KR20220040211A - 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 which can provide improved surface energy to a resin composition including the graft copolymer with no use of functional additives. The present invention also relates to a graft copolymer obtained from the method and a resin composition including the graft copolymer. The method according to the present invention includes the steps of: (S10) introducing a polymer agglomerating agent latex containing a polymer agglomerating agent to a rubbery polymer latex containing a rubbery polymer to perform agglomeration, thereby providing an enlarged rubber polymer latex containing an enlarged rubber polymer; and (S20) introducing an aromatic vinyl-based monomer and vinyl cyanide-based monomer to the enlarged rubbery polymer latex obtained from step (S10) and carrying out graft polymerization to prepare a graft copolymer latex containing a graft copolymer, wherein the polymer agglomerating agent includes 5-7 wt% of a (meth)acrylic acid-based monomer unit, and the enlarged rubber polymer obtained from step (S10) has an average particle diameter of 300-380 nm.

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, by using a polymer coagulant to enlarge the rubber polymer in the rubber polymer latex, a graft copolymer capable of improving the paintability of a resin composition containing the graft copolymer It relates to a method for manufacturing a coalescence, 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.

Among them, the ABS copolymer for coating the surface needs to improve the surface energy of the resin composition including the ABS copolymer in order to easily form a coating layer during the coating process. However, in a typical painting process, it is necessary to perform primer coating in order to improve the surface energy of the resin composition. Such primer coating is expensive, requires a separate facility for primer coating, and takes a long time. there is

In order to solve this problem, a method has been proposed to increase the surface energy of the resin composition itself including the ABS copolymer than the surface energy of a paint such as a paint to be applied at the time of painting. Here, the surface energy of the resin composition containing the general ABS copolymer is usually less than 38 dyne/cm, but the surface energy for exhibiting good paintability is required to be 40 dyne/cm or more.

In this regard, Korean Patent Application Laid-Open No. 10-2019-0112138 discloses that in order to increase the surface energy of the resin composition itself including the ABS copolymer, diester of sebacic acid and glycidyl epoxy during compounding of the resin composition It is disclosed to improve the surface energy of the resin composition itself including the ABS copolymer by mixing a mixture of alkoxysilane and/or a copolymer of methyl acrylate and ethylene (Dow's Elvaloy ^TM AC 1330) as a functional additive. However, the use of such a functional additive has a problem of causing a decrease in other physical properties such as impact resistance and appearance properties in the resin composition, and since the functional additive must be separately provided, it causes an increase in manufacturing cost.

KR10-2019-0112138A

The present invention has been devised to solve the problems of the prior art, and it is to provide a method for producing a graft copolymer capable of improving the surface energy of the resin composition itself including the graft copolymer without the use of a functional additive. The purpose.

In addition, the present invention is prepared by the above manufacturing method, as compared to a graft copolymer containing a rubbery polymer having an average particle diameter in the same or similar range, without the use of a functional additive, the resin composition containing the graft copolymer An object of the present invention is to provide a graft copolymer capable of improving its own surface energy and having excellent impact resistance and appearance characteristics.

In addition, an object of the present invention is to provide a resin composition having improved surface energy of the resin composition itself, including the graft copolymer, and excellent impact resistance and appearance characteristics.

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 coagulant comprises 5 wt% to 7 wt% of (meth)acrylic acid-based monomer units, and the average particle diameter of the enlarged rubbery polymer prepared in step (S10) is 300 nm to 380 nm graft A method for preparing a copolymer is provided.

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, the polymer coagulant includes a (meth)acrylic acid-based monomer unit, and provides a graft copolymer having an average particle diameter of the enlarged rubbery polymer of 300 nm to 380 nm.

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, the surface energy of the resin composition itself including the graft copolymer is improved without the use of a functional additive to improve the surface energy of the resin composition. There is an effect that can make it happen.

In addition, when the graft copolymer is prepared according to the method for preparing the graft copolymer of the present invention, the graft copolymer is included as compared to the graft copolymer containing the rubbery polymer having an average particle diameter in the same or similar range. There is an effect of improving the impact resistance and appearance characteristics of the resin composition.

