KR102157627B1 - Abs graft copolymer, method for preparing the graft copolymer, abs resin composition and molding product comprising the graft copolymer - Google Patents

Abstract

The present invention relates to an ABS-based graft copolymer, a method for producing the same, and an ABS-based resin composition and injection-molded product prepared including the same, and more particularly, to graft polymerization of an aromatic vinyl compound and a vinyl cyan compound to a diene-based rubber polymer. When ordered, an ABS-based graft copolymer having a high graft rate can be prepared by excluding the use of an emulsifier and containing a large-diameter rubber latex and a small-diameter rubber latex as a diene-based rubber polymer in a specific ratio, which is an aromatic vinyl compound-vinyl It may be mixed and processed with a cyan compound to provide an ABS-based resin composition with improved appearance quality such as colorability, glossiness, and clarity.

Description

ABS-based graft copolymer, its manufacturing method, and the ABS-based resin composition and injection-molded product manufactured including the same {ABS GRAFT COPOLYMER, METHOD FOR PREPARING THE GRAFT COPOLYMER, ABS RESIN COMPOSITION AND MOLDING PRODUCT COMPRISING THE GRAFT COPOLYMER}

The present invention relates to an ABS-based graft copolymer, a method for producing the same, and an ABS-based resin composition and injection molded article prepared including the same, and more particularly, to exclude the use of an emulsifier during graft polymerization, and Regarding ABS-based graft copolymers that can improve the graft rate of ABS-based resins by including a rubber polymer of the diameter in a specific ratio and improve the appearance quality such as colorability, glossiness, and clarity of the final resin composition including the same. will be.

ABS-based copolymers containing acrylonitrile-butadiene-styrene have relatively good physical properties such as moldability and gloss, as well as mechanical strength such as impact resistance, and thus electrical parts, electronic parts, and office equipment. Or, it is widely used in automobile parts and the like, and its usage is gradually increasing.

In recent years, in order to satisfy consumer preferences that value appearance characteristics such as color and gloss of products, appearance characteristics such as colorability and gloss in addition to mechanical properties such as impact resistance of ABS-based copolymers are emerging as important quality.

In the conventional ABS-based copolymer, in order to improve impact resistance, styrene and acrylonitrile are graft-copolymerized with diene-based rubber latex such as butadiene by an emulsion polymerization method, and then, this is a SAN-based resin such as a styrene-acrylonitrile copolymer, It is kneaded with a thermoplastic resin such as polystyrene and polymethyl methacrylate to form a resin composition.

However, rubber such as butadiene added to improve impact resistance has a problem in that the colorability, clarity, and gloss are inferior to monomer compounds such as styrene or acrylonitrile grafted thereto. That is, in the case of producing a high white ABS-based copolymer, increasing the content of the rubber is effective in increasing the whiteness of the resin itself, but as the rubber content increases, the grafting rate decreases, so the colorability, clarity, and gloss of the final product. There was a problem that caused a decrease in sex.

Accordingly, there is a demand for an ABS-based copolymer manufacturing technology capable of improving the appearance characteristics such as colorability and clarity of the final product while maintaining the mechanical properties such as impact strength at a high level.

Korean Patent Registration No. 10-0419230

In order to solve the problems of the prior art as described above, the present invention is an ABS-based graft copolymer capable of improving appearance quality such as coloring, gloss, and surface clarity while maintaining physical properties such as mechanical strength and processability inherent in ABS-based graft copolymers. It is an object of the present invention to provide a graft copolymer and a method for producing the same.

In addition, it is an object of the present invention to provide an ABS resin composition and an injection molded article excellent in appearance properties such as colorability and gloss including the ABS graft copolymer.

All of the above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention is a diene-based rubber polymer comprising 75 to 99% by weight of a large-diameter rubber polymer having an average particle diameter of 2,000 to 4,000Å and 1 to 25% by weight of a small-diameter rubber polymer having an average particle diameter of 500 to 1,500Å An aromatic vinyl compound and a vinyl cyanide compound are graft-polymerized to provide an ABS-based graft copolymer characterized in that it is emulsifier-free.

In addition, the present invention is a diene-based rubber comprising 75 to 99% by weight of a large-diameter rubber polymer latex (based on solid content) of 2,000 to 4,000Å and 1 to 25% by weight (based on solid content) of a small-diameter rubber polymer latex having an average particle diameter of 500 to 1,500Å. It includes a graft polymerization step of graft polymerization including latex, an aromatic vinyl compound, and a vinyl cyan compound, wherein the polymerization is an emulsifier-free polymerization. It provides a method for producing an ABS-based graft copolymer.

