KR20220039400A - Method for preparing graft copolymer, graft copolymer and resin composition comprising the copolymer - Google Patents

Abstract

The present invention relates to a method for preparing a graft copolymer, and more specifically, to a method for preparing a graft copolymer, which comprises the steps of: preparing an enlarged rubbery polymer latex including an enlarged rubbery polymer by injecting and coagulating a polymeric coagulant latex into a rubbery polymer latex containing a rubbery polymer (S10); and preparing a graft copolymer latex containing a graft copolymer by adding an aromatic vinyl monomer and a vinyl cyan monomer to the enlarged rubbery polymer latex prepared in S10 and carrying out graft polymerization (S20), in which the polymer coagulant includes two or more types of alkyl acrylate-based monomer units and (meth)acrylic acid-based monomer units, and the polymer coagulant includes 0.1% to 1.0% by weight of a (meth) acrylic acid-based monomer unit; a graft copolymer prepared therefrom, and a resin composition containing the same.

Description

Graft copolymer manufacturing method, graft copolymer, and resin composition comprising the same

The present invention relates to a method for producing a graft copolymer, and specifically, when the rubber polymer in the rubber polymer latex is enlarged using a polymer coagulant, the composition of the polymer coagulant, furthermore, by controlling the hypertrophy environment, coagulation of the graft copolymer latex It relates to a method for preparing a graft copolymer capable of improving the impact resistance and surface properties of a resin composition including the graft copolymer by reducing water generation, a graft copolymer prepared therefrom, and a resin composition comprising the same .

Acrylonitrile-butadiene-styrene (ABS) copolymer is prepared by graft copolymerization of styrene and acrylonitrile to butadiene rubbery polymer. ABS copolymer is superior in impact resistance, chemical resistance, thermal stability, colorability, fatigue resistance, rigidity and workability compared to conventional high-impact polystyrene (HIPS), so it is superior in interior and exterior materials for automobiles, office equipment, and various electrical appliances. ·It is used in parts such as electronic products or toys.

In particular, in order to prepare an ABS copolymer having excellent impact resistance, it is necessary to appropriately control the average particle diameter of the butadiene rubber polymer, and the average particle diameter is usually adjusted in the range of 250 nm to 500 nm. In this regard, when a large-diameter rubbery polymer having an average particle diameter in the range of 250 nm to 500 nm is directly prepared by emulsion polymerization, there is a problem in that the polymerization time is increased and productivity is lowered.

In order to solve this problem, a method for preparing a large-diameter rubbery polymer by preparing a small-diameter rubbery polymer having an average particle diameter of about 100 nm and then enlarging it has been proposed. An example of the hypertrophy method is an acetic acid aggregation method using acetic acid. However, in the case of the acetic acid coagulation method, since a large amount of coagulation due to coagulation occurs, the concentration of rubbery polymer latex has to be lowered in order to reduce coagulation, and thus productivity is inevitably reduced.

In addition, as another example of the hypertrophy method, a polymer aggregation method in which a polymer flocculant is applied may be mentioned. In the case of the polymer agglomeration method, the average particle diameter of the hypertrophic rubbery polymer is determined according to the content of the monomer unit containing an acid group in the polymer flocculant, and as the content of the monomer unit containing an acid group in the polymer flocculant increases, the The average particle diameter of the hypertrophic rubbery polymer increases. However, as the content of the monomer unit containing an acid group in the polymer coagulant increases, the stability of the rubbery polymer latex as well as the graft copolymer latex in the subsequent grafting step for producing the ABS copolymer is reduced, and eventually, the acetic acid aggregation method and Likewise, there is a problem in that a large amount of coagulation occurs in the graft copolymer latex. The coagulated material in the latex generated in this way causes a decrease in the surface properties of the resin composition.

KR10-1991-0002472B1

The present invention has been devised to solve the problems of the prior art, and in preparing a graft copolymer, when the rubber polymer is enlarged using a polymer coagulant, a monomer unit containing an acid group in the polymer coagulant By minimizing the content of rubbery polymer latex as well as reducing the coagulation of the graft copolymer latex, it is possible to improve the surface properties of the resin composition including the graft copolymer to provide a graft copolymer manufacturing method aim to do

In addition, in the present invention, in the preparation of the graft copolymer, when the rubber polymer is enlarged using the polymer coagulant, the content of the monomer unit containing an acid group in the polymer coagulant is minimized while controlling the hypertrophy environment. An object of the present invention is to provide a method for preparing a graft copolymer capable of improving the impact resistance of a resin composition containing the graft copolymer.

In addition, the present invention relates to the impact resistance and surface properties of the resin composition including the graft copolymer, compared to the graft copolymer including the rubbery polymer having an average particle diameter in the same or similar range, by being prepared by the above manufacturing method. An object of the present invention is to provide a graft copolymer that can improve at the same time.

Another object of the present invention is to provide a resin composition having excellent impact resistance and surface properties, including the graft copolymer.

In order to solve the above problems, the present invention is to prepare a hypertrophic rubbery polymer latex containing a hypertrophic rubbery polymer by adding and coagulating a polymeric flocculant latex containing a polymeric flocculant to a rubbery polymer latex containing a rubbery polymer ( S10); And to the hypertrophic rubbery polymer latex prepared in the step (S10), adding an aromatic vinyl-based monomer and a vinyl cyanide-based monomer and performing graft polymerization to prepare a graft copolymer latex containing the graft copolymer (S20) Including, wherein the polymer flocculant comprises two or more kinds of alkyl acrylate-based monomer units and (meth) acrylic acid-based monomer units, the polymer flocculant comprises 0.1 wt% to 1.0 wt% of (meth)acrylic acid-based monomer units It provides a method for preparing the graft copolymer.

Further, in the present invention, in the graft copolymer comprising an enlarged rubbery polymer, the enlarged rubbery polymer includes a polymer coagulant, and the graft copolymer includes an aromatic vinylic monomer unit and a vinylcyanic monomer unit. and wherein the polymer flocculant includes two or more kinds of alkyl acrylate-based monomer units and (meth)acrylic acid-based monomer units, and the polymer flocculant includes 0.1 wt% to 1.0 wt% of (meth)acrylic acid-based monomer units A graft copolymer is provided.

In addition, the present invention provides a resin composition comprising the graft copolymer.

When the graft copolymer is prepared according to the method for preparing the graft copolymer of the present invention, when the rubber polymer is enlarged using the polymer flocculant, the content of the monomer unit containing an acid group in the polymer flocculant is minimized. , rubbery polymer latex, as well as reducing the coagulation of the graft copolymer latex, there is an effect that can improve the surface properties of the resin composition containing the graft copolymer.

In addition, when preparing a graft copolymer according to the method for preparing a graft copolymer of the present invention, when the rubber polymer is enlarged using a polymer flocculant, the content of the monomer unit containing an acid group in the polymer flocculant By controlling the hypertrophy environment while minimizing, the effect of improving the impact resistance of the resin composition containing the graft copolymer compared to the graft copolymer including the rubbery polymer having an average particle diameter in the same or similar range there is.

In addition, the resin composition of the present invention has the effect of having excellent impact resistance and surface properties of the resin composition by including the graft copolymer.

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

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.

In the present invention, the term 'monomer unit' may refer to a component, structure, or material itself derived from a monomer. it could mean

As used herein, the term 'composition' includes reaction products and decomposition products formed from materials of the composition, as well as mixtures of materials comprising the composition.

