, and fatty acid soap as 0.15 parts by weight were added. .

Example 4

In Example 1, when preparing the copolymer composition, 40 parts by weight of butyl acrylate rubber latex (based on solid content), 30 parts by weight of butadiene rubber latex (based on solid content), 15 parts by weight of ion exchange water, and methyl meta It was carried out in the same manner as in Example 1, except that acrylate was added in 23 parts by weight, butyl acrylate in 4 parts by weight, styrene in 3 parts by weight, and fatty acid soap in 0.15 parts by weight.

Example 5

In Example 1, in the production of a butyl acrylate core, in the same manner as in Example 1, except that 0.35 parts by weight of fatty acid soap was added in a batch input step and 1.2 parts by weight of fatty acid soap in a continuous input step. Butyl acrylate rubber latex having an average particle diameter of 120 nm was prepared.

Next, in the production of a butadiene core, butadiene rubber latex having an average particle diameter of 230 nm was prepared in the same manner as in Example 1, except that 1.8 parts by weight of fatty acid soap and 1.2 parts by weight of sodium sulfate were added.

Then, when preparing the copolymer composition, the butyl acrylate rubber latex (average particle diameter: 120 nm) obtained above was 35 parts by weight (based on solid content), and the butadiene rubber latex (average particle diameter: 230 nm) obtained above was used. Same as Example 1 except that 40 parts by weight (based on solids), 12 parts by weight of ion-exchanged water, 19 parts by weight of methyl methacrylate, 3 parts by weight of styrene, and 0.12 parts by weight of fatty acid soap It was carried out by the method.

Comparative Example 1

In Example 1, in the production of a butyl acrylate core, in the same manner as in Example 1, except that the fatty acid soap was added in an amount of 0.08 parts by weight in the batch input step and the fatty acid soap was added in 1.6 parts by weight in the continuous input step. Butyl acrylate rubber latex having an average particle diameter of 200 nm was prepared.

Next, in preparing the copolymer composition, butadiene rubber latex was not added, but butyl acrylate rubber latex (average particle diameter: 200 nm) obtained above was added in 80 parts by weight (based on solid content), Example 1 It was carried out in the same manner as.

Comparative Example 2

In Example 1, in preparing the copolymer composition, butyl acrylate rubber latex was not added, but it was carried out in the same manner as in Example 1, except that 80 parts by weight (based on solids) of butadiene rubber latex was added.

Comparative Example 3

In Example 1, butadiene core preparation, butadiene rubber latex having an average particle diameter of 230 nm was carried out in the same manner as in Example 1, except that 1.8 parts by weight of fatty acid soap and 1.2 parts by weight of sodium sulfate were added. Was prepared.

Next, in preparing the copolymer composition, butyl acrylate rubber latex is 50 parts by weight, butadiene rubber latex (average particle size 230 nm) obtained above is 25 parts by weight (based on solid content), ion-exchanged water is 12 parts by weight, methyl It was carried out in the same manner as in Example 1, except that methacrylate was added at 19 parts by weight, styrene at 3 parts by weight, and fatty acid soap at 0.12 parts by weight.

Comparative Example 4

In Example 1, butadiene core preparation, butadiene rubber latex having an average particle diameter of 230 nm was carried out in the same manner as in Example 1, except that 1.8 parts by weight of fatty acid soap and 1.2 parts by weight of sodium sulfate were added. Was prepared.

Next, when preparing the copolymer composition, butyl acrylate rubber latex is 15 parts by weight (based on solid content), butadiene rubber latex (average particle diameter: 230 nm) obtained above is 50 parts by weight (based on solid content), ion-exchanged water Was carried out in the same manner as in Example 1, except that 18 parts by weight, 26 parts by weight of methyl methacrylate, 5 parts by weight of butyl acrylate, 4 parts by weight of styrene, and 0.18 parts by weight of fatty acid soap were added. .

Comparative Example 5

In Example 1, in the production of a butyl acrylate core, in the same manner as in Example 1, except that 0.35 parts by weight of fatty acid soap was added in a batch input step and 1.2 parts by weight of fatty acid soap in a continuous input step. Butyl acrylate rubber latex having an average particle diameter of 120 nm was prepared.

Next, in the production of a butadiene core, butadiene rubber latex having an average particle diameter of 230 nm was prepared in the same manner as in Example 1, except that 1.8 parts by weight of fatty acid soap and 1.2 parts by weight of sodium sulfate were added.