In addition, the resin composition of the present invention has the effect of improving the surface energy of the resin composition itself by including the graft copolymer, and having excellent impact resistance and appearance characteristics.

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, the polymer coagulant comprises 5% to 7% by weight of (meth)acrylic acid-based monomer units, and the average particle diameter of the hypertrophic rubbery polymer prepared in step (S10) is 300 nm to 380 nm. there is.

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 through emulsion polymerization of a conjugated diene-based monomer (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 polymer flocculant latex including the polymer flocculant added to the rubbery polymer latex in step (S10) may be prepared by polymerization of comonomers including (meth)acrylic acid monomers. As a specific example, the polymer coagulant latex may be prepared by emulsion polymerization of comonomers including (meth)acrylic acid monomers (S2).

According to an embodiment of the present invention, the emulsion polymerization in step (S2) 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 (S2) 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 (S2) 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 (S2) 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 (S2) may include 5 wt% to 7 wt%, or 6 wt% to 7 wt% of (meth)acrylic acid-based monomer units, , within this range, the aggregation ability of the rubbery polymer can be maximized, and the mechanical properties of the resin composition including the graft copolymer can be improved, and the surface energy can be improved. Here, the content of the (meth)acrylic acid-based monomer unit may be derived from the content of the (meth)acrylic acid-based monomer input in step (S2), and as a specific example, the (meth)acrylic acid-based monomer input in step (S2). 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 by the step (S2) may include a comonomer unit in addition to the (meth)acrylic acid-based monomer unit, and in this case, the comonomer unit is an alkyl ( It may be a meth)acrylate-based monomer unit. As a specific example, the polymer coagulant prepared by the step (S2) may include 93 wt% to 95 wt%, or 93 wt% to 94 wt% of an alkyl (meth)acrylate-based monomer unit, within this range It is possible to exert the maximum ability of the agglomeration of the rubbery polymer, and there is an effect that can improve the mechanical properties of the resin composition including the graft copolymer. Here, the content of the alkyl (meth) acrylate-based monomer unit may be derived from the content of the alkyl (meth) acrylate-based monomer added in step (S2), and specifically, the content of the alkyl (meth) acrylate-based monomer added in step (S2) ) may be the same as the content of the acrylate-based monomer.

According to an embodiment of the present invention, the alkyl (meth) acrylate-based monomer may be an alkyl (meth) acrylate-based monomer having 1 to 10 carbon atoms, or 1 to 4 carbon atoms, and specifically, methyl methacrylate, It may be at least one selected from the group consisting of ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate and n-butyl acrylate, and more specifically, ethyl acrylic It can be rate.

According to an embodiment of the present invention, the polymer coagulant is 93 wt% to 95 wt% of an alkyl (meth)acrylate-based monomer unit, or 93 wt% to 94 wt% and a (meth)acrylic acid-based monomer unit 5 wt% to 7% by weight, or 6% to 7% by weight of the binary copolymer.

According to an embodiment of the present invention, the polymer coagulant latex is 1 part by weight to 5 parts by weight (based on solid content), 1 part by weight to 3 parts by weight (based on solid content) with respect to 100 parts by weight (based on solid content) of the rubbery polymer latex ), 1.5 parts by weight to 2.5 parts by weight (based on solids), or 1.8 parts by weight to 2.0 parts by weight (based on solids), within this range, the amount of the polymer flocculant is minimized to minimize the productivity of the graft copolymer While improving the mechanical properties and surface energy of the resin composition including the graft copolymer, there is an effect that can be secured.

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 energy.

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.

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. A monomer unit may be included, and the polymer coagulant may include a (meth)acrylic acid-based monomer unit, and the enlarged rubbery polymer may have an average particle diameter of 300 nm to 380 nm.