In addition, the present invention is characterized in that the ABS produced by kneading and extruding 10 to 50% by weight of the ABS-based graft copolymer prepared by the emulsifier-free polymerization and 50 to 90% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer. It provides a resin composition.

In addition, the present invention provides an injection molded article, characterized in that produced by injecting the ABS-based resin composition.

According to the present invention, an ABS-based graft copolymer containing a large-diameter rubber polymer and a small-diameter rubber polymer in a specific ratio, and an emulsifier-free and optionally a molecular weight control agent-free with an improved graft rate can be prepared, and mixed with a matrix resin. The resulting resin composition has the effect of providing a high-quality resin composition and molded article by greatly improving the appearance quality such as colorability, clarity, and gloss.

The present inventors prepared an ABS-based graft copolymer with a greatly improved graft rate by introducing a small-diameter rubber polymer in a specific ratio and excluding the use of an emulsifier and optionally a molecular weight control agent to perform graft polymerization when preparing an ABS-based graft copolymer. It was confirmed that the external physical properties such as surface gloss, clarity, and colorability of the resin composition including the same are greatly improved, and the present invention was completed based on this.

The ABS-based graft copolymer of the present invention is a diene-based rubber polymer comprising 75 to 99% by weight of a large-diameter rubber polymer having an average particle diameter of 2,000 to 4,000Å and 1 to 25% by weight of a small-diameter rubber polymer having an average particle diameter of 500 to 1,500Å. A copolymer obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound, and is characterized in that it is emulsifier-free without the use of an emulsifier during the graft polymerization.

As another example, the ABS-based graft copolymer of the present invention may be characterized in that it is free of an emulsifier and a molecular weight control agent that excludes the use of an emulsifier and a molecular weight control agent during the graft polymerization.

In the present description, the average particle diameter can be measured using the Nicomp 380 equipment by the dynamic light scattering method.

In the present description, the emulsifier-free and molecular weight control agent-free mean that the emulsifier and molecular weight control agent are not used and/or prepared from the graft polymerization, respectively, but the polymerization of the diene-based rubber polymer used in the graft polymerization It does not mean that the emulsifier and molecular weight control agent are not used until manufacture.

Hereinafter, the ABS-based graft copolymer of the present invention and a method for producing the same will be described in detail.

The diene-based rubber polymer refers to a polymer of a conjugated diene-based compound having a structure in which a double bond and a single bond are arranged across one, for example, butadiene polymer, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer-ethylene- It may be one or more of a propylene copolymer or a polymer derived therefrom, and preferably includes a butadiene polymer.

The term "polymer derived" in the present description refers to a polymer prepared by polymerization of another monomer compound or a polymer in which a polymer is copolymerized or a derivative of a monomer compound not included in the original polymer.

In the present description, a derivative refers to a compound in which a hydrogen atom or an atomic group of the original compound is an example of another atom or atomic group, and is substituted with a halogen or an alkyl group.

The ABS-based graft copolymer of the present invention is a diene-based rubber polymer and contains a large-diameter rubber polymer having an average particle diameter of 2,000 to 4,000Å and a small-diameter rubber polymer having an average particle diameter of 500 to 1,500Å in a specific content, and in this case, the graft rate is high, While the final resin composition has excellent mechanical properties such as impact strength, there is an effect of improving appearance quality such as colorability and clarity.

For example, the diene-based rubber polymer may include 75 to 99% by weight of a large-diameter rubber polymer and 1 to 25% by weight of a small-diameter rubber polymer, and a copolymer having a high graft rate may be prepared within this range, and ultimately There is an effect of excellent appearance quality such as glossiness of the resin composition.

In another example, the diene-based rubber polymer may include 80 to 95% by weight of a large-diameter rubber polymer and 5 to 20% by weight of a small-diameter rubber polymer, and within this range, the graft rate is high, and the appearance quality of the final resin composition is improved. Has the effect of being.

In another example, the diene-based rubber polymer may include 80 to 90% by weight of a large-diameter rubber polymer and 10 to 20% by weight of a small-diameter rubber polymer, and within this range, the graft rate of the graft copolymer is greatly improved, While maintaining high mechanical properties such as impact strength of the final resin composition, there is an effect of greatly improving appearance quality such as glossiness and clarity.

