KR102280689B1 - Core-shell copolymer, method for preparing the copolymer and thermoplastic resin composition comprising the copolymer - Google Patents

Abstract

The present invention relates to a core-shell copolymer, and more particularly, based on the total content of the monomer-derived repeating unit included in the seed, 40 wt% or more to less than 90 wt% of the aromatic vinyl monomer-derived repeating unit and the bisphenol acrylate-based monomer a seed comprising more than 10% by weight to 60% by weight or less of the derived repeating unit; A core comprising a repeating unit derived from an alkyl (meth)acrylate monomer and a repeating unit derived from a crosslinkable monomer, and surrounding the seed; and 68.5 wt% to 99.8 wt% of an alkyl (meth)acrylate monomer-derived repeating unit, and 0.2 wt% to 31.5 wt% of a bisphenol acrylate-based monomer-derived repeating unit with respect to the total content of the monomer-derived repeating unit included in the shell. and a core-shell copolymer comprising a shell surrounding the core, a method for preparing the same, and a thermoplastic resin composition comprising the same.

Description

Core-shell copolymer, manufacturing method thereof, and thermoplastic resin composition comprising the same {CORE-SHELL COPOLYMER, METHOD FOR PREPARING THE COPOLYMER AND THERMOPLASTIC RESIN COMPOSITION COMPRISING THE COPOLYMER}

The present invention relates to a core-shell copolymer, a method for preparing the same, and a thermoplastic resin composition comprising the same.

Polycarbonate resin (hereinafter referred to as PC resin) is known as a resin with excellent impact resistance, electrical properties, and heat resistance, and is widely used as a resin for manufacturing molded products used in electric and electronic products, including automobiles, and the demand is continuously increasing. is increasing to However, PC resin has disadvantages such as high melt viscosity, poor moldability, high thickness dependence of impact resistance, and poor chemical resistance and hydrolysis resistance.

Therefore, in general, when manufacturing molded products using PC resin, rather than using PC resin alone, alloy with acrylonitrile-butadiene-styrene resin (hereinafter referred to as ABS resin) to compensate for the high melt viscosity of PC resin (alloy) PC/ABS alloy resin is used, or PC/PBT alloy resin, an alloy product, is mixed with polybutylene terephthalate resin (hereinafter referred to as PBT resin) to supplement the chemical resistance of PC resin. are using However, even when a PC/ABS alloy resin or a PC/PBT alloy resin is used, there are still problems in terms of thickness dependence of impact resistance, colorability and hydrolysis resistance.

In order to simultaneously improve the impact resistance and colorability of PC resin as a solution to this problem, in addition to PC/ABS alloy resin or PC/PBT alloy resin, a method of applying an acrylic resin as an impact modifier has been proposed. For example, Korean Patent Application Laid-Open No. 2004-0057069 proposes an acrylic impact modifier having a multilayer structure, and suggests that impact resistance and colorability can be improved when this is used for PC resin, but compared to the effect of improving impact resistance, , improvement of colorability is not sufficient to be applicable to products, and hydrolysis resistance still remains an unsolved problem. In addition, Korean Patent Laid-Open Publication No. 2010-0038611 also presents a butadiene-based impact modifier to which a butadiene-based rubber core is applied, and when used in PC resin, it is suggested that impact resistance and colorability can be improved, but during injection molding, There is a problem of poor thermal stability.

US 2004-0057069 A US 2010-0038611 A

The problem to be solved in the present invention is to improve thermal stability during molding of a molded article by applying an acrylic impact modifier to a polycarbonate-based resin in order to solve the problems mentioned in the technology that is the background of the invention, and furthermore, the molded article to improve the impact resistance and colorability of

That is, the present invention has been devised to solve the problems of the technology that is the background of the invention, and provides a core-shell copolymer, which is an acrylic impact modifier used together with a polycarbonate-based resin, and the core-shell copolymer By including, it aims to provide a thermoplastic resin composition excellent in thermal stability and excellent in impact resistance and colorability.

According to an embodiment of the present invention for solving the above problems, the present invention provides 40 wt% or more to less than 90 wt% of repeating units derived from aromatic vinyl monomers and less than 90 wt% of repeating units derived from aromatic vinyl monomers, based on the total content of repeating units derived from monomers included in the seed, and bisphenol acryl a seed comprising more than 10 wt% to 60 wt% or less of a repeating unit derived from a rate-based monomer; A core comprising a repeating unit derived from an alkyl (meth)acrylate monomer and a repeating unit derived from a crosslinkable monomer, and surrounding the seed; and 68.5 wt% to 99.8 wt% of an alkyl (meth)acrylate monomer-derived repeating unit, and 0.2 wt% to 31.5 wt% of a bisphenol acrylate-based monomer-derived repeating unit with respect to the total content of the monomer-derived repeating unit included in the shell. And, it provides a core-shell copolymer comprising a shell surrounding the core.

In addition, the present invention provides a step of preparing a seed by i) polymerizing a seed monomer mixture comprising 40 wt% to less than 90 wt% of an aromatic vinyl monomer and 10 wt% to 60 wt% or less of a bisphenol acrylate monomer (S1) ); ii) preparing a core by reacting a core monomer mixture including an alkyl (meth)acrylate monomer and a crosslinking monomer in the presence of the seed prepared in step (S1) (S2); and iii) in the presence of the core prepared in step (S2), 68.5 wt% to 99.8 wt% of an alkyl (meth)acrylate monomer and 0.2 wt% to 31.5 wt% of a bisphenol acrylate monomer A shell monomer mixture comprising It provides a method for preparing a core-shell copolymer comprising the step (S3) of preparing a core-shell copolymer by reacting.

In addition, the present invention provides a thermoplastic resin composition comprising the core-shell copolymer and a polycarbonate-based resin.