In the present invention, 'polymerization conversion rate' refers to the degree to which monomers are polymerized by polymerization to form a polymer, and may be calculated through Equation 1 below by collecting a portion of the polymer in the reactor during polymerization.

[Equation 1]

Polymerization conversion (%) = [(total content of inputted monomers-total content of unreacted monomers)/total content of inputted monomers]×100

The present invention provides a method for preparing a graft copolymer.

According to an embodiment of the present invention, the graft copolymer manufacturing method is a rubbery polymer latex containing a rubbery polymer, a polymeric flocculant latex containing a polymeric flocculant is added and agglomerated, and an enlarged rubbery containing an enlarged rubbery polymer Preparing a polymer latex (S10); And to the hypertrophic rubbery polymer latex prepared in the step (S10), adding an aromatic vinyl-based monomer and a vinyl cyanide-based monomer and performing graft polymerization to prepare a graft copolymer latex containing the graft copolymer (S20) Including, wherein the polymer flocculant comprises two or more kinds of alkyl acrylate-based monomer units and (meth) acrylic acid-based monomer units, the polymer flocculant comprises 0.1 wt% to 1.0 wt% of (meth)acrylic acid-based monomer units it could be

According to an embodiment of the present invention, the step (S10) is a step of enlarging the rubbery polymer latex containing the rubbery polymer prepared in advance with a polymer flocculant, and the polymer flocculant latex containing the polymer flocculant is added to the rubbery polymer latex. And it can be carried out by stirring.

According to an embodiment of the present invention, the rubbery polymer may be a conjugated diene-based polymer, and the rubbery polymer latex may be a conjugated diene-based polymer latex including a conjugated diene-based polymer.

According to an embodiment of the present invention, the conjugated diene-based polymer latex including the conjugated diene-based polymer may be prepared by polymerization of a conjugated diene-based monomer. As a specific example, the conjugated diene-based polymer latex may be prepared by emulsion polymerization of a conjugated diene-based monomer to prepare a conjugated diene-based rubbery polymer latex (S1).

According to an embodiment of the present invention, the emulsion polymerization of step (S1) may be carried out in the presence of an emulsifier, and the emulsifier may be a fatty acid-based emulsifier or a fatty acid dimer-based emulsifier.

According to an embodiment of the present invention, the content of the emulsifier in step (S1) is 0.1 parts by weight to 10.0 parts by weight, 0.8 parts by weight to 8.0 parts by weight, or 1.0 parts by weight to 6.0 parts by weight based on 100 parts by weight of the conjugated diene-based monomer. It may be a part by weight, and within this range, it is possible to prepare a rubbery polymer having an average particle diameter suitable for thickening with the polymer flocculant according to the present invention.

According to an embodiment of the present invention, the step (S1) may be carried out by radical polymerization using a peroxide-based, redox, or azo-based initiator that can be used during emulsion polymerization, and the re The dox initiator may be, for example, at least one selected from the group consisting of t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, and cumene hydroperoxide, and in this case, it has an effect of providing a stable polymerization environment. In addition, when the redox initiator is used, ferrous sulfate, dextrose and sodium pyrophosphate may be further included as a redox catalyst.

According to an embodiment of the present invention, the emulsion polymerization of step (S1) may be carried out in an aqueous solvent, and the aqueous solvent may be ion-exchanged water, and thus the conjugated diene-based emulsion polymerization in step (S1) The polymer may be obtained in the form of a latex in which conjugated diene-based polymer particles are colloidally dispersed in an aqueous solvent.

According to an embodiment of the present invention, the conjugated diene-based monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2 It may be at least one member selected from the group consisting of -phenyl-1,3-butadiene, and a more specific example may be 1,3-butadiene.

According to an embodiment of the present invention, the average particle diameter of the rubber polymer prepared in step (S1) and before being enlarged in step (S10) is 50 nm to 150 nm, 70 nm to 130 nm, or 80 nm to 120 nm may be, and while it is easy to enlarge by the polymer coagulant within this range, there is an effect that it is easy to control the average particle size during hypertrophy.

According to an embodiment of the present invention, the rubbery polymer latex containing the rubbery polymer adjusts the pH of the conjugated diene-based rubbery polymer latex prepared in the step (S1) to 7.0 to 9.0, 7.5 to 9.0 or 8.0 to 8.5 It may be prepared by including the step (S2).

According to an embodiment of the present invention, before adjusting the pH in step (S2), that is, the pH of the conjugated diene-based rubbery polymer latex prepared in step (S1) is 10.0 to 12.0, 10.0 to 11.0, or 10.0 to It can be 10.5.

According to an embodiment of the present invention, when the pH of the rubbery polymer latex is adjusted according to step (S2), when the rubbery polymer is enlarged by the polymer flocculant, the content of the acid group-containing monomer unit in the polymer flocculant is minimized. There is an effect that can improve the hypertrophy effect. That is, when the rubber polymer prepared in the step (S2) is enlarged through the step (S10), the content of the monomer unit containing an acid group in the polymer coagulant is minimized to prevent the formation of coagulation, and the thickening effect of the rubber polymer is improved It has the effect of securing impact resistance as well.

According to an embodiment of the present invention, the pH of the rubbery polymer latex in step (S2) may be controlled by CO ₂ bubbling. As a specific example, the CO ₂ bubbling is CO ₂ supplied to the rubbery polymer latex at a flow rate of 100 ml/min to 1,000 ml/min, 300 ml/min to 800 ml/min, or 400 ml/min to 600 ml/min. Thus, it may be carried out for 1 minute to 60 minutes, 1 minute to 30 minutes, or 2 minutes to 10 minutes. As such, when the pH of the rubbery polymer latex is adjusted by CO ₂ bubbling, an additive such as a separate acid is unnecessary, thereby preventing a decrease in the stability of the latex and securing the stability of the rubbery polymer.

According to an embodiment of the present invention, the polymer flocculant latex including the polymer flocculant added to the rubber polymer latex in step (S10) is prepared by polymerization of two or more kinds of alkyl acrylate-based monomers and (meth)acrylic acid-based monomers it may have been As a specific example, the polymer coagulant latex may be prepared by emulsion polymerization of two or more kinds of alkyl acrylate-based monomers and (meth)acrylic acid-based monomers (S3).

According to an embodiment of the present invention, the emulsion polymerization in step (S3) may be carried out in the presence of an emulsifier, and the emulsifier may be a sulfonic acid-based emulsifier, and a specific example may be sodium dodecylbenzenesulfonate.

According to an embodiment of the present invention, the content of the emulsifier in step (S3) is 0.001 parts by weight to 4.000 parts by weight, 0.005 parts by weight to 2.000 parts by weight, or 0.01 parts by weight to 100 parts by weight of all monomers of the polymer flocculant. It may be 1.00 parts by weight, and within this range, it is possible to prepare a polymer coagulant having an average particle diameter suitable for use as a polymer coagulant according to the present invention.

According to an embodiment of the present invention, step (S3) may be carried out by radical polymerization using a radical initiator that can be used during emulsion polymerization, and the radical initiator may be, for example, potassium persulfate.

According to an embodiment of the present invention, the emulsion polymerization of step (S3) may be carried out in an aqueous solvent, and the aqueous solvent may be ion-exchanged water. The polymer flocculant particles may be obtained in the form of a latex colloidally dispersed in an aqueous solvent.