The large-diameter rubber polymer may have an average particle diameter of 2,000 to 4,000Å as an example, more preferably 2,500 to 3,500Å, and most preferably 2,800 to 3,200Å. Within this range, there is an advantage of excellent mechanical properties such as impact strength of the ABS-based graft copolymer.

The small-diameter rubber polymer may have an average particle diameter of 500 to 1,500 Å as an example, more preferably 800 to 1,200 Å, and most preferably 900 to 1,100 Å. An ABS-based graft copolymer prepared by including a small-diameter rubber polymer having a particle diameter within the above-described range in a specific content can achieve a high graft rate under the same reaction conditions, and appearance properties such as gloss and clarity of the final resin composition Can be greatly improved.

The ABS graft copolymer of the present invention contains a small-diameter rubber polymer in a specific content as described above, and is prepared by excluding the use of an emulsifier or an emulsifier and a molecular weight control agent, so that the graft rate is 40 to 80%, 45 to 80%, for example. , 50 to 80% or 55 to 70%, and within this range, while maintaining high mechanical properties such as impact strength of the ABS-based resin composition, there is an effect of greatly improving appearance quality such as colorability and glossiness.

In the present description, the graft rate can be calculated by Equation 1 below.

[Equation 1]

Graft rate (%) = (weight of the monomer component grafted on the rubber polymer/total weight of the copolymer) * 100

The emulsifier-free ABS graft copolymer of the present disclosure may have a residual emulsifier content of 7,000 ppm or less, or 5,000 ppm or less, for example.

In this description, it is stated that the residual emulsifier was not added during the ABS graft polymerization.

In the present description, the residual emulsifier content can be measured by liquid chromatography/mass spectrometry (LC/MS) after pretreatment by dissolving a sample in an organic solvent such as tetrahydrofuran (THF), for example.

The ABS-based graft copolymer production method of the present invention is, for example, a large-diameter rubber polymer latex having an average particle diameter of 2,000 to 4,000Å 75 to 99% by weight (based on solid content) and a small-diameter rubber polymer latex having an average particle diameter of 500 to 1,500Å 1 to Including a graft polymerization step of graft polymerization including a diene rubber latex containing 25% by weight, an aromatic vinyl compound and a vinyl cyan compound, wherein the polymerization is emulsifier-free, or emulsifier- and molecular weight control agent-free It can be characterized.

The ABS-based graft copolymer production method of the present invention can achieve a high graft rate under the same conditions by excluding the addition of an emulsifier or a molecular weight control agent during graft polymerization, and ultimately, the colorability and clarity of the ABS-based resin composition. There is an effect of greatly improving the appearance quality.

In a specific example, the graft polymerization step is a diene-based rubber latex containing 75 to 99% by weight (based on solid content) and 1 to 25% by weight of a small diameter rubber polymer latex (based on solid content) , In 100 parts by weight of a monomer mixture containing 20 to 40% by weight of an aromatic vinyl compound and 5 to 20% by weight of a vinyl cyanide compound, 0.01 to 0.2 parts by weight of an initiator may be continuously or collectively added to perform graft polymerization.

The diene-based rubber latex includes the same diene-based rubber polymer as described above, which may be preferably contained in 50 to 70% by weight, 55 to 70% by weight, and 55 to 65% by weight based on solids in the monomer mixture. , Within this range, a high graft rate can be achieved, and mechanical properties such as impact resistance and processability of the final resin composition are excellent.

The aromatic vinyl compound may be, for example, one or more selected from styrene, alpha-methylstyrene, p-methylstyrene, o-ethyl styrene, o-methyl styrene, vinyltoluene, and the like, preferably styrene.

The aromatic vinyl compound may be preferably contained in an amount of 20 to 40% by weight, 25 to 40% by weight, and 25 to 35% by weight of the monomer mixture. In this case, the grafting rate is high and the physical property balance of the final resin composition is excellent. There is.

The vinyl cyan compound may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, and preferably includes acrylonitrile.

The vinyl cyanide compound may be preferably included in 5 to 20% by weight, 10 to 20% by weight, and 10 to 15% by weight of the monomer mixture, and within this range, a high graft rate can be achieved, and the final resin There is an effect excellent in appearance characteristics and mechanical properties such as colorability of the composition.

The initiator is not particularly limited as long as it is an initiator commonly used in the technical field to which the present invention belongs, and for example, t-butyl hydroperoxide, t-hexyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroper Oxide, dicumyl peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, lauroyl peroxide, t-butyl peroxy It may be one or more selected from the group consisting of benzoate, paramethane hydroperoxide, benzoyl peroxide and azobis isobutyronitrile, and preferably t-butyl hydroperoxide.