When the core-shell copolymer provided in the present invention is included as an impact modifier in a thermoplastic resin composition containing a polycarbonate-based resin, the thermoplastic resin composition has excellent thermal stability and excellent impact resistance and colorability.

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor must properly understand the concept of the term in order to best describe his invention. Based on the principle that can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

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

The core-shell copolymer according to the present invention contains 40 wt% or more to less than 90 wt% of a repeating unit derived from an aromatic vinyl monomer and 10 wt% of a repeating unit derived from a bisphenol acrylate monomer based on the total content of the repeating unit derived from the monomer included in the seed. seeds comprising more than 60% by weight; A core comprising a repeating unit derived from an alkyl (meth)acrylate monomer and a repeating unit derived from a crosslinkable monomer, and surrounding the seed; and 68.5 wt% to 99.8 wt% of an alkyl (meth)acrylate monomer-derived repeating unit, and 0.2 wt% to 31.5 wt% of a bisphenol acrylate-based monomer-derived repeating unit with respect to the total content of the monomer-derived repeating unit included in the shell. and a shell surrounding the core.

The core-shell copolymer may be a graft copolymer in which a repeating unit derived from a monomer forming a core on a seed is polymerized, and a repeating unit derived from a monomer forming a shell on a core is graft polymerized. It may be an acrylic impact modifier used together with the resin.

According to the core-shell copolymer of the present invention, there is an effect that can prevent deterioration of optical properties, colorability and thermal stability due to differences in refractive index and compatibility with polycarbonate-based resins in the thermoplastic resin composition.

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

In the present invention, the term 'seed' refers to a polymer polymerized prior to polymerization of the core in the manufacturing process so that the mechanical properties of the core-shell copolymer can be supplemented and the polymerization of the core can be easily carried out. It may mean a component or a copolymer component, and in the present invention, the term 'core' refers to a form in which a monomer forming a core is polymerized on the surface of the seed, and the core surrounds the seed. , a core-shell copolymer may mean a rubber component or a rubber polymer component constituting the core or core layer, and in the present invention, the term 'shell' is a monomer forming a shell. is graft polymerized to the core of the core-shell copolymer, indicating a form in which the shell surrounds the core, which means a polymer component, or a copolymer component, constituting the shell or shell layer of the core-shell copolymer it could be

In the core-shell copolymer of the present invention, the seed facilitates the polymerization of the core during polymerization of the core-shell copolymer, improves the mechanical properties of the thermoplastic resin composition, and the difference in refractive index with the polycarbonate-based resin In order to reduce the , it may include a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a bisphenol acrylate-based monomer.

According to an embodiment of the present invention, the repeating unit derived from the aromatic vinyl monomer may be a repeating unit derived from an aromatic vinyl monomer participating in a polymerization reaction, and the aromatic vinyl monomer may include, for example, styrene, α-methylstyrene, and 3-methyl It may be at least one selected from the group consisting of styrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene; , in this case, the difference in refractive index with the polycarbonate-based resin is low, so that optical properties and colorability are excellent.

In addition, according to an embodiment of the present invention, the repeating unit derived from the aromatic vinyl monomer is 40 wt% or more to less than 90 wt%, 40 wt% to 80 wt%, based on the total content of the monomer-derived repeating unit included in the seed , or may be included in an amount of 50 wt% to 70 wt%, and within this range, the impact resistance and colorability of the thermoplastic resin composition including the core-shell copolymer as an acrylic impact modifier are excellent.

Meanwhile, according to an embodiment of the present invention, the repeating unit derived from the bisphenol acrylate monomer may be a repeating unit derived from the bisphenol acrylate monomer participating in the polymerization reaction. According to the present invention, when a repeating unit derived from a bisphenol acrylate-based monomer is included in the seed, there is an effect excellent in compatibility between the seed and the core in the core-shell copolymer, and thus, the core-shell copolymer is subjected to acrylic impact There is an effect excellent in impact resistance, colorability and thermal stability of the thermoplastic resin composition including the reinforcing agent.

The bisphenol acrylate-based monomer may refer to a monomer including a bisphenol group and an acrylate group capable of participating in a polymerization reaction in the compound, and in a specific example, one or two hydroxyl groups (-OH) of the bisphenol group is a single bond (single bonding) or may be a compound substituted with an acrylate group by a linking group, and more specifically, one or two hydroxyl groups of the bisphenol group are acrylated by a single bond, alkylene oxide, or polyalkylene oxide It may be a compound substituted with a group. In addition, the bisphenol acrylate-based bisphenol may be bisphenol A or bisphenol F, and bisphenol F may be preferable in terms of compatibility with the core.

According to an embodiment of the present invention, the bisphenol acrylate-based monomer may be a compound represented by the following formula (1).

[Formula 1]

In Formula 1, R ¹ and R ² may each independently be hydrogen or a methyl group, R ³ and R ⁴ may each independently be an alkylene group having 1 to 10 carbon atoms, and R ⁵ and R ⁶ are Each independently may be hydrogen or an alkyl group having 1 to 5 carbon atoms, and m and n may each independently be 0 or an integer of 1 to 30.

As a specific example, R ¹ and R ² may each independently be hydrogen or a methyl group, R ³ and R ⁴ may each independently be an alkylene group having 1 to 5 carbon atoms, and R ⁵ and R ⁶ are each independently may be hydrogen or an alkyl group having 1 to 2 carbon atoms, and m and n may each independently be 0 or an integer of 1 to 20.

As a more specific example, R ¹ and R ² may each independently be hydrogen, R ³ and R ⁴ may each independently be an alkylene group having 1 to 3 carbon atoms, and R ⁵ and R ⁶ are each independently It may be hydrogen, and m and n are each independently an integer of 1 to 10, and m+n may be 4 to 20.