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. As a specific example, the content of the polymer coagulant is 0.15 parts by weight to 0.75 parts by weight, 0.15 parts by weight to 0.45 parts by weight, 0.225 parts by weight to 0.375 parts by weight, based on 100 parts by weight of the rubbery polymer, the aromatic vinyl-based monomer unit and the vinyl cyan-based monomer unit. It may be in an amount of parts by weight, or 0.27 parts by weight to 0.30 parts by weight, and within this range, the surface energy of the resin composition including the graft copolymer is improved without functional additives.

According to one embodiment of the present invention, the graft copolymer may include a rubbery polymer that is not enlarged together with the rubbery polymer enlarged by the polymer flocculant. As a specific example, the non-enlarged rubbery polymer may be the same as the non-enlarged rubbery polymer described above, and the average particle diameter of the non-enlarged rubbery polymer is 50 nm to 150 nm, 70 nm to 130 nm, or 80 nm to 120 nm may be nm. As such, when the hypertrophic rubbery polymer and the non-enlarged rubbery polymer are included at the same time, there is an excellent effect in the balance of mechanical properties of the resin composition including the graft copolymer.

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 30 wt% of the graft copolymer; and 60 wt% to 90 wt%, 65 wt% to 85 wt%, or 70 wt% to 80 wt% of a copolymer comprising an aromatic vinylic monomer unit and a vinylcyanic monomer unit, in 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 ° C., 10 kg) measured according to ASTM D1238 of 20.0 g/10 min or more, 21.0 g/10 min or more, or 21.1 g/10 min to It may be 21.2 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 30.0 kgf·m/m or more, 32.0 kgf·m/m measured at 1/4 inch thickness according to ASTM D256. above, or 32.0 kgf m/m to 33.0 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 has an impact strength of 34.0 kgf·m/m or more, 35.0 kgf·m/m measured at 1/8 inch thickness according to ASTM D256. above, or 35.2 kgf m/m to 36.0 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 energy of 40 dyne/cm or more, 41 dyne/cm or more, or 41 dyne/cm to 42 dyne/cm measured by the dyne pen test, Within this range, there is an effect that can sufficiently ensure the paintability of the resin composition containing the graft copolymer.

According to an embodiment of the present invention, the resin composition may have a surface gloss of 95.0 or more, 97.0 or more, or 97.8 to 98.0 measured at 45 ° according to ASTM D523, and includes a graft copolymer within this range There is an effect that can sufficiently ensure the appearance characteristics of the resin composition.

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

A prepolymerization solution was prepared by mixing 93 parts by weight of ethyl acrylate, 7 parts by weight of methacrylic acid, 0.4 parts by weight of potassium persulfate, 0.5 parts by weight of sodium dodecylbenzenesulfonate and 98 parts by weight of ion-exchanged water.

After raising the internal temperature of the nitrogen-substituted polymerization reactor to 80° C., polymerization was performed while continuously introducing the pre-polymerization solution at a constant rate for 5 hours to prepare an ethyl acrylate-methacrylic acid copolymer latex.

Preparation 2

96 parts by weight of ethyl acrylate, 4 parts by weight of methacrylic acid, 0.4 parts by weight of potassium persulfate, 0.5 parts by weight of sodium dodecylbenzenesulfonate and 98 parts by weight of ion-exchanged water were mixed to prepare a prepolymerization solution.

After raising the internal temperature of the nitrogen-substituted polymerization reactor to 80° C., polymerization was performed while continuously introducing the pre-polymerization solution at a constant rate for 5 hours to prepare an ethyl acrylate-methacrylic acid copolymer latex.

Preparation 3

A prepolymerization solution was prepared by mixing 92 parts by weight of ethyl acrylate, 8 parts by weight of methacrylic acid, 0.4 parts by weight of potassium persulfate, 0.5 parts by weight of sodium dodecylbenzenesulfonate and 98 parts by weight of ion-exchanged water.

After raising the internal temperature of the nitrogen-substituted polymerization reactor to 80° C., polymerization was performed while continuously introducing the pre-polymerization solution at a constant rate for 5 hours to prepare an ethyl acrylate-methacrylic acid copolymer latex.

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: 110 nm, solid content: 40 wt%).