According to an embodiment of the present invention, the polymer coagulant prepared by the step (S3) is 0.1 wt% to 1.0 wt%, 0.3 wt% to 0.8 wt% of (meth)acrylic acid-based monomer units (meth)acrylic acid-based monomer units , or 0.4 wt% to 0.6 wt%, it is possible to maximize the aggregation ability of the rubbery polymer within this range, and at the same time improve the mechanical properties of the resin composition including the graft copolymer and surface properties has the effect of improving Here, the content of the (meth)acrylic acid-based monomer unit may be derived from the content of the (meth)acrylic acid-based monomer added in step (S3), and as a specific example, the (meth)acrylic acid-based monomer added in step (S3). It may be the same as the content.

According to an embodiment of the present invention, the (meth)acrylic acid-based monomer may be methacrylic acid or acrylic acid, for example, methacrylic acid.

According to an embodiment of the present invention, the polymer coagulant prepared in step (S3) may include two or more types of alkyl acrylate-based monomer units in addition to the (meth)acrylic acid-based monomer unit. As a specific example, the polymer coagulant prepared by the step (S3) is 99.0 wt% to 99.9 wt%, 99.2 wt% to 99.7 wt%, or 99.4 wt% to 99.6 wt% of two or more alkyl (meth)acrylate-based monomer units %, it is possible to maximize the aggregation ability of the rubbery polymer within this range, and has the effect of improving the mechanical properties of the resin composition including the graft copolymer. Here, the content of the two or more kinds of alkyl (meth) acrylate-based monomer units may be derived from the content of the two or more kinds of alkyl (meth) acrylate-based monomers added in step (S3), as a specific example, (S3) It may be the same as the content of two or more kinds of alkyl (meth)acrylate-based monomers added in the step.

According to an embodiment of the present invention, the two or more kinds of alkyl (meth) acrylate-based monomers may be alkyl (meth) acrylate-based monomers having 1 to 10 carbon atoms, or 1 to 4 carbon atoms, respectively, and specifically, methyl It may be at least two selected from the group consisting of methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate and n-butyl acrylate, and more Specific examples may be methyl acrylate and ethyl acrylate. That is, the two or more types of alkyl acrylate-based monomer units may include a methyl acrylate monomer unit and an ethyl acrylate monomer unit. In this case, even if the content of the (meth)acrylic acid-based monomer unit that is the acid group-containing monomer unit in the polymer coagulant is minimized, methyl acrylate as one kind of alkyl (meth)acrylate-based monomer unit as the alkyl (meth)acrylate-based monomer unit Compared to the case of including only the monomer unit or the ethyl acrylate monomer unit, there is an effect of further improving mechanical properties, particularly, impact resistance.

According to an embodiment of the present invention, the polymer coagulant is 10.0 wt% to 89.9 wt% of a methyl acrylate monomer unit, 10.0 wt% to 89.9 wt% of an ethyl acrylate monomer unit, and 0.1 wt% to 1.0 wt% of a methacrylic acid monomer unit % comprising a terpolymer.

According to an embodiment of the present invention, the average particle diameter of the polymer coagulant prepared in step (S3) may be 50 nm to 150 nm, 70 nm to 130 nm, or 80 nm to 120 nm, and within this range, the polymer While it is easy to enlarge the rubbery polymer from the coagulant, there is an effect that it is easy to control the average particle diameter of the rubbery polymer during the thickening.

According to an embodiment of the present invention, the polymer coagulant latex is 1.0 parts by weight to 5.0 parts by weight (based on solids), 1.0 parts by weight to 3.0 parts by weight (based on solids) with respect to 100 parts by weight (based on solids) of the rubbery polymer latex ), or 1.0 parts by weight to 2.5 parts by weight (based on solid content), the amount of the polymer flocculant used within this range is minimized to improve the productivity of the graft copolymer, while the resin containing the graft copolymer There is an effect of securing the mechanical properties and surface properties of the composition.

According to an embodiment of the present invention, the step (S10) may be carried out by adding a polymer flocculant latex containing a polymer flocculant to the rubbery polymer latex and stirring, and the stirring is 30 ℃ to 70 ℃, or 40 ℃ to It may be carried out at a temperature of 60 ℃ 100 rpm to 1,000 rpm, 200 rpm to 700 rpm, or a stirring speed of 300 rpm to 500 rpm. In this way, when the polymer flocculant latex containing the polymer coagulant is added to the rubber polymer latex and stirred, there is an effect that the rubber polymer is uniformly coagulated by the polymer coagulant.

According to an embodiment of the present invention, the average particle diameter of the rubbery polymer enlarged in step (S10) may be 300 nm to 380 nm, 320 nm to 350 nm, or 330 nm to 340 nm, within this range, the graft It is possible to maximize mechanical properties, particularly impact resistance, while preventing a decrease in processability of the resin composition including the copolymer, and there is an effect of improving surface properties.

According to an embodiment of the present invention, in the step (S20), an aromatic vinyl-based monomer and a vinyl cyanide-based monomer are graft polymerized to the enlarged rubbery polymer prepared in the step (S10) to prepare a graft copolymer. It may be a step to

According to an embodiment of the present invention, the graft polymerization in step (S20) may be carried out by graft emulsion polymerization. In addition, the graft polymerization in step (S20) may be carried out on the hypertrophic rubbery polymer latex prepared in step (S10).

According to an embodiment of the present invention, the step (S20) may be carried out by radical polymerization using a peroxide-based, redox, or azo-based initiator that can be used during graft emulsion polymerization, The redox initiator may be, for example, at least one selected from the group consisting of t-butyl hydroperoxide, diisopropylbenzene hydroperoxide and cumene hydroperoxide, and in this case, it has an effect of providing a stable polymerization environment. In addition, when the redox initiator is used, ferrous sulfate, dextrose and sodium pyrophosphate may be further included as a redox catalyst.

According to an embodiment of the present invention, the graft emulsion polymerization of step (S20) may be carried out in an aqueous solvent, and the aqueous solvent may be ion-exchanged water, and thus the graft polymerization in step (S20) may be performed. The graft copolymer may be obtained in the form of a latex in which graft copolymer particles are colloidally dispersed in an aqueous solvent.

According to an embodiment of the present invention, the aromatic vinyl-based monomer is styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- It may be at least one selected from the group consisting of (p-methylphenyl)styrene and 1-vinyl-5-hexylnaphthalene, and a specific example may be styrene.

According to an embodiment of the present invention, the vinyl cyan-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, and , a specific example may be acrylonitrile.

According to an embodiment of the present invention, the content of the hypertrophic rubbery polymer latex input in the step (S20) is, with respect to the total content of the hypertrophic rubbery polymer latex (based on the solid content), the aromatic vinyl-based monomer and the vinyl cyan-based monomer, the solid content As a basis, it may be 40 wt% to 90 wt%, 50 wt% to 80 wt%, or 50 wt% to 70 wt%, and there is an effect of securing the mechanical properties of the graft copolymer within this range .

According to an embodiment of the present invention, the content of the aromatic vinyl-based monomer input in the step (S20) is 5 weight based on the total content of the hypertrophic rubbery polymer latex (based on solid content), the aromatic vinyl-based monomer and the vinyl cyan-based monomer % to 50 wt%, 15 wt% to 45 wt%, or 25 wt% to 40 wt%, while ensuring mechanical properties of the graft copolymer within this range, the amount of the graft copolymer in the resin composition It has the effect of improving dispersibility.