According to one embodiment of the present invention, a bisphenol acrylate-based monomer-derived repeating unit contained in the seed is a bisphenol F (ethylene oxide) ₄ diacrylate (Bisphenol F (ethylene oxide) ₄ diacrylate) and Bisphenol A (ethylene oxide) ₂₀ diacrylate (Bisphenol A (ethylene oxide) ₂₀ diacrylate) may be one or more monomer-derived repeating units selected from the group consisting of, in this case, the core-shell copolymer has an excellent compatibility effect between the seed and the core, , and thus, the thermoplastic resin composition including the core-shell copolymer as an acrylic impact modifier has excellent impact resistance, colorability and thermal stability.

In addition, according to an embodiment of the present invention, the repeating unit derived from the bisphenol acrylate-based monomer included in the seed is more than 10 wt% to 60 wt% or less, based on the total content of the repeating unit derived from the monomer included in the seed, It may be included in an amount of 20 wt% to 60 wt%, or 30 wt% to 50 wt%, and within this range, the thermoplastic resin composition including the core-shell copolymer as an acrylic impact modifier has excellent impact resistance and colorability. .

According to an embodiment of the present invention, the seed may be included in an amount of 2 wt% to 20 wt%, 5 wt% to 15 wt%, or 8 wt% to 12 wt%, based on the total content of the core-shell copolymer , within this range, the impact resistance, colorability and thermal stability of the thermoplastic resin composition including the core-shell copolymer as an acrylic impact modifier is excellent.

On the other hand, in the core-shell copolymer of the present invention, the core is for improving impact resistance when mixed with a polycarbonate-based resin, and may be an acrylate rubbery core, an embodiment of the present invention According to an example, the core may include a repeating unit derived from an alkyl (meth)acrylate monomer and a repeating unit derived from a crosslinkable monomer. As another example, the core may exist in a form surrounding the seed.

According to an embodiment of the present invention, the repeating unit derived from the alkyl (meth) acrylate monomer may be a repeating unit derived from the alkyl (meth) acrylate monomer participating in the polymerization reaction, and specifically, an alkyl group having 2 to 12 carbon atoms It may be an alkyl (meth)acrylate monomer containing. In this case, the alkyl group having 2 to 12 carbon atoms may mean including both a linear alkyl group having 2 to 12 carbon atoms and a branched alkyl group having 3 to 12 carbon atoms. As a specific example, the alkyl (meth) acrylate monomer is ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) ) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylic It can be rate. As another example, the alkyl (meth) acrylate monomer may be an alkyl (meth) acrylate monomer containing an alkyl group having 2 to 8 carbon atoms. Here, the alkyl (meth)acrylate monomer may mean an alkyl acrylate or an alkyl methacrylate. In addition, the repeating unit derived from the alkyl (meth)acrylate monomer included in the core may include repeating units derived from two or more monomers selected from the group consisting of alkyl (meth)acrylate monomers having 2 to 12 carbon atoms. That is, the alkyl (meth) acrylate monomer may be a mixture of two or more kinds of alkyl (meth) acrylates containing different alkyl groups.

In addition, according to an embodiment of the present invention, the crosslinkable monomer is a comonomer for easily performing polymerization during core polymerization, and includes ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth) (meth)acrylic crosslinkable monomers such as acrylate, allyl (meth)acrylate, trimethylolpropane tri(meth)acrylate and pentaerythritol tetra(meth)acrylate; It may be at least one selected from vinyl-based crosslinking monomers such as divinylbenzene, divinylnaphthalene and diallylphthalate.

According to an embodiment of the present invention, the repeating unit derived from the alkyl (meth)acrylate monomer is 98.5 wt% to 99.9 wt%, 98.5 wt% to 99.5 wt%, based on the total content of the monomer-derived repeating unit included in the core. , or 98.8 wt% to 99.2 wt%, wherein the crosslinkable monomer-derived repeating unit is 0.1 wt% to 1.5 wt%, 0.5 wt% to 1.5 wt%, based on the total content of the monomer-derived repeating unit included in the core %, or 0.8 wt% to 1.2 wt%, excellent in polymerization productivity within this range, and excellent impact resistance of the thermoplastic resin composition including the core-shell copolymer as an acrylic impact modifier.

In addition, according to an embodiment of the present invention, the core is 40 wt% to 88 wt%, 50 wt% to 80 wt%, or 60 wt% to 70 wt%, based on the total content of the core-shell copolymer It may be included, and within this range, there is an excellent effect in impact resistance, colorability and thermal stability of the thermoplastic resin composition including the core-shell copolymer as an acrylic impact modifier.

In the core-shell copolymer of the present invention, when the shell is mixed with a polycarbonate-based resin, to improve dispersibility in the matrix resin, the shell according to an embodiment of the present invention is an alkyl (meth)acrylic It may include a repeating unit derived from a rate monomer and a repeating unit derived from a bisphenol acrylate-based monomer. As another example, the shell may exist in a form surrounding the core.

As a specific example, the alkyl (meth) acrylate monomer may be derived from the same monomer as the repeating unit derived from the alkyl (meth) acrylate monomer of the core, or methyl (meth) derived from a methyl (meth) acrylate monomer. It may be a repeating unit derived from an acrylate monomer. As described above, when an alkyl (meth) acrylate monomer is used as a monomer for forming a shell, it is easy to form a shell on the core, and it is excellent in dispersibility in the matrix resin, and there is an effect of very excellent impact resistance .