The initiator may be used in an example of 0.01 to 0.2 parts by weight, 0.05 to 0.2 parts by weight, or 0.1 to 0.2 parts by weight based on 100 parts by weight of the monomer mixture, and within this range, overreaction is prevented and polymerization efficiency is excellent. .

The graft polymerization step is, for example, one or more oxidation-reduction systems selected from the group consisting of sodium pyrrolate, dextrose, ferrous sulfate, sodium sulfite, sodium formaldehyde sulfoxylate, sodium ethylene diamine tetraacetate. It may be possible to use a catalyst together with the initiator, and in this case, there is an effect of improving the reaction rate by increasing the efficiency of the initiator.

The oxidation-reduction catalyst may be preferably used in an amount of 0.001 to 0.5 parts by weight, 0.01 to 0.3 parts by weight, or 0.05 to 0.2 parts by weight based on 100 parts by weight of the monomer mixture, and within this range, the action of the initiator is It is promoted to improve polymerization efficiency.

The graft polymerization step is further performed by including polymerization water, and the polymerization water may preferably be included in an amount of 100 to 200 parts by weight or 140 to 180 parts by weight based on 100 parts by weight of the monomer mixture. When the polymerization water is included within the above-described range, there is an advantage in that heat removal is easy.

The graft polymerization step may be performed within a reaction temperature of 50 to 75°C or 60 to 70°C, for example, and polymerization efficiency is excellent within this range.

In addition, the graft polymerization step may be preferably performed for 2 to 5 hours or 3 to 4 hours at the reaction temperature condition, for example, there is an effect of increasing the graft efficiency within this range.

The ABS-based graft copolymer production method of the present invention is, for example, after the graft polymerization step, by adding 0.01 to 0.3 parts by weight of an initiator and 0.001 to 0.5 parts by weight of an oxidation-reduction catalyst based on 100 parts by weight of the monomer mixture. It may further include an additional polymerization step of polymerization, in which case, the graft rate is further improved, and the mechanical strength or appearance quality of the final resin composition is more excellent due to the reduction of unreacted monomers.

As another example, the initiator introduced in the additional polymerization step may be 0.01 to 0.1 parts by weight, and the oxidation-reduction catalyst may be 0.05 to 0.3 parts by weight, and a high graft rate can be achieved within this range, and the final There is an effect of further improving the physical properties of the composition.

The additional polymerization step may be preferably carried out within the range of, for example, a reaction temperature of 60 to 95°C or 70 to 90°C (higher than the reaction temperature of the graft polymerization step), and in this case, a high graft rate can be achieved. In addition, there is an effect of improving appearance properties such as gloss and clarity of the final resin composition.

In addition, in the additional polymerization step, it may be preferable to react for 1 to 2 hours while raising the reaction temperature to within the above range, and in this case, a high graft rate can be achieved.

As a specific example, the method for producing an ABS-based graft copolymer of the present invention is i) 75 to 99% by weight of a large-diameter rubber polymer latex (based on solid content) with an average particle diameter of 2,000 to 4,000Å in the reactor, and a small diameter with an average particle diameter of 500 to 1,500Å 100 parts by weight of a monomer mixture comprising 50 to 70% by weight of a diene rubber latex (based on solid content) including 1 to 25% by weight of a rubber polymer latex, 20 to 40% by weight of an aromatic vinyl compound, and 5 to 20% by weight of a vinylcyan compound Graft polymerization step of graft polymerization by adding 0.01 to 0.2 parts by weight of an initiator to; ii) adding 0.001 to 0.5 parts by weight of an oxidation-reduction catalyst based on 100 parts by weight of the monomer mixture; iii) adding 0.01 to 0.3 parts by weight of an initiator and 0.001 to 0.5 parts by weight of an oxidation-reduction catalyst based on 100 parts by weight of the monomer mixture after the step ii) is added; iv) an additional polymerization step of increasing the reaction temperature and performing graft polymerization after the additional addition; And v) aggregating, washing, and drying the obtained latex after the completion of the additional polymerization to obtain an ABS-based graft copolymer powder; including, an emulsifier that does not add an emulsifier during the graft polymerization and further polymerization- It can be characterized in that it is pre-polymerization.

In addition, the ABS-based graft copolymer production method may be a molecular weight control agent-free polymerization that does not add a molecular weight control agent during graft polymerization and additional polymerization, and by excluding the use of an emulsifier and a molecular weight control agent, a high graft rate is achieved under the same conditions. can do.