According to an embodiment of the present invention, the content of the vinyl cyan-based monomer input in the step (S20) is 1 weight based on the total content of the hypertrophic rubbery polymer latex (based on the solid content), the aromatic vinyl-based monomer and the vinyl cyan-based monomer % to 20 wt%, 3 wt% to 15 wt%, or 5 wt% to 10 wt%, while ensuring mechanical properties of the graft copolymer within this range, the amount of the graft copolymer in the resin composition It has the effect of improving dispersibility.

According to an embodiment of the present invention, the average particle diameter of the graft copolymer prepared in step (S20) is 100 nm to 350 nm, 120 nm to 330 nm, 130 nm to 320 nm, or 270 nm to 320 nm. In this range, there is an effect of maximizing mechanical properties, particularly impact resistance, while preventing a decrease in the workability of the resin composition including the graft copolymer within this range.

According to an embodiment of the present invention, the coagulation content of the graft copolymer latex prepared in step (S20) is 500 ppm or less, 450 ppm or less, or It may be 400 ppm or less, and within this range, the protrusion properties of the resin composition are excellent, the surface gloss is excellent, and the surface properties are excellent.

In addition, the present invention provides a graft copolymer prepared according to the method for preparing the graft copolymer.

According to an embodiment of the present invention, the graft copolymer includes an enlarged rubbery polymer, the hypertrophic rubbery polymer includes a polymer coagulant, and the graft copolymer includes an aromatic vinyl-based monomer unit and a vinyl cyanide-based polymer. Including a monomer unit, the polymer flocculant includes at least two kinds of alkyl acrylate monomer units and (meth) acrylic acid monomer units, and the polymer flocculant contains 0.1 wt % to 1.0 wt % of (meth) acrylic acid monomer units. may include.

According to an embodiment of the present invention, the polymer coagulant, the enlarged rubbery polymer and the graft copolymer may be the polymer flocculant, the enlarged rubbery polymer and the graft copolymer described above in the method for preparing the graft copolymer, and aromatic The vinyl-based monomer unit and the vinyl cyan-based monomer unit may refer to a repeating unit formed by participating in the graft polymerization reaction of the aromatic vinyl-based monomer and the vinyl cyan-based monomer described in the above-described method for preparing the graft copolymer.

According to an embodiment of the present invention, the content of each of the polymer coagulant, the enlarged rubbery polymer, the aromatic vinyl-based monomer unit and the vinyl cyan-based monomer unit may be the same as the content of each component added during the preparation of the graft copolymer. there is.

In addition, the present invention provides a resin composition comprising the graft copolymer.

According to an embodiment of the present invention, the resin composition may include the graft copolymer and the styrenic copolymer. The styrenic copolymer may be a non-graft copolymer including an aromatic vinyl-based monomer unit, and as a specific example, may be a copolymer including an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit. Here, the styrenic copolymer may be a matrix resin that is kneaded with the graft copolymer in the resin composition to form a matrix.

According to one embodiment of the present invention, the aromatic vinyl-based monomer forming the aromatic vinyl-based monomer unit of the styrenic copolymer is styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, It may be at least one selected from the group consisting of 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and a specific example may be styrene.

According to an embodiment of the present invention, the vinyl cyan-based monomer forming the vinyl cyan-based monomer unit of the styrenic copolymer is acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile and α-chloro It may be at least one selected from the group consisting of acrylonitrile, and a specific example may be acrylonitrile.

According to an embodiment of the present invention, the resin composition comprises 10 wt% to 40 wt%, 15 wt% to 35 wt%, or 20 wt% to 25 wt% of the graft copolymer; and 60 wt% to 90 wt%, 65 wt% to 85 wt%, or 75 wt% to 80 wt% of a copolymer comprising an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit, within this range There is an effect of maximizing mechanical properties, particularly impact resistance, while preventing deterioration of the processability of the resin composition including the graft copolymer in the interior.

According to an embodiment of the present invention, the resin composition has a melt index (220 ℃, 10 kg) measured according to ASTM D1238 of 17.0 g/10 min or more, 21.0 g/10 min or more, 17.0 g/10 min to 22.0 It may be g/10 min, or 21.0 g/10 min to 22.0 g/10 min, and within this range, there is an effect of sufficiently securing the processability of the resin composition including the graft copolymer.

According to an embodiment of the present invention, the resin composition has an impact strength of 15.0 kgf·m/m or more, 27.0 kgf·m/m measured at 1/4 inch thickness according to ASTM D256. or more, 15.0 kgf m/m to 31.0 kgf m/m, or 27.0 kgf m/m to 31.0 It may be kgf·m/m, and within this range, there is an effect of sufficiently securing the impact resistance of the resin composition including the graft copolymer.

According to an embodiment of the present invention, the resin composition may have a surface gloss of 95.0 or more, 98.0 to 110.0, or 98.0 to 105.0, measured at 45 ° according to ASTM D2457, and a graft copolymer within this range There is an effect that can sufficiently secure the surface properties of the resin composition containing.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

production example

Preparation Example 1

Prepolymerization by mixing 79.5 parts by weight of ethyl acrylate (EA), 20 parts by weight of methyl acrylate (MA), 0.5 parts by weight of methacrylic acid (MAA), 0.5 parts by weight of sodium dodecylbenzenesulfonate and 40 parts by weight of ion-exchanged water A solution was prepared.

After raising the internal temperature of the nitrogen-substituted polymerization reactor to 80° C., the pre-polymerization solution and 0.5 parts by weight of potassium persulfate were each continuously introduced at a constant rate for 5 hours while polymerization was carried out to carry out polymerization to ethyl acrylate-methyl acrylate- A methacrylic acid copolymer latex was prepared. The average particle diameter of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer in the prepared ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex was 100 nm.

Preparation 2

Prepolymerization by mixing 59.5 parts by weight of ethyl acrylate (EA), 40 parts by weight of methyl acrylate (MA), 0.5 parts by weight of methacrylic acid (MAA), 0.5 parts by weight of sodium dodecylbenzenesulfonate and 40 parts by weight of ion-exchanged water A solution was prepared.

After raising the internal temperature of the nitrogen-substituted polymerization reactor to 80° C., the pre-polymerization solution and 0.5 parts by weight of potassium persulfate were each continuously introduced at a constant rate for 5 hours while polymerization was carried out to carry out polymerization to ethyl acrylate-methyl acrylate- A methacrylic acid copolymer latex was prepared. The average particle diameter of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer in the prepared ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex was 100 nm.

Preparation 3

Prepolymerization by mixing 39.5 parts by weight of ethyl acrylate (EA), 60 parts by weight of methyl acrylate (MA), 0.5 parts by weight of methacrylic acid (MAA), 0.5 parts by weight of sodium dodecylbenzenesulfonate and 40 parts by weight of ion-exchanged water A solution was prepared.

After raising the internal temperature of the nitrogen-substituted polymerization reactor to 80° C., the pre-polymerization solution and 0.5 parts by weight of potassium persulfate were each continuously introduced at a constant rate for 5 hours while polymerization was carried out to carry out polymerization to ethyl acrylate-methyl acrylate- A methacrylic acid copolymer latex was prepared. The average particle diameter of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer in the prepared ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex was 100 nm.