On the other hand, the repeating unit derived from the bisphenol acrylate monomer of the shell may be derived from the same monomer as the repeating unit derived from the bisphenol acrylate monomer of the seed, and when the repeating unit derived from the bisphenol acrylate monomer is included in the shell , there is an effect of excellent impact resistance, colorability and thermal stability of the thermoplastic resin composition comprising the core-shell copolymer as an acrylic impact modifier.

According to one embodiment of the present invention, a bisphenol acrylate-based monomer-derived repeating units contained in the shell include bisphenol F (ethylene oxide) ₄ diacrylate (Bisphenol F (ethylene oxide) ₄ diacrylate) and Bisphenol A (ethylene oxide) ₂₀ diacrylate (Bisphenol A (ethylene oxide) ₂₀ diacrylate) may be a repeating unit derived from at least one monomer selected from the group consisting of, in this case, the impact resistance of the thermoplastic resin composition comprising the core-shell copolymer as an acrylic impact modifier , colorability and thermal stability are excellent.

In addition, according to an embodiment of the present invention, the alkyl (meth) acrylate monomer-derived repeating unit is 68.5 wt% to 99.8 wt%, 70 wt% to 95 wt%, based on the total content of the monomer-derived repeating unit included in the shell. It may be included in wt%, or 80 wt% to 92 wt%, and the bisphenol acrylate monomer-derived repeating unit included in the shell is 0.2 wt% to 31.5 wt% based on the total content of the monomer-derived repeating unit included in the shell. 5, 5 to 30% by weight 5, or 8 to 20% by weight may be included, and within this range, the dispersibility of the core-shell copolymer in the matrix resin is excellent, and the core-shell copolymer is used as an acrylic impact modifier. There is an effect excellent in the impact resistance and colorability of the thermoplastic resin composition comprising

In addition, according to an embodiment of the present invention, the shell is 10 wt% to 40 wt%, 15 wt% to 35 wt%, or 22 wt% to 28 wt%, based on the total content of the core-shell copolymer It may be included, and within this range, there is an excellent effect in impact resistance, colorability and thermal stability of the thermoplastic resin composition including the core-shell copolymer as an acrylic impact modifier.

In addition, according to an embodiment of the present invention, each of the seed, core, and shell included in the core-shell copolymer may be a random copolymer in which repeating units derived from monomers constituting the seed, core and shell are randomly distributed. there is.

The method for preparing a core-shell copolymer according to the present invention comprises i) polymerizing a seed monomer mixture comprising 40 wt% or more to less than 90 wt% of an aromatic vinyl monomer and 10 wt% to 60 wt% or less of a bisphenol acrylate monomer preparing a seed (S1); ii) preparing a core by reacting a core monomer mixture including an alkyl (meth)acrylate monomer and a crosslinking monomer in the presence of the seed prepared in step (S1) (S2); and iii) in the presence of the core prepared in step (S2), 68.5 wt% to 99.8 wt% of an alkyl (meth)acrylate monomer, and 0.2 wt% to 31.5 wt% of a bisphenol acrylate-based monomer shell monomer mixture reacting to prepare a core-shell copolymer (S3).

According to an embodiment of the present invention, step (S1) is a step for preparing a seed according to the present invention, and may be carried out by radical polymerization in the presence of an aromatic vinyl monomer and a bisphenol acrylate monomer, and emulsification. It can be carried out by a polymerization method. In addition, the step (S1) may be carried out at 30 °C to 65 °C, or 40 °C to 60 °C. According to an embodiment of the present invention, the type of the monomer input in step (S1) and the input content of the monomer are aromatic for forming a repeating unit derived from an aromatic vinyl monomer included in the seed described in the core-shell copolymer. It may be the same type and the same content as the bisphenol acrylate monomer for forming the repeating unit derived from the vinyl monomer and the bisphenol acrylate monomer.

In addition, according to an embodiment of the present invention, step (S2) is a step for preparing a core according to the present invention, and in the presence of the seed prepared in step (S1), an alkyl (meth)acrylate monomer and It can be carried out by reacting the crosslinkable monomer. Like step (S1), the step (S2) may be carried out by radical polymerization or may be carried out by an emulsion polymerization method. In addition, the step (S2) may be carried out at 40 °C to 70 °C, or 50 °C to 65 °C. According to an embodiment of the present invention, the type of the monomer input in step (S2) and the input content of the monomer are the repeating units derived from the alkyl (meth) acrylate monomer included in the core described in the core-shell copolymer. It may be the same type and the same content as the crosslinkable monomer for forming the repeating unit derived from the alkyl (meth)acrylate monomer and the crosslinkable monomer for forming.

In addition, according to an embodiment of the present invention, step (S3) is a step for preparing a core-shell copolymer according to the present invention, and in the presence of the core prepared in step (S2), alkyl (meth) It may be carried out by reacting at least one monomer selected from the group consisting of an acrylate monomer, an aromatic vinyl monomer, and a vinyl cyan monomer, and a bisphenol acrylate-based monomer. The step (S3) may be carried out by graft polymerization or may be carried out by an emulsion polymerization method. According to an embodiment of the present invention, the type of the monomer and the amount of the monomer input in the step (S3) are the alkyl (meth) acrylate monomer and the aromatic vinyl monomer included in the shell described in the core-shell copolymer. And at least one monomer selected from the group consisting of alkyl (meth)acrylate monomers, aromatic vinyl monomers and vinyl cyan monomers for forming a repeating unit derived from at least one monomer selected from the group consisting of vinyl cyan monomers, and bisphenol acrylate monomers It may be the same kind and the same content as the bisphenol acrylate monomer for forming the derived repeating unit.

On the other hand, according to an embodiment of the present invention, the core-shell copolymer manufacturing method comprises the steps of agglomeration, aging, dehydration and drying in order to obtain the core-shell copolymer latex obtained by emulsion polymerization in powder form. may include each. The core-shell copolymer powder obtained through the above step may serve as an impact modifier in the thermoplastic resin composition.