Aggregation of the latex is not particularly limited if it is within the range commonly practiced in the technical field to which the present invention belongs, and preferably one selected from acid flocculants such as hydrochloric acid sulfate or metal salt flocculants such as magnesium sulfate, aluminum sulfate and calcium chloride. It can be carried out at 90 to 140 ℃ by adding the above coagulant.

After the latex coagulation as described above, it can be washed and dried in a conventional manner to obtain a dry ABS-based graft copolymer.

Furthermore, the ABS-based graft copolymer may be mixed with a matrix resin, and may be manufactured into an ABS-based resin composition and an injection-molded product through processes such as extrusion and injection, and the following will be described with respect to the ABS-based resin composition and injection-molded product. do.

The ABS resin composition of the present invention may be prepared by kneading and extruding 10 to 50% by weight of the ABS graft copolymer and 50 to 90% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer, as an example. It has the advantage of excellent balance of physical properties within and excellent processing and moldability.

As another example, the ABS-based resin composition may include 15 to 40% by weight of an ABS-based graft copolymer and 60 to 85% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer, and has excellent physical property balance within this range. It has an effect that has excellent processability.

In another example, the ABS resin composition may include 20 to 30% by weight of an ABS graft copolymer and 70 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer, and mechanical properties within the above-described range , It has the advantage of being easy to process while having excellent physical properties such as appearance characteristics.

The kneading and extrusion are not particularly limited, and as an example, a single screw extruder or a twin screw extruder may be used.

In addition, the kneading and extrusion may be performed under conditions of 180 to 250° C. or 200 to 220° C. and 200 to 300 rpm or 230 to 270 rpm, for example, but is not limited thereto.

The ABS-based resin composition of the present invention has an excellent impact resistance of 18.5kgcm/cm or more, 19.5 to 25 kgcm/cm, or 20 to 25 kgcm/cm, as measured according to ASTM D256 as an example.

The ABS resin composition has, for example, a value of 24.5 or less, 23 or less, 21 or less, 15 to 23, 15 to 21, or 18 to 21, as measured according to ASTM D1925, and has excellent colorability.

In addition, the ABS-based resin composition has an excellent glossiness of 98 or more or 99 or more as measured according to ASTM D528, for example, so that the appearance quality is excellent.

Further, the ABS resin composition of the present disclosure may be manufactured as an injection molded article by injection under conditions of 200 to 250° C. and 50 to 100 bar, for example.

In the description of the ABS-based graft copolymer of the present disclosure and its manufacturing method, and the ABS-based resin composition and injection-molded product including the same, other conditions not explicitly described are commonly practiced in the technical field to which the present invention belongs. It can be appropriately selected and implemented within the range, and it is stated that there is no particular limitation.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It is natural that such modifications and modifications fall within the appended claims.

[Example]

Example One

1. ABS Graft Copolymer Preparation

After adding 59 parts by weight of large-diameter butadiene rubber latex with an average particle diameter of 3,000Å (based on solid content), 1 part by weight of small-diameter butadiene rubber latex with an average particle diameter of 1,000Å (based on solid content) and 160 parts by weight of ion-exchanged water into a nitrogen-substituted polymerization reactor. , In a separate mixing device, 11.2 parts by weight of acrylonitrile, 28.8 parts by weight of styrene, and 0.16 parts by weight of t-butyl hydroperoxide were mixed to prepare a mixture, and the mixture was added to the polymerization reactor at a reaction temperature of 70° C. for 3.5 hours. . At this time, 0.081 parts by weight of dextrose, 0.036 parts by weight of sodium pyrrolate, and 0.009 parts by weight of ferrous sulfate were continuously or collectively added. After the addition of the mixed solution was completed, 0.08 parts by weight of dextrose, 0.05 parts by weight of sodium pyrrolate, 0.001 parts by weight of ferrous sulfate and 0.05 parts by weight of t-butyl hydroperoxide were collectively added to the reactor and reacted over 1 hour. After raising the temperature to 80° C., the reaction was terminated.

The obtained ABS graft copolymer latex was aggregated with magnesium sulfate, washed and dried to obtain an ABS graft copolymer powder.

2. ABS resin composition manufacturing

25 parts by weight of the powder and 75 parts by weight of a SAN resin (manufactured by LG Chem, product name: 92HR) are mixed in a mixer, and then extruded at 200 to 220°C to prepare an ABS resin composition in the form of a pellet, and then injected (200°C) , 70bar) to prepare a specimen for measuring physical properties.