<Production of hypertrophic rubbery polymer latex>

Into a reactor equipped with a stirrer, 100 parts by weight (based on solid content) of the prepared rubbery polymer latex was added, and while stirring at 50° C. at 380 rpm, the ethyl acrylate-methacrylic acid air prepared in Preparation Example 1 as a polymer flocculant 1.8 parts by weight of the coalescing latex (based on solid content) was added, and the rubbery polymer was agglomerated for 15 minutes to prepare an enlarged rubbery polymer latex.

At this time, the average particle diameter of the prepared enlarged rubbery polymer particles was 330 nm.

<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, 2 parts by weight of magnesium sulfate (MgSO ₄ ) was added, and agglomerated at 82 °C. Thereafter, it was aged at 82° C. for 94 hours, washed, dehydrated and dried to prepare a graft copolymer powder.

<Preparation of resin composition>

25 parts by weight of the prepared graft copolymer powder, 75 parts by weight of a styrene-acrylonitrile copolymer (manufactured by LG Chem, product name 92HR), 1.5 parts by weight of a lubricant, and 0.15 parts by weight of a heat stabilizer are put into a twin-screw extruder, and at 220° C. The resin composition pellets were prepared by kneading and extruding.

Example 2

In Example 1, when preparing the hypertrophic rubbery polymer latex, the ethyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 was added in 2.0 parts by weight (based on solids) instead of 1.8 parts by weight (based on solids) Except it was carried out in the same manner as in Example 1. At this time, the average particle diameter of the prepared enlarged rubbery polymer particles was 340 nm.

Example 3

In Example 2, when preparing the resin composition, 28 parts by weight of the graft copolymer powder was added instead of 25 parts by weight, and 72 parts by weight instead of 75 parts by weight of the styrene-acrylonitrile copolymer (manufactured by LG Chem, product name 92HR) was added. Except for the above, it was carried out in the same manner as in Example 2.

Comparative Example 1

In Example 1, when preparing the hypertrophic rubbery polymer latex, the ethyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 2 instead of the ethyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 was used in the same amount It was carried out in the same manner as in Example 1, except that it was added as At this time, the average particle diameter of the prepared enlarged rubbery polymer particles was 280 nm.

Comparative Example 2

In Example 1, when preparing the hypertrophic rubbery polymer latex, the ethyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 3 instead of the ethyl acrylate-methacrylic acid copolymer latex prepared in Preparation Example 1 was used in the same amount It was carried out in the same manner as in Example 1, except that it was added as At this time, the average particle diameter of the prepared enlarged rubbery polymer particles was 400 nm.

Comparative Example 3

<Production of rubbery polymer latex>

In a polymerization reactor substituted with nitrogen, 65 parts by weight of ion-exchanged water, 70 parts by weight of 1,3-butadiene, 1.0 parts by weight of potassium rosin salt, 1.2 parts by weight of oleic acid dimer potassium salt, 0.3 parts by weight of t-dodecyl mercaptan, K 0.8 parts by weight of ₂ CO ₃ , 0.3 parts by weight of potassium persulfate, and 0.1 parts by weight of a crosslinking agent represented by the following Chemical Formula 1 were all added, and the reaction was carried out at 70° C.

[Formula 1]

[CH ₂ =CHCO ₂ (C ₂ H ₄ O) ₅ CH ₂ ] ₃ CC ₂ H ₅

Then, at a polymerization conversion rate of 30%, 20 parts by weight of 1,3-butadiene and 0.15 parts by weight of a potassium rosin acid salt were put in a batch and reacted at 75° C., and at a polymerization conversion rate of 53%, 0.1 parts by weight of t-dodecyl mercaptan After the addition, the reaction was carried out until the polymerization conversion rate was 60%. At a polymerization conversion rate of 61%, 0.35 parts by weight of an oleic acid dimer potassium salt and 10 parts by weight of 1,3-butadiene were put in a batch, and then the temperature was raised to 82° C. A polymer latex (average particle diameter: 330 nm) was obtained.