According to an embodiment of the present invention, the coagulation step may be carried out by adding 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 core-shell copolymer latex. When performing the aging step after the aggregation step, there is an effect that can remove residual monomers that did not participate in polymerization by volatilization. The dehydration and drying step can be carried out using a hot air drying method after removing moisture from the agglomerated and / or aged copolymer composition latex with a dehydrator to separate it into solid content, and in this case, the drying time is shortened through dehydration, There is an effect of removing residual monomers that did not participate in polymerization through hot air drying.

The thermoplastic resin composition according to the present invention may include the core-shell copolymer and the polycarbonate-based resin. The thermoplastic resin composition may include, for example, the core-shell copolymer as an impact modifier.

According to an embodiment of the present invention, the polycarbonate-based resin may be a polycarbonate-based resin in which a bisphenol-based monomer and a carbonate precursor are copolymerized. The bisphenol-based monomer is, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis( 4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA ), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z; BPZ), 2,2-bis(4-hydroxy-3, 5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2, 2-bis(4-hydroxy-3chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl) Propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane and α,ω-bis[3-(ο-hydroxyphenyl)propyl]poly It may be at least one selected from the group consisting of dimethylsiloxane. The carbonate precursor is, for example, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m- cresyl carbonate, dinaphthyl carbonate, bis ( diphenyl) carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, and bishaloformate may be at least one selected from the group consisting of.

According to an embodiment of the present invention, the content of the core-shell copolymer is 0.1 wt% to 50 wt%, 0.1 wt% to 30 wt%, or 0.1 wt% to 20 wt% based on the total content of the thermoplastic resin composition may be, and the content of the polycarbonate-based resin may be 50 wt% to 99.9 wt%, 70 wt% to 99.9 wt%, or 80 wt% to 99.9 wt%, based on the total content of the thermoplastic resin composition, in this range There is an effect excellent in the impact resistance, colorability and heat resistance of the thermoplastic resin composition within the composition.

As another example, the thermoplastic resin composition may include a heat stabilizer, antioxidant, light stabilizer, pigment, dye, antistatic agent, antibacterial agent, and metal in the range that does not affect the physical properties, in addition to the core-shell copolymer and polycarbonate-based resin. At least one additive selected from the group consisting of an inactivating agent, a flame retardant, and a fluorine-based anti-drip agent may be further included.

The thermoplastic resin composition according to the present invention has an impact strength of 10 kgf·cm/cm to 20 kgf·cm/cm, 12 of 1/8" thick specimen according to standard measurement ASTM D-256, method A at -30°C. kgf·cm/cm to 18 kgf·cm/cm, or 14 kgf·cm/cm to 16 kgf·cm/cm, the impact strength at room temperature (15°C to 25°C) is 55 kgf·cm/cm excess, from 60 kgf·cm/cm to 80 kgf·cm/cm, or from 70 kgf·cm/cm to 75 kgf·cm/cm.

In addition, the thermoplastic resin composition according to the present invention uses an EC100 Φ30 injection machine from ENGEL, and the amount of change in yellowness measured after the specimen is kept at 330° C. for 10 minutes (= yellowness of the non-retained specimen - retention for 10 minutes) The yellowness of the prepared specimen) may be 20 or less, 0.1 to 15, or 6 to 9.

In addition, the thermoplastic resin composition according to the present invention measures the CIE lab color value using a spectrophotometer Color-eye 3100 instrument, and based on the CIE lab color value of the control specimen, the difference in color values The reflected ΔE (= [ΔL ² + Δa ² + Δb ² ] ^1/2 ) may be 10 or less, 0.1 to 10, or 5 to 7.

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are intended to illustrate the present invention, and it is clear to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, and the scope of the present invention is not limited thereto.

Example

Example 1

<Seed Manufacturing>

In a reactor of a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet and a circulation condenser, 190 parts by weight of ion-exchanged water was added, and the temperature inside the reactor was raised to 50° C. under a nitrogen atmosphere and maintained. After the reactor internal temperature reached 50 °C, 7 parts by weight of styrene (SM), 3 parts by weight of bisphenol F (ethylene oxide) ₄ diacrylate (BPF (EO) ₄ DA), sodium lauryl sulfonate (sodium) as an emulsifier 0.1 parts by weight of laulyl sulfonate, 0.01 parts by weight of t-butyl hydroperoxide as a polymerization initiator, Ferrous sulfate, Ethylene diamine tetraacetic acid, and sodium sulfoxylate formaldehyde (Sodium formaldehyde sulfoxylate) 0.025 parts by weight of redox activator containing (redox activator) was added at once to proceed with the reaction. After aging for 3 hours, the reaction was terminated to prepare a seed latex, wherein the polymerization conversion rate was 96%, and the average particle diameter of the seed particles distributed on the latex was 100 nm.

<Core manufacturing>

In the presence of the prepared seed latex, the internal temperature of the reactor was maintained at 60 °C. Then, a monomer mixture of 49.35 parts by weight of butyl acrylate (BA), 15 parts by weight of 2-ethylhexyl acrylate (2-EHA), and 0.65 parts by weight of allyl methacrylate (AMA) was added to an emulsifier sodium lauryl sulfonate by 0.3 parts by weight. Part, 0.1 parts by weight of t-butyl hydroperoxide as a polymerization initiator, and redox activation containing ferrous sulfate, ethylene diamine tetraacetic acid and sodium formaldehyde sulfoxylate The reaction was progressed by continuously adding 0.15 parts by weight of a redox activator for 3 hours. After the addition of the monomer mixture was completed, the reaction was terminated after aging for 2 hours to prepare a core latex, wherein the polymerization conversion rate was 98%, and the average particle diameter of the core particles distributed on the latex was 225 nm.