Preparation 4

Prepolymerization by mixing 19.5 parts by weight of ethyl acrylate (EA), 80 parts by weight of methyl acrylate (MA), 0.5 parts by weight of methacrylic acid (MAA), 0.5 parts by weight of sodium dodecylbenzenesulfonate and 40 parts by weight of ion-exchanged water A solution was prepared.

After raising the internal temperature of the nitrogen-substituted polymerization reactor to 80° C., the pre-polymerization solution and 0.5 parts by weight of potassium persulfate were each continuously introduced at a constant rate for 5 hours while polymerization was carried out to carry out polymerization to ethyl acrylate-methyl acrylate- A methacrylic acid copolymer latex was prepared. The average particle diameter of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer in the prepared ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex was 100 nm.

Comparative Preparation Example 1

A prepolymerization solution was prepared by mixing 95 parts by weight of ethyl acrylate (EA), 5 parts by weight of methacrylic acid (MAA), 0.5 parts by weight of sodium dodecylbenzenesulfonate and 40 parts by weight of ion-exchanged water.

After raising the internal temperature of the nitrogen-substituted polymerization reactor to 80 ° C., the pre-polymerization solution and 0.5 parts by weight of potassium persulfate were each continuously introduced at a constant rate for 5 hours while polymerization was carried out to conduct polymerization in ethyl acrylate-methacrylic acid air. Coalesced latex was prepared. The average particle diameter of the ethyl acrylate-methacrylic acid copolymer in the prepared ethyl acrylate-methacrylic acid copolymer latex was 100 nm.

Comparative Preparation Example 2

A prepolymerization solution was prepared by mixing 95 parts by weight of methyl acrylate (MA), 5 parts by weight of methacrylic acid (MAA), 0.5 parts by weight of sodium dodecylbenzenesulfonate and 40 parts by weight of ion-exchanged water.

After raising the internal temperature of the nitrogen-substituted polymerization reactor to 80° C., the pre-polymerization solution and 0.5 parts by weight of potassium persulfate were each continuously added at a constant rate for 5 hours while polymerization was carried out to conduct methyl acrylate-methacrylic acid air Coalesced latex was prepared. The average particle diameter of the methyl acrylate-methacrylic acid copolymer in the prepared methyl acrylate-methacrylic acid copolymer latex was 100 nm.

Comparative Preparation Example 3

A prepolymerization solution was prepared by mixing 99.5 parts by weight of ethyl acrylate (EA), 0.5 parts by weight of methacrylic acid (MAA), 0.5 parts by weight of sodium dodecylbenzenesulfonate and 40 parts by weight of ion-exchanged water.

After raising the internal temperature of the nitrogen-substituted polymerization reactor to 80 ° C., the pre-polymerization solution and 0.5 parts by weight of potassium persulfate were each continuously introduced at a constant rate for 5 hours while polymerization was carried out to conduct polymerization in ethyl acrylate-methacrylic acid air. Coalesced latex was prepared. The average particle diameter of the ethyl acrylate-methacrylic acid copolymer in the prepared ethyl acrylate-methacrylic acid copolymer latex was 100 nm.

Comparative Preparation Example 4

A prepolymerization solution was prepared by mixing 99.5 parts by weight of methyl acrylate (MA), 0.5 parts by weight of methacrylic acid (MAA), 0.5 parts by weight of sodium dodecylbenzenesulfonate and 40 parts by weight of ion-exchanged water.

After raising the internal temperature of the nitrogen-substituted polymerization reactor to 80° C., the pre-polymerization solution and 0.5 parts by weight of potassium persulfate were each continuously added at a constant rate for 5 hours while polymerization was carried out to conduct methyl acrylate-methacrylic acid air Coalesced latex was prepared. The average particle diameter of the methyl acrylate-methacrylic acid copolymer in the prepared methyl acrylate-methacrylic acid copolymer latex was 100 nm.

Comparative Preparation Example 5

A prepolymerization solution was prepared by mixing 97.0 parts by weight of ethyl acrylate (EA), 3.0 parts by weight of methacrylic acid (MAA), 0.5 parts by weight of sodium dodecylbenzenesulfonate and 40 parts by weight of ion-exchanged water.

After raising the internal temperature of the nitrogen-substituted polymerization reactor to 80 ° C., the pre-polymerization solution and 0.5 parts by weight of potassium persulfate were each continuously introduced at a constant rate for 5 hours while polymerization was carried out to conduct polymerization in ethyl acrylate-methacrylic acid air. Coalesced latex was prepared. The average particle diameter of the ethyl acrylate-methacrylic acid copolymer in the prepared ethyl acrylate-methacrylic acid copolymer latex was 100 nm.

Comparative Preparation Example 6

A prepolymerization solution was prepared by mixing 98.5 parts by weight of ethyl acrylate (EA), 1.5 parts by weight of methacrylic acid (MAA), 0.5 parts by weight of sodium dodecylbenzenesulfonate, and 40 parts by weight of ion-exchanged water.

After raising the internal temperature of the nitrogen-substituted polymerization reactor to 80 ° C., the pre-polymerization solution and 0.5 parts by weight of potassium persulfate were each continuously introduced at a constant rate for 5 hours while polymerization was carried out to conduct polymerization in ethyl acrylate-methacrylic acid air. Coalesced latex was prepared. The average particle diameter of the ethyl acrylate-methacrylic acid copolymer in the prepared ethyl acrylate-methacrylic acid copolymer latex was 100 nm.

Example

Example 1

<Production of rubbery polymer latex>

100 parts by weight of ion-exchanged water, 90 parts by weight of 1,3-butadiene, 3 parts by weight of oleic acid dimer potassium salt, 0.1 parts by weight of t-dodecyl mercaptan, 0.1 parts by weight of K ₂ CO ₃ in a polymerization reactor substituted with nitrogen, t - After adding 0.15 parts by weight of butyl hydroperoxide, it was thoroughly mixed by stirring. Then, after raising the internal temperature of the polymerization reactor to 45° C., 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrophosphate, and 0.0025 parts by weight of ferrous sulfate were all added together, and polymerization was initiated. At a polymerization conversion rate of 35%, 1.0 parts by weight of potassium persulfate was added, and the temperature was raised to 70° C. for polymerization reaction. At a polymerization conversion rate of 65%, 10 parts by weight of 1,3-butadiene was added, followed by a polymerization conversion rate of 93%. At this point, the reaction was terminated to obtain a rubbery polymer latex (average particle diameter: 100 nm, solid content: 40 wt%). The pH of the prepared rubbery polymer latex was 10.5.

<Production of hypertrophic rubbery polymer latex>

Into a reactor equipped with a stirrer, 100 parts by weight (based on solid content) of the prepared rubber polymer latex was added, and while stirring at 50 ° C. at 380 rpm, ethyl acrylate prepared in Preparation Example 1 as a polymer flocculant-methyl acrylate- 1.0 parts by weight of methacrylic acid copolymer latex (based on solid content) was added, and the rubbery polymer was agglomerated for 10 minutes to prepare an enlarged rubbery polymer latex.