Example 2

In Example 1, it was carried out in the same manner as in Example 1, except that 55 parts by weight was added instead of 59 parts by weight of the large-diameter rubber latex, and 5 parts by weight were added instead of 1 part by weight of the small-diameter rubber latex.

Example 3

In Example 1, it was carried out in the same manner as in Example 1, except that 50 parts by weight was added instead of 59 parts by weight of the large-diameter rubber latex, and 10 parts by weight were added instead of 1 part by weight of the small-diameter rubber latex.

Example 4

1. ABS Graft Copolymer Preparation

In a polymerization reactor substituted with nitrogen, add 54 parts by weight of average particle diameter 3,000Å large-diameter rubber latex (based on solid content), 1,000Å small-diameter rubber latex 1 part by weight (based on solid content) and 160 parts by weight of ion-exchanged water, and mix separately A mixture was prepared by mixing 11.2 parts by weight of acrylonitrile, 28.8 parts by weight of styrene, and 0.16 parts by weight of t-butyl hydroperoxide in an apparatus, and then the mixture was added to a polymerization reactor at a reaction temperature of 70° C. for 4 hours. At this time, 0.081 parts by weight of dextrose, 0.036 parts by weight of sodium pyrrolate, and 0.009 parts by weight of ferrous sulfate were continuously or collectively added. After the addition of the mixed solution was completed, 0.08 parts by weight of dextrose, 0.05 parts by weight of sodium pyrrolate, 0.001 parts by weight of ferrous sulfate and 0.05 parts by weight of t-butyl hydroperoxide were collectively added to the reactor and reacted over 1 hour. After raising the temperature to 80° C., the reaction was terminated.

The obtained ABS graft copolymer latex was aggregated with magnesium sulfate, washed and dried to obtain an ABS graft copolymer powder.

2. ABS resin composition manufacturing

25 parts by weight of the powder and 75 parts by weight of a SAN resin (manufactured by LG Chem, product name: 92HR) are mixed in a mixer, and then extruded at 200 to 220°C to prepare an ABS resin composition in the form of a pellet, and then injected (200°C) , 70bar) to prepare a specimen for measuring physical properties.

Example 5

In Example 4, it was carried out in the same manner as in Example 4, except that 50 parts by weight was added instead of 54 parts by weight of the large-diameter rubber latex, and 5 parts by weight were added instead of 1 part by weight of the small-diameter rubber latex.

Example 6

In Example 4, it was carried out in the same manner as in Example 4, except that 45 parts by weight was added instead of 54 parts by weight of the large-diameter rubber latex, and 10 parts by weight were added instead of 1 part by weight of the small-diameter rubber latex.

Example 7

1. ABS Graft Copolymer Preparation

In a polymerization reactor substituted with nitrogen, an average particle diameter of 3,000Å large diameter rubber latex 64 parts by weight (based on solid content), an average particle diameter 1,000Å small diameter rubber latex 1 part by weight (solid content) and 160 parts by weight of ion-exchanged water are added and mixed separately. In an apparatus, 11.2 parts by weight of acrylonitrile, 28.8 parts by weight of styrene, and 0.16 parts by weight of t-butyl hydroperoxide were mixed to prepare a mixture, and the mixture was added to a polymerization reactor at a reaction temperature of 70° C. for 3 hours. At this time, 0.081 parts by weight of dextrose, 0.036 parts by weight of sodium pyrrolate, and 0.009 parts by weight of ferrous sulfate were continuously or collectively added. After the addition of the mixed solution was completed, 0.08 parts by weight of dextrose, 0.05 parts by weight of sodium pyrrolate, 0.001 parts by weight of ferrous sulfate and 0.05 parts by weight of t-butyl hydroperoxide were collectively added to the reactor and reacted over 1 hour. After raising the temperature to 80° C., the reaction was terminated.

The obtained ABS graft copolymer latex was aggregated with magnesium sulfate, washed and dried to obtain an ABS graft copolymer powder.

2. ABS resin composition manufacturing

25 parts by weight of the powder and 75 parts by weight of a SAN resin (manufactured by LG Chem, product name: 92HR) are mixed in a mixer, and then extruded at 200 to 220°C to prepare an ABS resin composition in the form of a pellet, and then injected (200°C) , 70bar) to prepare a specimen for measuring physical properties.

Example 8

In Example 7, it was carried out in the same manner as in Example 7, except that 60 parts by weight was added instead of 64 parts by weight of the large-diameter rubber latex, and 5 parts by weight were added instead of 1 part by weight of the small-diameter rubber latex.

Example 9

In Example 7, it was carried out in the same manner as in Example 7, except that 55 parts by weight was added instead of 64 parts by weight of the large-diameter rubber latex, and 10 parts by weight were added instead of 1 part by weight of the small-diameter rubber latex.

Comparative example One

1. ABS Graft Copolymer Preparation

After adding 60 parts by weight of rubber latex (based on solid content) and 145 parts by weight of ion-exchanged water to a polymerization reactor substituted with nitrogen, 11.2 parts by weight of acrylonitrile, 28.8 parts by weight of styrene, and ion-exchanged water in a separate mixing device An emulsion was prepared by mixing 25 parts by weight, 0.12 parts by weight of t-butyl hydroperoxide, 1.1 parts by weight of potassium rosinate (emulsifier), and 0.3 parts by weight of t-dodecylmercaptan (molecular weight control agent). The emulsion was added to the polymerization reactor at a reaction temperature of 70° C. for 4 hours. At this time, 0.054 parts by weight of dextrose, 0.024 parts by weight of sodium pyrrolate, and 0.006 parts by weight of ferrous sulfate were continuously added. After the addition of the emulsion was completed, 0.08 parts by weight of dextrose, 0.05 parts by weight of sodium pyrrolate, 0.001 parts by weight of ferrous sulfate and 0.05 parts by weight of t-butyl hydroperoxide were collectively added to the reactor and reacted over 1 hour. After raising the temperature to 80° C., the reaction was terminated.

The obtained ABS graft copolymer latex was aggregated with magnesium sulfate, washed and dried to obtain an ABS graft copolymer powder.

2. ABS resin composition manufacturing

25 parts by weight of the powder and 75 parts by weight of a SAN resin (manufactured by LG Chem, product name: 92HR) are mixed in a mixer, and then extruded at 200 to 220°C to prepare an ABS resin composition in the form of a pellet, and then injected (200°C) , 70bar) to prepare a specimen for measuring physical properties.

[Test Example]

The properties of the ABS graft copolymer and the specimen prepared in the Examples and Comparative Examples were measured by the following method, and the results are shown in Table 1 below.

1. Graft rate: 2 g of ABS resin powder obtained by coagulating, washing and drying the latex on which the graft polymerization was completed was added to 300 ml of acetone and stirred for 24 hours. After separating this solution using an ultracentrifuge, the separated acetone solution was dropped into methanol to obtain an ungrafted portion, which was dried at 60 to 120°C to measure the weight. From this weight, the graft rate was calculated according to Equation 1 below.

[Equation 1]

Graft rate (%) = (weight of the monomer component grafted on the rubber polymer/total weight of the copolymer) * 100

2. Izod Impact Strength (IMP): Izod impact strength of a 1/4" specimen was measured according to ASTM D256.

3. Colorability (whiteness index; WI): When preparing the ABS resin composition, the degree of coloration was evaluated by measuring the whiteness of the colored specimen prepared by adding 0.05 parts by weight of a blue pigment during the kneading process. The whiteness of the specimen was measured according to ASTM D1925 using the Spectrogard Color System. The lower the value, the more black it is, which means that the colorability is excellent.

4. Sharpness (L value): L, a, and b values of the colored specimen were measured using a color difference meter (Color Quest II, Hunter Lab Co.). L represents brightness and can have a value from 0 to 100, and the closer to 0, the better the sharpness.

5. Gloss: According to ASTM D528, the glossiness of the specimen was measured at a 45° angle.

6. Content of residual emulsifier: After dissolving 0.3 g of a sample in THF, a polymer was precipitated with methanol, and the supernatant was filtered, and then the residual emulsifier content was analyzed using LC/MS.

division Comparative example Example One One 2 3 4 5 6 7 8 9 Rubber polymer Large diameter 60 59 55 50 54 50 45 64 60 55 Small diameter - One 5 10 One 5 10 One 5 10 Emulsifier ○ X Molecular weight regulator ○ Graft rate [%] 30.8 49.9 51.8 53.7 60.7 62.8 65.4 42.3 44.0 45.8 IMP[kgcm/cm] 19.5 22.0 21.6 20.3 22.5 21.8 20.5 20.1 19.5 18.7 Coloring (WI) 25.1 23.0 21.2 19.8 21.5 20.0 18.7 24.2 23.0 21.5 Sharpness (L value) 23.0 21.5 20.9 18.1 19.8 20.1 17.2 22.7 21.4 19.8 Gloss 97.5 98.4 98.7 99.2 98.8 99.0 99.6 98.2 98.5 97.9 Residual emulsifier [ppm] 12,400 5,800 5,700 5,600 4,900 4,800 4,700 6,700 6,600 6,500

As shown in Table 1, it was confirmed that the ABS graft copolymer according to the present invention omits the addition of the emulsifier and the molecular weight control agent, and the graft rate is 10% or more higher than that of Comparative Example 1.