<Preparation of core-shell copolymer>

In the presence of the prepared core latex, the internal temperature of the reactor was raised to 70 °C and maintained. After the reactor internal temperature reached 70 ° C., a monomer mixture of 23 parts by weight of methyl methacrylate (MMA) and 2 parts by weight of bisphenol F (ethylene oxide) ₄ diacrylate (BPF(EO) ₄ DA) was added as a polymerization initiator. A redox activator comprising 0.1 parts by weight of potassium persulfate, Ferrous sulfate, Ethylene diamine tetraacetic acid and Sodium formaldehyde sulfoxylate ) was continuously added with 0.05 parts by weight for 2 hours to proceed the reaction. After completion of the addition of the monomer mixture, the reaction was terminated after aging for 1 hour and 30 minutes to prepare a core-shell copolymer latex, wherein the polymerization conversion rate was 99%, and the average particle diameter of the core-shell copolymer particles was 250 nm, The composition of the core-shell copolymer is shown in Table 1 below.

<Preparation of core-shell copolymer powder>

To the obtained core-shell copolymer latex, 1 part by weight aqueous solution of magnesium sulfate (concentration of 15%) based on 100 parts by weight of the solid core-shell copolymer was added as a coagulant at one time to coagulate, and after obtaining a slurry, the The slurry was washed three times with ion-exchanged water to wash off by-products, and the washing water was removed by filtration. Then, it was dried at 80° C. for 2 hours using a fluidized-bed dryer to obtain a core-shell copolymer powder.

Example 2

In Example 1, the same method as in Example 1 was carried out, except that 6.5 parts by weight of styrene and _{3.5 parts by weight of bisphenol F (ethylene oxide) 4 diacrylate were added during the preparation of the seed, and the prepared core} - The composition of the shell copolymer is described in Table 1 below.

Example 3

In Example 1, the same method as in Example 1, except that 20 parts by weight of methyl methacrylate and 5 parts by weight of bisphenol F (ethylene oxide) _{4 diacrylate were added when preparing the core-shell copolymer.} was carried out, and the composition of the prepared core-shell copolymer is shown in Table 1 below.

Example 4

In Example 1, the same method as in Example 1 was carried out, except that 5 parts by weight of styrene and 5 parts by weight of bisphenol F (ethylene oxide) _{4 diacrylate were added during seed preparation, and the prepared core} - The composition of the shell copolymer is described in Table 1 below.

Example 5

In Example 1, when preparing the seed, 3 parts by weight of bisphenol A (ethylene oxide) _{20 diacrylate was added instead of bisphenol F (ethylene oxide) 4} diacrylate, and when preparing the shell, bisphenol F (ethylene oxide) ₄ diacrylate It was carried out in the same manner as in Example 1 except that 2 parts by weight of bisphenol A (ethylene oxide) ₂₀ diacrylate was added instead of acrylate, and the composition of the prepared core-shell copolymer is shown in Table 1 below.

Comparative Example 1

In Example 1, when preparing the seed, styrene was added in an amount of 10 parts by weight, bisphenol F (ethylene oxide) ₄ diacrylate was not added, and when preparing the shell, methyl methacrylate was added in an amount of 25 parts by weight, and bisphenol It was carried out in the same manner as in Example 1, except that F (ethylene oxide) ₄ diacrylate was not added, and the composition of the prepared core-shell copolymer is shown in Table 2 below.

Comparative Example 2

In Example 1, during seed preparation, 9 parts by weight of styrene and 1 part by weight of bisphenol F (ethylene oxide) ₄ diacrylate were added in the same manner as in Example 1, except that the prepared core - The composition of the shell copolymer is described in Table 2 below.

Comparative Example 3

In Example 1, during seed preparation, 2 parts by weight of styrene and 8 parts by weight of bisphenol F (ethylene oxide) ₄ diacrylate were added in the same manner as in Example 1, except that the prepared core - The composition of the shell copolymer is described in Table 2 below.

Comparative Example 4

In Example 1, when preparing the seed, 2 parts by weight of styrene was added, bisphenol F (ethylene oxide) ₄ diacrylate was not added, and 57.35 parts by weight of butyl acrylate was added at the time of preparing the core, except that 57.35 parts by weight was added. was carried out in the same manner as in Example 1, and the composition of the prepared core-shell copolymer is shown in Table 2 below.

Comparative Example 5

In Example 1, when preparing the core, 64.35 parts by weight of butyl acrylate was added, and when preparing the shell, 10 parts by weight of methyl methacrylate was added, and bisphenol F (ethylene oxide) ₄ diacrylate was not added. Except that, it was carried out in the same manner as in Example 1, and the composition of the prepared core-shell copolymer is shown in Table 2 below.

Comparative Example 6

In Example 1, when preparing the core-shell copolymer, 11.4 parts by weight of methyl methacrylate was added, and 5.8 parts by weight of styrene and 5.8 parts by weight of acrylonitrile were added in the same manner as in Example 1, except that was carried out, and the composition of the prepared core-shell copolymer is described in Table 1 below.