<Production of graft copolymer latex>

60 parts by weight of the prepared rubbery polymer latex and 93.9 parts by weight of ion-exchanged water were added to a polymerization reactor substituted with nitrogen, and the mixture was sufficiently 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, 2 parts by weight of magnesium sulfate (MgSO ₄ ) was added, and agglomerated at 82 °C. Thereafter, it was aged at 82° C. for 94 hours, washed, dehydrated and dried to prepare a graft copolymer powder.

<Preparation of resin composition>

25 parts by weight of the prepared graft copolymer powder, 75 parts by weight of a styrene-acrylonitrile copolymer (manufactured by LG Chem, product name 92HR), 1.5 parts by weight of a lubricant, and 0.15 parts by weight of a heat stabilizer are put into a twin-screw extruder, and at 220° C. The resin composition pellets were prepared by kneading and extruding.

Comparative Example 4

In Comparative Example 3, when preparing the resin composition, 3 parts by weight of the methyl acrylate-ethylene copolymer (Dow's Elvaloy ^TM AC 1330) was added to the twin-screw extruder in the same manner as in Comparative Example 3, except that it was carried out in the same manner.

Comparative Example 5

In Comparative Example 3, when preparing the resin composition, 5 parts by weight of the methyl acrylate-ethylene copolymer (Dow's Elvaloy ^TM AC 1330) was added to the twin-screw extruder in the same manner as in Comparative Example 3, except that it was carried out in the same manner.

Experimental example

220 of the pellets prepared in Examples 1 to 3 and Comparative Examples 1 to 5 Injection at ℃, melt index, impact strength, surface energy and surface gloss measured by the following method, and gel evaluation, along with the composition of the resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5 Table 1 shows.

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

* 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 1/4 inch thick and 1/8 inch thick specimens was measured by ASTM D256 method, respectively.

* Surface energy (dyne/cm): Measured by the dyne pen test. Specifically, using a wettability measurement kit (ACCY DYNE TEST ^TM , Diversified Enterprises), using 6 types of dyne pens in the range of 38 dyne/cm to 48 dyne/cm included in the kit, the dyne pen on the surface of the specimen When the test was conducted, the surface energy value of the dyne pen showing the uniform diffusion of the ink without the shrinkage of the boundary observed when the surface energy of the specimen matches the surface energy of the dyne pen ink is expressed as the surface energy value of the specimen.

* Surface gloss: According to the ASTM D523 method, the 45 ° surface gloss of the specimen was measured using a gloss meter (VG-7000+Cu-2, Nippon Denshoku).

* Gel evaluation: By extruding the resin composition pellets prepared in each Example and Comparative Example into a film using a film extruder, and real-time evaluation with an optical gel counter, by measuring the size and number of gels per unit area, It was evaluated according to the following evaluation criteria.

○: The size of the gel is 100 μm or more, the number of gels is 100 or less

△: the size of the gel 100 μm or more, the number of gels more than 100, 250 or less

×: The size of the gel is 100 μm or more, the number of gels exceeds 250

division Example comparative example One 2 3 One 2 3 4 5 polymer flocculant Preparation Example 1 Preparation Example 1 Preparation Example 1 Preparation 2 Preparation 3 - - - rubbery polymer average particle size (nm) 110 110 110 110 110 330 330 330 Hypertrophic rubbery polymer average particle size (nm) 330 340 340 280 400 - - - Methyl acrylate-ethylene copolymer (parts by weight) - - - - - - 3 5 melt index (g/10 min) 21.2 21.1 19.5 22.0 not measurable 21.4 21.3 21.0 1/4" impact strength (kgf m/m) 32.0 33.0 34.5 26.5 not measurable 28.9 29.0 28.8 1/8" impact strength (kgf m/m) 35.2 36.0 37.0 28.4 not measurable 30.9 31.0 30.0 surface energy (dyne/cm) 41 42 43 39 not measurable 37 41 43 surface gloss 98.0 97.8 97.5 99.0 not measurable 98.2 94.0 93.5 Gel evaluation ○ ○ ○ ○ not measurable ○ X X

As shown in Table 1 above, the average particle diameter of the enlarged rubbery polymer was obtained by using the polymer coagulant in which the content of (meth)acrylic acid monomer units in the polymer flocculant was adjusted within the range of 5 wt% to 7 wt% according to the present invention. In the case of Examples 1 to 3 adjusted to 300 nm to 380 nm, especially 330 nm to 340 nm, melt index and impact strength are excellent, as well as 40 dyne / without using methyl acrylate-ethylene copolymer in the resin composition It was confirmed that the surface energy of more than cm was shown. In addition, the resin compositions of Examples 1 to 3 showed excellent results in gel evaluation as well as surface gloss, confirming that they were excellent in appearance characteristics.