<Production of graft copolymer latex>

60 parts by weight of the prepared hypertrophic rubbery polymer latex and 93.9 parts by weight of ion-exchanged water were added to a polymerization reactor substituted with nitrogen, and then thoroughly mixed by stirring at 50°C. Then, 0.12 parts by weight of cumene hydroperoxide, 0.11 parts by weight of dextrose, 0.08 parts by weight of sodium pyrophosphate, and 0.0016 parts by weight of ferrous sulfate were added in a batch, and while the temperature inside the reactor was raised to 70 ° C. for 60 minutes, acrylonitrile 7.5 parts by weight of nitrile, 32.5 parts by weight of styrene, 0.35 parts by weight of t-dodecyl mercaptan, and 0.2 parts by weight of cumene hydroperoxide were continuously added at a constant rate for 3 hours, and the reaction was terminated to prepare a graft copolymer latex.

<Preparation of graft copolymer powder>

To 100 parts by weight of the prepared graft copolymer latex (based on solid content), 2 parts by weight of magnesium sulfate (MgSO ₄ ) was added, and agglomerated at 82 °C. Thereafter, the temperature was raised from 82°C to 98°C, aged for 30 minutes, washed, dehydrated and dried to prepare a graft copolymer powder.

Example 2

In Example 1, when preparing the hypertrophic rubbery polymer latex, instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1, the ethyl acrylate-methyl acrylate prepared in Preparation Example 2- It was carried out in the same manner as in Example 1, except that the methacrylic acid copolymer latex was added in the same amount.

Example 3

In Example 1, when preparing the hypertrophic rubbery polymer latex, the ethyl acrylate-methyl acrylate prepared in Preparation Example 3 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 - It was carried out in the same manner as in Example 1, except that the methacrylic acid copolymer latex was added in the same amount.

Example 4

In Example 1, when preparing the hypertrophic rubbery polymer latex, instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1, the ethyl acrylate-methyl acrylate prepared in Preparation Example 4- It was carried out in the same manner as in Example 1, except that the methacrylic acid copolymer latex was added in the same amount.

Example 5

<Production of rubbery polymer latex>

100 parts by weight of ion-exchanged water, 90 parts by weight of 1,3-butadiene, 3 parts by weight of oleic acid dimer potassium salt, 0.1 parts by weight of t-dodecyl mercaptan, 0.1 parts by weight of K ₂ CO ₃ in a polymerization reactor substituted with nitrogen, t - After adding 0.15 parts by weight of butyl hydroperoxide, it was thoroughly mixed by stirring. Then, after raising the internal temperature of the polymerization reactor to 45° C., 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrophosphate, and 0.0025 parts by weight of ferrous sulfate were all added together, and polymerization was initiated. At a polymerization conversion rate of 35%, 1.0 parts by weight of potassium persulfate was added, and the temperature was raised to 70° C. for polymerization reaction. At a polymerization conversion rate of 65%, 10 parts by weight of 1,3-butadiene was added, followed by a polymerization conversion rate of 93%. At this point, the reaction was terminated to obtain a rubbery polymer latex (average particle diameter: 100 nm, solid content: 40 wt%). The pH of the prepared rubbery polymer latex was 10.5.

<Rubber polymer latex pH adjustment>

Then, CO ₂ gas was supplied to the obtained rubbery polymer latex at a flow rate of 500 ml/min while CO ₂ bubbling was performed for 10 minutes to adjust the pH of the rubbery polymer latex. After CO ₂ bubbling, the pH of the rubbery polymer latex was 8.5.

<Production of hypertrophic rubbery polymer latex>

Into a reactor equipped with a stirrer, 100 parts by weight (based on solid content) of the rubbery polymer latex whose pH was adjusted was added, and while stirring at 50° C. at 380 rpm, ethyl acrylate-methyl acryl prepared in Preparation Example 1 as a polymer coagulant. 1.0 parts by weight of the late-methacrylic acid copolymer latex (based on solid content) was added, and the rubbery polymer was agglomerated for 10 minutes to prepare an enlarged rubbery polymer latex.

<Production of graft copolymer latex>

60 parts by weight of the prepared hypertrophic rubbery polymer latex and 93.9 parts by weight of ion-exchanged water were added to a polymerization reactor substituted with nitrogen, and then stirred at 50° C. to sufficiently mix. Then, 0.12 parts by weight of cumene hydroperoxide, 0.11 parts by weight of dextrose, 0.08 parts by weight of sodium pyrophosphate, and 0.0016 parts by weight of ferrous sulfate were added in a batch, and while the temperature inside the reactor was raised to 70 ° C. for 60 minutes, acrylo 7.5 parts by weight of nitrile, 32.5 parts by weight of styrene, 0.35 parts by weight of t-dodecyl mercaptan, and 0.2 parts by weight of cumene hydroperoxide were continuously added at a constant rate for 3 hours, and the reaction was terminated to prepare a graft copolymer latex.

<Preparation of graft copolymer powder>

To 100 parts by weight of the prepared graft copolymer latex (based on solid content), 2 parts by weight of magnesium sulfate (MgSO ₄ ) was added, and agglomerated at 82 °C. Thereafter, the temperature was raised from 82°C to 98°C, aged for 30 minutes, washed, dehydrated and dried to prepare a graft copolymer powder.

Example 6

In Example 5, when preparing the hypertrophic rubbery polymer latex, instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1, the ethyl acrylate-methyl acrylate prepared in Preparation Example 2- It was carried out in the same manner as in Example 5, except that the methacrylic acid copolymer latex was added in the same amount.

Example 7

In Example 5, when preparing the hypertrophic rubbery polymer latex, instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1, the ethyl acrylate-methyl acrylate prepared in Preparation Example 3- It was carried out in the same manner as in Example 5, except that the methacrylic acid copolymer latex was added in the same amount.

Example 8

In Example 5, when preparing the hypertrophic rubbery polymer latex, the ethyl acrylate-methyl acrylate prepared in Preparation Example 4 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 - It was carried out in the same manner as in Example 5, except that the methacrylic acid copolymer latex was added in the same amount.

Comparative Example 1

In Example 1, when preparing the hypertrophic rubbery polymer latex, ethyl acrylate-methacrylic acid prepared in Comparative Preparation Example 1 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 It was carried out in the same manner as in Example 1, except that the copolymer latex was added in the same amount.

Comparative Example 2

In Example 1, when preparing the hypertrophic rubbery polymer latex, methyl acrylate-methacrylic acid prepared in Comparative Preparation Example 2 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 It was carried out in the same manner as in Example 1, except that the copolymer latex was added in the same amount.

Comparative Example 3

In Example 1, when preparing the hypertrophic rubbery polymer latex, ethyl acrylate-methacrylic acid prepared in Comparative Preparation Example 3 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 It was carried out in the same manner as in Example 1, except that the copolymer latex was added in the same amount.

Comparative Example 4

In Example 1, when preparing the hypertrophic rubbery polymer latex, methyl acrylate-methacrylic acid prepared in Comparative Preparation Example 4 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 It was carried out in the same manner as in Example 1, except that the copolymer latex was added in the same amount.

Comparative Example 5

In Example 1, when preparing the hypertrophic rubbery polymer latex, ethyl acrylate-methacrylic acid prepared in Comparative Preparation Example 5 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 It was carried out in the same manner as in Example 1, except that the copolymer latex was added in the same amount.