Then, when preparing the copolymer composition, the butyl acrylate rubber latex (average particle diameter: 120 nm) obtained above was 35 parts by weight (based on solid content), and the butadiene rubber latex (average particle diameter: 230 nm) obtained above was used. Excluding 50 parts by weight (based on solids), 8 parts by weight of ion-exchanged water, 11 parts by weight of methyl methacrylate, 2 parts by weight of butyl acrylate, 2 parts by weight of styrene, and 0.08 parts by weight of fatty acid soap Then, it was carried out in the same manner as in Example 1.

Comparative Example 6

Unlike Example 1 above, based on 100 parts by weight of butyl acrylate monomer content in a nitrogen-substituted polymerization reactor, 1 part by weight of fatty acid soap and 200 parts by weight of ion-exchanged water are added as an emulsifier, and the reactor internal temperature is 40 ° C to 45 ° C. After raising to 99 parts by weight of butyl acrylate, 1 part by weight of allyl methacrylate, 1.5 parts by weight of fatty acid soap as an emulsifier, 0.2 parts by weight of t-butyl hydroperoxide as a polymerization initiator, and 0.08% of iron sulfide as an activator Part, 0.16 parts by weight of ethylene diamine acetate, 0.2 parts by weight of sodium formaldehyde sulfoxylate, and 126 parts by weight of ion-exchanged water were continuously introduced into the reactor for 3 hours at 45 ° C to 55 ° C to react for 3 hours, butyl acrylate having an average particle diameter of 80 nm Rubber latex was prepared.

Next, in the production of a butadiene core, butadiene rubber latex having an average particle diameter of 230 nm was prepared in the same manner as in Example 1, except that 1.8 parts by weight of fatty acid soap and 1.2 parts by weight of sodium sulfate were added.

Then, in preparing the copolymer composition, the butyl acrylate rubber latex (average particle diameter: 80 nm) obtained above was 35 parts by weight (based on solid content), and the butadiene rubber latex (average particle diameter: 230 nm) obtained above was used. Same as Example 1 except that 40 parts by weight (based on solids), 12 parts by weight of ion-exchanged water, 19 parts by weight of methyl methacrylate, 3 parts by weight of styrene, and 0.12 parts by weight of fatty acid soap It was carried out by the method.

Comparative Example 7

Unlike Example 1, based on 100 parts by weight of 1,3-butadiene monomer in a nitrogen-substituted polymerization reactor, 70 parts by weight of ion-exchanged water, 75 parts by weight of 1,3-butadiene, 2.0 parts by weight of fatty acid soap as an emulsifier, electrolyte 1.2 parts by weight of sodium sulfate, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight modifier, and 0.4 parts by weight of potassium persulfate (K2S208) as an initiator, and the polymerization conversion rate at 70 ° C is 30% to 40% After reacting to, 25 parts by weight of 1,3-butadiene and 0.4 parts by weight of fatty acid soap were added and the reaction was terminated at the time when the polymerization conversion rate was 95% (required time: 23 hours), butadiene rubber latex having an average particle diameter of 280 nm Was prepared.

Next, in preparing the copolymer composition, butyl acrylate rubber latex is 35 parts by weight (based on solid content), butadiene rubber latex (average particle diameter: 280 nm) obtained above is 40 parts by weight (based on solid content), ion-exchanged water Was carried out in the same manner as in Example 1, except that 12 parts by weight, 19 parts by weight of methyl methacrylate, 3 parts by weight of styrene, and 0.12 parts by weight of fatty acid soap were added.

Comparative Example 8

In Example 1, in preparing the butyl acrylate core, in a batch input step, butyl acrylate was 29.7 parts by weight, allyl methacrylate was 0.3 parts by weight, fatty acid soap was 0.05 parts by weight, ion-exchanged water was 140 parts by weight, and continuous In the input step, except that butyl acrylate was added to 69.3 parts by weight, allyl methacrylate to 0.7 parts by weight, fatty acid soap to 1.6 parts by weight, and ion-exchanged water to 40 parts by weight, the same method as in Example 1 was carried out. Butyl acrylate rubber latex having an average particle diameter of 280 nm was prepared.

Next, when manufacturing the butadiene core, butadiene rubber latex having an average particle diameter of 120 nm was prepared in the same manner as in Example 1, except that sodium sulfate was added at 0.4 parts by weight.

Then, in preparing the copolymer composition, the butyl acrylate rubber latex obtained above (average particle diameter: 280 nm) is 40 parts by weight (based on solid content), butadiene rubber latex obtained above (average particle diameter: 120 nm) It was carried out in the same manner as in Example 1, except that 40 parts by weight (based on solids).

Experimental Example

Experimental Example 1

The average particle diameter of each core prepared in Examples 1 to 5 and Comparative Examples 1 to 8 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 (D ₅₀ , nm): After preparing a sample of the prepared copolymer composition powder diluted to 200 ppm or less, using Nicomp 380 at room temperature (23 ° C), dynamic laser light scattering ) Method, the average particle diameter (D ₅₀ ) of the powder particles of the copolymer composition was measured according to the intensity Gaussian distribution.