Comparative Example 7

In Example 1, when preparing the core-shell copolymer, 17 parts by weight of methyl methacrylate _{and 8 parts by weight of bisphenol F (ethylene oxide) 4} diacrylate were added in the same manner as in Example 1 was carried out, and the composition of the prepared core-shell copolymer is shown in Table 1 below.

division Example One 2 3 4 5 seed SM ¹⁾ (parts by weight) 7 6.5 7 5 7 BPF(EO) ₄ DA ²⁾
(parts by weight) 3 3.5 3 5 - BPA(EO) ₂₀ DA ³⁾
(parts by weight) - - - - 3 core BA ⁴⁾ (parts by weight) 49.35 49.35 49.35 49.35 49.35 2-EHA ⁵⁾ (parts by weight) 15 15 15 15 15 AMA ⁶⁾ (parts by weight) 0.65 0.65 0.65 0.65 0.65 shell MMA ⁷⁾ (parts by weight) 23 23 20 23 23 SM ¹⁾ (parts by weight) - - - - - AN ⁸⁾ (parts by weight) - - - - - BPF(EO) ₄ DA ²⁾
(parts by weight) 2 2 5 2 - BPA(EO) ₂₀ DA ³⁾
(parts by weight) - - - - 2 Total monomer content (parts by weight) 100 100 100 100 100 1) SM: Styrene
2) BPF (EO) ₄ DA: bisphenol F (ethylene oxide) ₄ diacrylate
3) BPA (EO) ₂₀ DA: bisphenol A (ethylene oxide) ₂₀ diacrylate
4) BA: butyl acrylate
5) 2-EHA: 2-ethylhexyl acrylate
6) AMA: allyl methacrylate
7) MMA: methyl methacrylate
8) AN: acrylonitrile

division comparative example One 2 3 4 5 6 7 seed SM ¹⁾ (parts by weight) 10 9 2 2 7 7 7 BPF(EO) ₄ DA ²⁾
(parts by weight) - One 8 - 3 3 3 core BA ³⁾ (parts by weight) 49.35 49.35 49.35 57.35 64.35 49.35 49.35 2-EHA ⁴⁾ (parts by weight) 15 15 15 15 15 15 15 AMA ⁵⁾ (parts by weight) 0.65 0.65 0.65 0.65 0.65 0.65 0.65 shell MMA ⁶⁾ (parts by weight) 25 23 23 23 10 11.4 17 SM ¹⁾ (parts by weight) - - - - - 5.8 - AN ⁷⁾ (parts by weight) - - - - - 5.8 - BPF(EO) ₄ DA ²⁾
(parts by weight) - 2 2 2 - 2 8 Total monomer content (parts by weight) 100 100 100 100 100 100 100 1) SM: Styrene
2) BPF (EO) ₄ DA: bisphenol F (ethylene oxide) ₄ diacrylate
3) BA: butyl acrylate
4) 2-EHA: 2-ethylhexyl acrylate
5) AMA: Allyl Methacrylate
6) MMA: methyl methacrylate
7) AN: acrylonitrile

Experimental example

Based on 100 parts by weight of the total content of the core-shell copolymer powder and polycarbonate resin, 4 parts by weight of the core-shell copolymer prepared in Examples 1 to 5 and Comparative Examples 1 to 6, polycarbonate resin (LG-Dow) Co., Ltd., product name PC 1300-15) 96 parts by weight, 0.5 parts by weight of processing additive and 0.02 parts by weight of pigment were mixed as additives, and 200 parts by weight using a twin screw extruder of Leistritz. rpm, a metering rate of 60 kg/hr, and extruding under the conditions of a temperature of 250 °C to 320 °C, to obtain pellets. The obtained pellets were injected using an EC100 Φ30 injection machine from ENGEL, at a temperature of 250° C. to 320° C., to prepare a specimen for physical property evaluation, and then the physical properties were measured by the following method, Table 3 4 is shown.

* Impact strength (Notched Izod Impact Strengte, kgf cm/cm): According to the standard measurement method ASTM D256, Method A using a 1/8" thick specimen with a notch, -30 ℃ and room temperature ( The impact strength at 15 ℃ to 25 ℃) was measured.

* Heat resistance - Injection retention stability (YI): Measure the yellowness (YI, Yellow Index) at room temperature (15 ℃ to 25 ℃) using Hunterlab UltraScan Pro, a colorimeter for pellet specimens yellowness), and the pellet specimen was allowed to stay at 330 ° C. for 10 minutes using an EC100 Φ30 injection machine from ENGEL, and then the yellowness at room temperature (15 ° C. to 25 ° C.) was measured in the same manner. The amount of change (= yellowness of the non-retained specimen minus the yellowness of the specimen retained for 10 minutes) was calculated.

* Colorability (E): Among the pellet specimens prepared by the same method as in Example 3, a specimen having the color and color of the colorant most similar to that of the colorant was used as a control specimen. CIE lab color values were measured for five pellet specimens for each Example and Comparative Example using a spectrophotometer Color-eye 3100 instrument, and the difference in color values was measured based on the CIE lab color value of the control specimen. ΔE (= [ΔL ^* ₂ + Δa ^* ₂ + Δb ^* ₂ ] _{1 / 2} ) was calculated by reflecting, and the average value of ΔE for 5 pellet specimens measured for each Example and Comparative Example indicated as At this time, the smaller ΔE, the smaller the color difference with the colorant is, so the coloring is excellent, and the larger the ΔE is, the greater the color difference is, indicating that the colorability is poor because the color is not well done. The value of ΔE is 5 There is an error in the average value for the colorability of the pellet specimens, and within the error range 3, the same specimen was considered and measured.

division Example One 2 3 4 5 impact strength
(kgf cm/cm) room temperature 75 73 75 70 70 -30℃ 16 15 14 15 15 heat resistance
(Injection retention stability) YI 8 9 6 9 9 colorability E 7 7 4 5 8

division comparative example One 2 3 4 5 6 7 impact strength
(kgf cm/cm) room temperature 45 48 48 52 30 55 40 -30℃ 7 6 7 8 3 10 5 heat resistance
(Injection retention stability) YI 26 31 28 25 30 6 25 colorability E 12 15 13 30 20 6 15