On the other hand, in Comparative Examples 1 and 2 using a polymer flocculant in which the content of (meth)acrylic acid monomer units in the polymer flocculant was adjusted to less than 5% by weight and more than 7% by weight, the average particle diameter of each enlarged rubbery polymer was 280 nm and 400 nm, and in the case of Comparative Example 1, the average particle diameter of the rubber polymer was not sufficiently large, so that the impact resistance was lowered, and it was confirmed that the surface energy was still low. In particular, in the case of Comparative Example 2, the average particle diameter of the rubbery polymer was too large, and it was solidified during the preparation of the graft copolymer, and thus the graft copolymer could not be prepared, and thus the preparation of the resin composition was also impossible.

In addition, in the case of Comparative Examples 3 to 5, in which rubber polymers having an average particle diameter of 330 nm were prepared without using a polymer coagulant, the surface energy gradually increased depending on the inclusion and content of the methyl acrylate-ethylene copolymer in the resin composition. However, in the case of Comparative Example 3, which did not contain the methyl acrylate-ethylene copolymer, the impact strength was not sufficiently secured and the surface energy was also low, and the methyl acrylate-ethylene copolymer was added by 3 weight. In the case of Comparative Examples 4 and 5 including parts by weight and 5 parts by weight, it was confirmed that the effect of improving the impact strength did not appear at all, but the results according to the surface gloss and gel evaluation were rather poor, and the appearance characteristics were lowered.

From these results, in the case of preparing a graft copolymer by the method for preparing a graft copolymer according to the present invention, the resin composition itself including the graft copolymer without the use of a functional additive to improve the surface energy of the resin composition It was confirmed that the surface energy of

In addition, the graft copolymer prepared according to the method for preparing the graft copolymer of the present invention, compared to the graft copolymer including the rubbery polymer having an average particle diameter in the same or similar range, contains the graft copolymer. It was confirmed that the impact resistance and appearance characteristics of the resin composition were improved.

Claims (11)

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 5 wt% to 7 wt% of (meth)acrylic acid-based monomer units,
The average particle diameter of the enlarged rubbery polymer prepared in step (S10) is 300 nm to 380 nm. According to claim 1,
The rubbery polymer is a conjugated diene-based polymer graft copolymer manufacturing method. The method of 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 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. According to claim 1,
The average particle diameter of the enlarged rubbery polymer is 320 nm to 350 nm. 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 a (meth)acrylic acid-based monomer unit,
The graft copolymer having an average particle diameter of 300 nm to 380 nm of the enlarged rubbery polymer. 7. The method of claim 6,
The content of the polymer coagulant is 0.15 parts by weight to 0.75 parts by weight based on 100 parts by weight of the rubbery polymer, the aromatic vinyl-based monomer unit and the vinyl cyan-based monomer unit. 7. The method of claim 6,
wherein the graft copolymer comprises a non-enlarged rubbery polymer;
The non-enlarged rubbery polymer has an average particle diameter of 50 nm to 150 nm. A resin composition comprising the graft copolymer according to any one of claims 6 to 8. 10. The method of claim 9,
The resin composition comprises 10 wt% to 40 wt% of the graft copolymer; and 60 wt% to 90 wt% of a copolymer comprising an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit. 10. The method of claim 9,
The resin composition has an impact strength of 30.0 kgf·m/m or more measured at 1/4 inch thickness according to ASTM D256, and a surface energy measured by a dyne pen test of 40 dyne/cm or more.