* Average overall particle diameter: The average particle diameter of the copolymer composition powder particles measured by the above average particle diameter measurement method was converted and measured based on the weight of the core.

division Example One 2 3 4 5 (Meth) acrylic core BA ¹⁾ derived repeat unit
(Parts by weight) 29.7 49.5 19.8 39.6 34.6 AMA ²⁾ derived repeat unit
(Parts by weight) 0.3 0.5 0.2 0.4 0.4 Average particle diameter (nm) 180 180 180 180 120 Conjugated diene-based core BD ³⁾ derived repeat unit
(Parts by weight) 50 30 50 30 40 Average particle diameter
(nm) 180 230 230 180 230 Average core diameter (nm) 180 200 215 180 180 First shell and second shell MMA ⁴⁾ derived repeat unit
(Parts by weight) 15 15 23 23 19 BA ¹⁾ derived repeat unit
(Parts by weight) 3 3 4 4 3 SM ⁵⁾ Derived repeating unit
(Parts by weight) 2 2 3 3 3 1) BA: Butyl acrylate
2) AMA: Allyl methacrylate
3) BD: 1,3-butadiene
4) MMA: methyl methacrylate
5) SM: Styrene

division Comparative example One 2 3 4 5 6 7 8 (Meth) acrylic core BA ¹⁾ derived repeat unit
(Parts by weight) 79.2 - 49.5 14.8 34.6 34.6 34.6 39.6 AMA ^{2 )} derived repeat unit
(Parts by weight) 0.8 - 0.5 0.2 0.4 0.4 0.4 0.4 Average particle diameter (nm) 200 - 180 180 120 80 180 280 Conjugated diene-based core BD ³⁾ derived repeat unit
(Parts by weight) - 80 25 50 50 40 40 40 Average particle diameter
(nm) - 180 230 230 230 230 280 120 Average core diameter (nm) 200 180 200 220 205 160 235 200 First shell and second shell MMA ^{4 )} derived repeat unit
(Parts by weight) 15 15 19 26 11 19 19 15 BA ¹⁾ derived repeat unit
(Parts by weight) 3 3 3 5 2 3 3 3 SM ⁵⁾ Derived repeating unit
(Parts by weight) 2 2 3 4 2 3 3 2 1) BA: Butyl acrylate
2) AMA: Allyl methacrylate
3) BD: 1,3-butadiene
4) MMA: methyl methacrylate
5) SM: Styrene

Experimental Example  2

A polycarbonate resin as a base resin and a thermoplastic resin composition each containing the copolymer compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 8 as impact modifiers were prepared by a conventionally known method. At this time, the content of the polycarbonate resin was 96 parts by weight, and the content of the copolymer composition was 4 parts by weight. The properties of the prepared thermoplastic resin composition were evaluated and measured by the following methods, and the results are shown in Tables 3 and 4 below.

* Impact strength: 1/8 inch notched specimens at 23 ° C and -40 ° C were aged for 6 hours, respectively, and then the samples were taken out and evaluated by ASTM D256 test method.

* Hydrolysis Resistance Heat Stability: After aging the 1/8 inch notched specimen in a chamber at a temperature of 90 ° C and a humidity of 95% for 1000 hours, the specimen was taken out and evaluated by the ASTM D256 test method.

* Injection heat stability: evaluated by ASTM D1925 test method. At this time, the △ YI value is the Yellow Index (YI ₁ ) of the specimen obtained by injection without staying under the condition of 330 ° C. in the injection machine nozzle and the Yellow Index (YI of the specimen obtained by staying for 10 minutes under the condition of 330 ° C. _This is the value obtained by calculating the change amount of ₂ ).

division Example One 2 3 4 5 Impact strength Izod 1/8 ", 23 ℃
(Kgfcm / cm) 76 78 77 79 78 Izod 1/8 ", -40 ℃
(Kgfcm / cm) 42 38 41 36 39 Hydrolysis
Thermal stability
(90 ℃, 95% 1000h) Izod 1/8 "
(Kgfcm / cm) 58 56 60 61 60 Thermal stability of injection stay
(330 ℃, 10min) △ YI 1.4 1.6 1.7 1.3 1.5

division Comparative example One 2 3 4 5 6 7 8 Impact strength Izod 1/8 ", 23 ℃
(Kgfcm / cm) 76 79 78 76 76 74 75 77 Izod 1/8 ", -40 ℃
(Kgfcm / cm) 18 35 30 27 22 24 32 24 Hydrolysis
Thermal stability
(90 ℃, 95% 1000h) Izod 1/8 "
(Kgfcm / cm) 55 41 57 44 27 56 38 55 Thermal stability of injection stay
(330 ℃, 10min) △ YI 1.7 3.8 1.8 1.6 3.7 1.8 2.0 1.8

As shown in Tables 3 and 4, when the copolymer composition of the present invention was used as an impact modifier in a thermoplastic resin composition, it was confirmed that the impact strength was high and the thermal stability was excellent. On the other hand, the first core-shell polymer was used. In the case of Comparative Example 1 using the copolymer composition containing alone as an impact modifier in the thermoplastic resin composition, it was confirmed that the impact strength at low temperature was very low, and the copolymer composition comprising the second core-shell polymer alone was used. In the case of Comparative Example 2 used as an impact modifier in the thermoplastic resin composition, it was confirmed that the thermal stability was very poor.

In addition, in the case of Comparative Examples 3 to 5 in which the content of the (meth) acrylic core, the conjugated diene core, the first shell and the second shell is outside the scope of the present invention, the impact strength at low temperature and the thermal stability are lower than those of the present invention. I could confirm that it was falling.

In addition, in Comparative Examples 6 to 8 in which the average particle diameter of each of the (meth) acrylic core and the conjugated diene core was outside the scope of the present invention, it was confirmed that the impact strength at low temperature was low and the thermal stability was poor compared to the present invention. .

Claims (10)

In the copolymer composition comprising a first core-shell copolymer and a second core-shell copolymer,
The first core-shell copolymer includes a (meth) acrylic core including a repeating unit derived from an alkyl (meth) acrylate monomer, a repeating unit derived from a methyl (meth) acrylate monomer, and a repeating unit derived from an alkyl (meth) acrylate monomer. And a first shell comprising a repeating unit derived from an aromatic vinyl monomer,
The second core-shell copolymer is a conjugated diene-based core including 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, and an aromatic vinyl monomer. A second shell including a repeating unit,
The average particle diameter of the (meth) acrylic core is 100 nm to 200 nm, and the average particle diameter of the conjugated diene core is 150 nm to 250 nm,
With respect to the total content of the copolymer composition, the content of the (meth) acrylic core is 18 parts by weight to 50 parts by weight, the content of the conjugated diene core is 28 parts by weight to 50 parts by weight, the first shell and the The content of the second shell is 18 parts by weight to 32 parts by weight of the copolymer composition. According to claim 1,
The copolymer composition having an average particle diameter of the (meth) acrylic core of 120 nm to 180 nm, and an average particle diameter of the conjugated diene core of 180 nm to 230 nm. According to claim 1,
The average particle diameter of the (meth) acrylic core is less than or equal to the average particle diameter of the conjugated diene core. According to claim 1,
The (meth) acrylic core and the conjugated diene-based core having a total average particle diameter of 175 nm to 220 nm. According to claim 1,
The copolymer composition having a total average particle diameter of the (meth) acrylic core and the conjugated diene core is 180 nm to 215 nm. According to claim 1,
The (meth) acrylic core copolymer composition further comprising a repeating unit derived from a crosslinkable monomer. According to claim 1,
With respect to the total content of the copolymer composition, the content of the (meth) acrylic core is 20 parts by weight to 50 parts by weight, the content of the conjugated diene core is 30 parts by weight to 50 parts by weight, the first shell and the Copolymer composition having a second shell content of 20 parts by weight to 30 parts by weight. i) polymerizing an alkyl (meth) acrylate monomer 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 step (S10) and the conjugated diene core prepared in step (S20) are introduced into a reactor, and methyl (meth) acrylate monomer, alkyl (meth) acrylate monomer, and Including an aromatic vinyl monomer, the first shell on the (meth) acrylic core, the second shell on the conjugated diene-based core, simultaneously graft polymerization to prepare a copolymer composition (S30),
The average particle diameter of the (meth) acrylic core prepared in the step (S10) is 100 nm to 200 nm, and the average particle diameter of the conjugated diene core prepared in the step (S20) is 150 nm to 250 nm,
The copolymer composition prepared in (S30), the total content of the copolymer composition, the content of the (meth) acrylic core is 18 parts by weight to 50 parts by weight, the content of the conjugated diene-based core is 28 parts by weight to It is 50 parts by weight, the content of the first shell and the second shell is a method for producing a copolymer composition of 18 parts by weight to 32 parts by weight. The copolymer composition of any one of claims 1 to 7; And a polycarbonate resin. The method of claim 9,
With respect to the total content of the thermoplastic resin composition, a thermoplastic resin composition comprising 1 part by weight to 20 parts by weight of the copolymer composition and 80 parts by weight to 99 parts by weight of the polycarbonate resin.