Comparative Example 6

In Example 1, when preparing the hypertrophic rubbery polymer latex, ethyl acrylate-methacrylic acid prepared in Comparative Preparation Example 6 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 It was carried out in the same manner as in Example 1, except that the copolymer latex was added in the same amount.

Comparative Example 7

In Example 5, when preparing the hypertrophic rubbery polymer latex, ethyl acrylate-methacrylic acid prepared in Comparative Preparation Example 1 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 It was carried out in the same manner as in Example 5, except that the copolymer latex was added in the same amount.

Comparative Example 8

In Example 5, when preparing the hypertrophic rubbery polymer latex, methyl acrylate-methacrylic acid prepared in Comparative Preparation Example 2 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 It was carried out in the same manner as in Example 5, except that the copolymer latex was added in the same amount.

Comparative Example 9

In Example 5, when preparing the hypertrophic rubbery polymer latex, ethyl acrylate-methacrylic acid prepared in Comparative Preparation Example 3 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 It was carried out in the same manner as in Example 5, except that the copolymer latex was added in the same amount.

Comparative Example 10

In Example 5, when preparing the hypertrophic rubbery polymer latex, methyl acrylate-methacrylic acid prepared in Comparative Preparation Example 4 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 It was carried out in the same manner as in Example 5, except that the copolymer latex was added in the same amount.

Comparative Example 11

In Example 5, when preparing the hypertrophic rubbery polymer latex, ethyl acrylate-methacrylic acid prepared in Comparative Preparation Example 5 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 It was carried out in the same manner as in Example 5, except that the copolymer latex was added in the same amount.

Comparative Example 12

In Example 5, when preparing the hypertrophic rubbery polymer latex, ethyl acrylate-methacrylic acid prepared in Comparative Preparation Example 6 instead of the ethyl acrylate-methyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 It was carried out in the same manner as in Example 5, except that the copolymer latex was added in the same amount.

Experimental example

When preparing the graft copolymer in Examples 1 to 8 and Comparative Examples 1 to 12, with respect to the graft copolymer latex, the average particle diameter of the graft copolymer in the graft copolymer latex was measured by the following method, and the graft By measuring the coagulant content of the copolymer latex, it is shown in Tables 1 to 3 below, together with the type of polymer coagulant and whether the pH of the rubbery polymer latex is adjusted.

In addition, 25 parts by weight of the graft copolymer powder prepared in Examples 1 to 8 and Comparative Examples 1 to 12, 75 parts by weight of a styrene-acrylonitrile copolymer (manufactured by LG Chem, product name 92HR), 1.5 parts by weight of lubricant And 0.15 parts by weight of a heat stabilizer was put into a twin-screw extruder, and the resin composition pellets were prepared by kneading and extruding at 220 °C. During pellet production, the protrusion characteristics of the extruded strain were confirmed by the following method and shown in Tables 1 to 3 below.

In addition, the prepared pellets 220 By injection at ℃, melt index, impact strength, and surface gloss were measured by the following method, and are shown in Tables 1 to 3 below.

* Average particle diameter (nm): The average particle diameter of the particles dispersed in the graft copolymer latex was measured by dynamic light scattering using Nicomp 380 HPL equipment (Nicomp).

* Coagulation content (ppm): After each graft copolymer latex prepared in Examples and Comparative Examples was filtered through a sieve of 100 mesh, dried at 70 ° C. for 10 hours to obtain a coagulated product, and the weight was measured Therefore, it was expressed as the content of the graft copolymer.

* Projection characteristics: Based on the strain 2 m extruded with a diameter of 2 mm, the number of unspecified protrusions was checked and classified as follows.

○: number of projections 0 or 1

△: 2 to 5 projections

X: 6 or more projections

* Melt index (g/10 min): measured under the conditions of 220 °C and 10 kg according to ASTM D1238.

* Impact strength (kgf·m/m): Notched izod impact strength for a 1/4 inch thick specimen was measured by ASTM D256 method, respectively.

* Surface gloss: According to ASTM D2457 method, using a gloss meter (VG-7000, Nippon Denshoku), angle 45 ° surface gloss of the specimen was measured.

division Example One 2 3 4 5 6 7 8 Polymer Flocculant Type Preparation Example 1 Preparation 2 Preparation 3 Preparation 4 Preparation Example 1 Preparation 2 Preparation 3 Preparation 4 Whether to adjust the pH X X X X ○ ○ ○ ○ graft copolymer average particle size (nm) 130 145 155 170 275 295 305 315 coagulum content (ppm) <100 <100 200 250 <100 150 250 400 resin composition protrusion characteristics ○ ○ ○ ○ ○ ○ ○ ○ melt index (g/10 min) 17.5 17.8 18.1 18.1 21.5 21.8 21.9 21.8 impact strength (kgf m/m) 15.7 15.4 16.2 16.2 27.9 29.4 30.1 29.5 surface gloss 110 110 104 105 105 100 99 98

division comparative example One 2 3 4 5 6 Polymer Flocculant Type Comparative Preparation Example 1 Comparative Preparation Example 2 Comparative Preparation Example 3 Comparative Preparation Example 4 Comparative Preparation Example 5 Comparative Preparation Example 6 Whether to adjust the pH X X X X X X graft copolymer average particle size (nm) 320 425 110 180 250 150 coagulum content (ppm) 750 3,500 <100 300 500 150 resin composition protrusion characteristics △ X ○ ○ △ ○ melt index (g/10 min) 20.5 20.3 16.8 18.3 20.8 18.1 impact strength (kgf m/m) 26.4 26.0 14.6 15.8 24.2 15.9 surface gloss 98 93 110 100 99 103

division comparative example 7 8 9 10 11 12 Polymer Flocculant Type Comparative Preparation Example 1 Comparative Preparation Example 2 Comparative Preparation Example 3 Comparative Preparation Example 4 Comparative Preparation Example 5 Comparative Preparation Example 6 Whether to adjust the pH ○ ○ ○ ○ ○ ○ graft copolymer average particle size (nm) 420 510 235 345 340 255 coagulum content (ppm) 1,350 7,000 150 1,200 750 250 resin composition protrusion characteristics △ X ○ ○ △ ○ melt index (g/10 min) 20.8 20.3 21.3 21.0 21.1 20.0 impact strength (kgf m/m) 26.9 24.5 24.1 27.1 24.9 24.5 surface gloss 95 89 103 96 97 99

As shown in Tables 1 to 3, in Examples 1 to 8 prepared by the method for preparing the graft copolymer according to the present invention, when the rubbery polymer was enlarged using the polymer coagulant, an acid group in the polymer coagulant was formed. By minimizing the content of the monomer unit containing It was confirmed that the mechanical properties were improved.

In particular, in the case of Examples 5 to 8, in which the pH of the conjugated diene-based polymer latex was adjusted, while increasing the average particle diameter of the rubber polymer and the graft copolymer compared to Examples 1 to 4, the content of the coagulated product of the graft copolymer latex was reduced. It was confirmed that mechanical properties such as melt index and impact strength were further improved, as well as securing protrusion properties and surface gloss.

On the other hand, in Comparative Examples 1 and 7 in which the ethyl acrylate-methacrylic acid copolymer latex containing the ethyl acrylate-methacrylic acid copolymer containing 5% by weight of the methacrylic acid monomer unit was applied as a polymer coagulant, the implementation Compared to Examples 1 to 4 or 5 to 8, due to the increase in the content of methacrylic acid monomer unit, which is a monomer unit containing an acid group in the polymer coagulant, the average particle diameter of the rubbery polymer and the graft copolymer was further increased, but the It was confirmed that the coagulant content in the coagulant copolymer latex increased, and the protrusion properties as well as the surface gloss decreased.