As shown in Tables 3 and 4 above, in the case of Examples 1 to 5, in which the core-shell copolymer prepared by including the bisphenol acrylate monomer in the seed and the shell according to the present invention was used in the thermoplastic resin composition, the seed and shell Compared to Comparative Example 1 prepared without the bisphenol acrylate-based monomer, it was confirmed that the impact resistance and colorability were excellent, and the thermal stability was very excellent. On the other hand, in the case of Comparative Examples 2 and 3 prepared outside the range limited by the present invention, the content of the repeating unit derived from the bisphenol acrylic monomer included on the seed even if the seed and the shell include the repeating unit derived from the bisphenol acrylate monomer. It was confirmed that both the impact resistance and the colorability were poor, and the thermal stability was rather lowered, and even in Comparative Examples 4 and 5, which did not contain a repeating unit derived from a bisphenol acrylate-based monomer in either the seed or the shell, the impact resistance , it was confirmed that not only the colorability but also the thermal stability was greatly reduced. In addition, in the case of Comparative Example 6 in which styrene and acrylonitrile monomers were used for the shell, the shell was not formed normally, and thus compatibility with the matrix resin was lowered, and it was confirmed that the impact strength was very poor. It was confirmed that even in the case of Comparative Example 7 containing an excess of the rate-based monomer-derived repeating unit, the impact resistance, colorability and thermal stability were very deteriorated.

From the above results, the present inventors prepared a core-shell copolymer by including a bisphenol acrylate-based monomer in a specific content in the seed and shell according to the present invention, and when using it in a thermoplastic resin composition, a core using polystyrene seeds - Compared to the thermoplastic resin composition containing the shell copolymer, it was confirmed that the impact resistance, colorability and thermal stability of the thermoplastic resin composition can be significantly improved.

Claims (10)

A seed comprising 40 wt% or more to less than 90 wt% of an aromatic vinyl monomer-derived repeating unit and more than 10 wt% to 60 wt% or less of a bisphenol acrylate-based monomer-derived repeating unit with respect to the total content of the monomer-derived repeating unit included in the seed ;
A core comprising a repeating unit derived from an alkyl (meth)acrylate monomer and a repeating unit derived from a crosslinkable monomer, and surrounding the seed; and
With respect to the total content of the monomer-derived repeating unit included in the shell, 68.5 wt% to 99.8 wt% of the alkyl (meth)acrylate monomer-derived repeating unit, and 0.2 wt% to 31.5 wt% of the bisphenol acrylate-based monomer-derived repeating unit, and , A core-shell copolymer comprising a shell surrounding the core. According to claim 1,
The repeating units derived from the bisphenol acrylate monomer included in the seed and the shell are each independently a core-shell copolymer, which is a repeating unit derived from a monomer represented by the following formula (1):
[Formula 1]

In Formula 1,
R ¹ and R ² are each independently hydrogen or a methyl group,
R ³ and R ⁴ are each independently an alkylene group having 1 to 10 carbon atoms,
R ⁵ and R ⁶ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms,
m and n are each independently 0 or an integer from 1 to 30. 3. The method of claim 2,
The repeating unit derived from the monomer represented by Formula 1 is bisphenol F (ethylene oxide) ₄ diacrylate (Bisphenol F (ethylene oxide) ₄ diacrylate) and bisphenol A (ethylene oxide) ₂₀ diacrylate (Bisphenol A (ethylene oxide) ₂₀ diacrylate), a core-shell copolymer that is a repeating unit derived from at least one monomer selected from the group consisting of diacrylate). According to claim 1,
The core is a core-shell copolymer comprising 98.5 wt% to 99.9 wt% of a repeating unit derived from an alkyl (meth)acrylate monomer and 0.1 wt% to 1.5 wt% of a repeating unit derived from a crosslinkable monomer. According to claim 1,
The repeating unit derived from the alkyl (meth) acrylate monomer included in the core is a core-shell copolymer comprising two or more monomer-derived repeating units selected from the group consisting of alkyl (meth) acrylate monomers having 2 to 12 carbon atoms. . According to claim 1,
Based on the total content of the core-shell copolymer, the content of the seed is 2 wt% to 20 wt%, the content of the core is 40 wt% to 88 wt%, and the content of the shell is 10 wt% to 40 wt% % of the core-shell copolymer. i) preparing a seed by polymerizing a seed monomer mixture comprising 40 wt% to less than 90 wt% of an aromatic vinyl monomer and 10 wt% to 60 wt% or less of a bisphenol acrylate monomer (S1);
ii) preparing a core by reacting a core monomer mixture including an alkyl (meth)acrylate monomer and a crosslinking monomer in the presence of the seed prepared in step (S1) (S2); and
iii) In the presence of the core prepared in step (S2), 68.5 wt% to 99.8 wt% of an alkyl (meth)acrylate monomer and 0.2 wt% to 31.5 wt% of a bisphenol acrylate-based monomer A shell monomer mixture is reacted. A core-shell copolymer manufacturing method comprising the step (S3) of preparing a core-shell copolymer. A thermoplastic resin composition comprising a core-shell copolymer and a polycarbonate-based resin according to any one of claims 1 to 6. 9. The method of claim 8,
Based on the total content of the thermoplastic resin composition, the content of the core-shell copolymer is 0.1 wt% to 50 wt%, and the content of the polycarbonate-based resin is 50 wt% to 99.9 wt% of the thermoplastic resin composition. 9. The method of claim 8,
The thermoplastic resin composition has an impact strength of 10 kgf·cm/cm to 20 kgf·cm/cm at -30°C of a 1/8″ thick specimen according to standard measurement ASTM D-256, method A, and at room temperature (15°C) to 25 ° C.) of a thermoplastic resin composition having an impact strength greater than 55 kgf·cm/cm.