In addition, it was confirmed that the specimen prepared including the ABS graft copolymer according to the present invention had an impact strength equal to or superior to that of Comparative Example 1, which was not according to the present invention, but excellent colorability, clarity, and gloss.

In addition, as shown in Table 1, it was confirmed that as the content of the small-diameter rubber polymer increased under the same conditions, the graft rate and gloss were further improved.

Claims (16)

An aromatic vinyl compound and a vinyl cyan compound are grafted to a diene rubber polymer containing 80 to 95% by weight of a large-diameter rubber polymer having an average particle diameter of 2,000 to 4,000Å and 5 to 20% by weight of a small-diameter rubber polymer having an average particle diameter of 500 to 1,500Å It is a polymerized copolymer, emulsifier-free, characterized in that the aromatic vinyl compound is styrene
ABS-based graft copolymer. The method of claim 1,
The graft copolymer is characterized in that the graft rate is 40 to 80%
ABS-based graft copolymer. The method of claim 1,
The graft copolymer is characterized in that the molecular weight regulator-free
ABS-based graft copolymer. Diene rubber latex, aromatic vinyl compound and vinyl comprising 80 to 95% by weight of a large-diameter rubber polymer latex (based on solid content) with an average particle diameter of 2,000 to 4,000Å and 5 to 20% by weight of a small-diameter rubber polymer latex with an average particle diameter of 500 to 1500Å Including a graft polymerization step of graft polymerization including a cyan compound, wherein the polymerization is emulsifier-free, wherein the aromatic vinyl compound is styrene.
Method for producing an ABS-based graft copolymer. The method of claim 4,
The graft polymerization step includes 100 parts by weight of a monomer mixture comprising 50 to 70% by weight of a diene rubber latex (based on solid content), 20 to 40% by weight of an aromatic vinyl compound, and 5 to 20% by weight of a vinyl cyan compound, an initiator 0.01 to Graft polymerization by adding 0.2 parts by weight, characterized in that
Method for producing an ABS-based graft copolymer. The method of claim 5,
The graft polymerization step is characterized in that the graft polymerization further comprises 0.001 to 0.5 parts by weight of an oxidation-reduction catalyst based on 100 parts by weight of the monomer mixture.
Method for producing an ABS-based graft copolymer. The method of claim 5,
The graft polymerization step is characterized in that the graft polymerization comprises 100 to 200 parts by weight of polymerization water based on 100 parts by weight of the monomer mixture.
Method for producing an ABS-based graft copolymer. The method of claim 4,
The graft polymerization step is characterized in that the reaction temperature is carried out within the range of 50 to 75 ℃
Method for producing an ABS-based graft copolymer. The method of claim 4,
After the graft polymerization step, 0.01 to 0.3 parts by weight of an initiator and 0.001 to 0.5 parts by weight of an oxidation-reduction catalyst based on 100 parts by weight of a monomer mixture including the diene rubber latex, an aromatic vinyl compound and a vinyl cyan compound are further added. It characterized in that it comprises an additional polymerization step of graft polymerization
Method for producing an ABS-based graft copolymer. The method of claim 9,
The additional polymerization step is characterized in that the reaction temperature is carried out within the range of 60 to 95 ℃ (higher than the reaction temperature of the graft polymerization step)
Method for producing an ABS-based graft copolymer. The method of claim 4,
The polymerization is characterized in that the molecular weight regulator-free
Method for producing an ABS-based graft copolymer. It is characterized in that produced by kneading and extruding 10 to 50% by weight of the ABS-based graft copolymer according to any one of claims 1 to 3 and 50 to 90% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer.
ABS resin composition. The method of claim 12,
The composition is characterized in that the impact strength measured according to ASTM D256 is 18.5kgcm / cm or more.
ABS resin composition. The method of claim 12,
The composition is characterized in that the whiteness measured according to ASTM D1925 is 24.5 or less.
ABS resin composition. The method of claim 12,
The composition is characterized in that the glossiness measured according to ASTM D528 is 98 or more.
ABS resin composition. It is characterized in that produced by injecting the ABS resin composition according to claim 12
Injection molded products.