In addition, in Comparative Examples 2 and 8 in which methyl acrylate-methacrylic acid copolymer latex containing a methyl acrylate-methacrylic acid copolymer containing 5% by weight of a methacrylic acid monomer unit was applied as a polymer coagulant, Due to the increase in the content of the methacrylic acid monomer unit, which is a monomer unit containing an acid group in the polymer coagulant, compared to Examples 1 to 4 or 5 to 8, the average particle diameter of the rubbery polymer and the graft copolymer became larger, It was confirmed that the content of coagulate in the graft copolymer latex increased rapidly, and the surface gloss as well as the protrusion properties were significantly reduced.

In addition, ethyl acrylate-methacrylic comprising an ethyl acrylate-methacrylic acid copolymer containing methacrylic acid monomer units in an amount of 0.5 wt%, but including an ethyl acrylate unit which is one kind of alkyl acrylate-based monomer unit. In Comparative Examples 3 and 9 in which the acid copolymer latex was applied as a polymer coagulant, the hypertrophy efficiency of the average particle diameter of the rubber polymer and the graft copolymer was lowered compared to Examples 1 to 4 or 5 to 8, and accordingly, the melt index and impact It was confirmed that the improvement of mechanical properties such as strength was very insignificant.

In addition, methyl acrylate-methacrylic comprising a methyl acrylate-methacrylic acid copolymer containing a methacrylic acid monomer unit in an amount of 0.5 wt%, but including a methyl acrylate unit, which is one kind of alkyl acrylate-based monomer unit. In Comparative Examples 4 and 10 in which the acid copolymer latex was applied as a polymer coagulant, the average particle diameter of the rubber polymer and the graft copolymer was increased compared to Examples 1 to 4 or 5 to 8, but, accordingly, coagulation in the graft copolymer latex It was confirmed that the water content increased, and thus the surface gloss was also decreased.

In addition, through Comparative Examples 5 and 11, the ethyl acrylate-methacrylic acid copolymer latex comprising the ethyl acrylate-methacrylic acid copolymer of Comparative Preparation Example 5 in which the methacrylic acid monomer unit was adjusted to 3.0 wt% was prepared As a result of application as a polymer coagulant, the content of methacrylic acid monomer unit, which is a monomer unit containing an acid group in the polymer coagulant, is still high, and as in Comparative Examples 1 and 7, the average of the rubber polymer and the graft copolymer Although the particle size was increased, it was confirmed that the coagulant content in the graft copolymer latex was increased, and the protrusion properties as well as the surface gloss were decreased.

In addition, through Comparative Examples 6 and 12, the ethyl acrylate-methacrylic acid copolymer latex comprising the ethyl acrylate-methacrylic acid copolymer of Comparative Preparation Example 6 in which the methacrylic acid monomer unit was adjusted to 1.5 wt% was prepared. As a result of application as a polymer coagulant, the content of methacrylic acid monomer unit, a monomer unit containing an acid group in the polymer coagulant, was reduced compared to Comparative Examples 1, 5, 7 and 11, and coagulation in the graft copolymer latex Although the water content was reduced, it was confirmed that mechanical properties such as melt index and impact strength and surface gloss of the resin composition including the graft copolymer could not be improved at the same time to a sufficient level.

From these results, when a graft copolymer is prepared by the method for preparing a graft copolymer according to the present invention, when the rubbery polymer is enlarged using a polymer flocculant, a monomer unit containing an acid group in the polymer flocculant By minimizing the content of rubbery polymer latex, as well as reducing the coagulation of the graft copolymer latex, it was confirmed that the surface properties of the resin composition including the graft copolymer can be improved.

In addition, the graft copolymer prepared according to the method for preparing the graft copolymer of the present invention minimizes the content of monomer units containing an acid group in the polymer flocculant when the rubber polymer is enlarged using the polymer flocculant. However, by controlling the hypertrophy environment, it was confirmed that the impact resistance of the resin composition including the graft copolymer was improved as compared to the graft copolymer including the rubbery polymer having an average particle diameter in the same or similar range.

Claims (12)

A step (S10) of preparing an enlarged rubbery polymer latex containing an enlarged rubbery polymer by adding and coagulating a polymeric flocculant latex containing a polymeric flocculant to the rubbery polymer latex containing the rubbery polymer (S10); and
In the hypertrophic rubbery polymer latex prepared in step (S10), an aromatic vinyl-based monomer and a vinyl cyan-based monomer are added and graft-polymerized to prepare a graft copolymer latex containing the graft copolymer (S20) including,
The polymer coagulant comprises two or more kinds of alkyl acrylate-based monomer units and (meth)acrylic acid-based monomer units,
The polymer coagulant is a (meth) acrylic acid-based monomer unit is a method for producing a graft copolymer comprising 0.1 wt% to 1.0 wt%. According to claim 1,
The rubbery polymer is a conjugated diene-based polymer graft copolymer manufacturing method. According to claim 1,
The average particle diameter of the rubbery polymer is 50 nm to 150 nm graft copolymer manufacturing method. According to claim 1,
The rubbery polymer latex comprising the rubbery polymer,
Preparing a conjugated diene-based rubbery polymer latex by emulsion polymerization of a conjugated diene-based monomer (S1); and
A method for preparing a graft copolymer prepared including the step (S2) of adjusting the pH of the conjugated diene-based rubbery polymer latex to 7.0 to 9.0. 5. The method of claim 4,
In the step (S2), the pH of the rubbery polymer latex is CO ₂ A method for producing a graft copolymer that is controlled by bubbling. 6. The method of claim 5,
The CO ₂ bubbling is a graft copolymer manufacturing method that is carried out for 1 minute to 60 minutes by supplying CO ₂ to the rubbery polymer latex at a flow rate of 100 ml/min to 1,000 ml/min. According to claim 1,
The two or more types of alkyl acrylate-based monomer units include a methyl acrylate monomer unit and an ethyl acrylate monomer unit. According to claim 1,
The polymer flocculant comprises 10.0 wt% to 89.9 wt% of methyl acrylate monomer units, 10.0 wt% to 89.9 wt% of ethyl acrylate monomer units, and 0.1 wt% to 1.0 wt% of methacrylic acid monomer units. How to make a composite. According to claim 1,
The polymer flocculant latex is a graft copolymer manufacturing method that is added in an amount of 1 to 5 parts by weight (based on solids) based on 100 parts by weight (based on solids) of the rubbery polymer latex. A graft copolymer comprising an enlarged rubbery polymer, the graft copolymer comprising:
The hypertrophic rubbery polymer comprises a polymeric flocculant,
The graft copolymer includes an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit,
The polymer coagulant comprises two or more kinds of alkyl acrylate-based monomer units and (meth)acrylic acid-based monomer units,
The polymer coagulant is a (meth) acrylic acid-based monomer unit comprising 0.1% by weight to 1.0% by weight of the graft copolymer. A resin composition comprising the graft copolymer according to claim 10 . 12. The method of claim 11,
The resin composition comprises 10 wt% to 40 wt% of the graft copolymer; and 60 wt% to 90 wt% of a copolymer including an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit.