KR102105472B1 - MBS based impact modifier, preparation method thereof, and polycarbonate resin composition comprising the same - Google Patents

Abstract

The present invention relates to an MBS-based impact modifier, a method for manufacturing the same, and a polycarbonate composition comprising the same, and more specifically, an MBS-based impact modifier using a large-diameter MBS-based nanoparticle mixed with a small-diameter acrylate-based crosslinked nanoparticle. When manufacturing and applying it to a polycarbonate-based resin, it relates to an MBS-based impact modifier having excellent impact resistance at both low and normal temperatures, a method for manufacturing the same, and a polycarbonate composition comprising the same.

Description

MBS-based impact modifier, manufacturing method thereof and polycarbonate composition comprising the same {MBS based impact modifier, preparation method thereof, and polycarbonate resin composition comprising the same}

The present invention relates to an MBS-based impact modifier that exhibits excellent impact resistance at low and normal temperatures, a manufacturing method, and a polycarbonate composition.

Polycarbonate (PC) has excellent impact resistance, electrical properties, and heat resistance, and is widely used as an interior and exterior agent throughout the industry. These PCs may be blended with other polymers, among which PC / ABS (Polycarbonate / Acrylonitrile-Butadiene-Styrene) and PC / SAN (Polycarbonate / Styrene-Acrylonitrile) blend resins are typical. These blend resins are excellent in processability and mechanical strength, and are widely used in various fields including automobiles and electric / electronic parts.

PC-based resins such as PC, PC / ABS, or PC / SAN blend resins generally use impact modifiers as additives to improve impact resistance.

Impact modifiers are MBS-based (MMA-Butadiene-Styrene), acrylic-based, ABS-based polymer rubber-based graft polymerization; Thermoplastic polymers of CPE and EVA; And inorganic impact modifiers coated with stearin on calcium carbonate as an inorganic system.

Among them, the use of MBS-based impact modifiers is common, and for example, the US patent

3,761,455, 4,443,586, 5,204,406, 5,294,659 and 5,599,854, and the like. In order to have a core-shell structure and a heterogeneous structure, MBS-based graft copolymers are prepared by emulsion polymerization divided into 2 and 4 steps, and applied to PC-based resins. Is disclosed.

Among PC-based resins, PC-based resins such as PC / ABS or PC / SAN generally use phosphorus-based flame retardants. At this time, the phosphorus-based flame retardant lowers the viscosity of the continuous phase and causes coalescence of the dispersed phase, thereby deteriorating the processability, impact strength and gloss properties of the resin. In order to solve this problem, the use of a large-diameter MBS-based impact modifier has been proposed, and as a result, the impact resistance of the PC blend resin can be significantly improved.

However, when a large-diameter MBS-based impact modifier is applied to a PC-based resin, the PC-only resin and the PC- blend resin show different aspects. That is, when a large-diameter MBS-based impact modifier is applied to a PC blend resin such as PC / ABS and PC / SAN, the impact resistance is improved, but when applied to a PC-only resin, the distance between the particles of the MBS impact modifier increases and the impact is reduced. The effect of dispersing was lowered, so that a sufficient level of impact resistance could not be secured, and this occurred more severely at low temperatures.

Accordingly, US Patent Publication No. 2011-0160338 and Registration No. 7,524,898 mention that it is possible to improve the impact resistance of a PC by applying an impact modifier having different particle sizes. However, the bimodal type using two types of MBS impact modifiers, such as small diameter and large diameter, has a complicated manufacturing method, and as a result of the actual process application, it uses a mixture of large and small diameters, rather than a synergistic effect. There was only an improvement effect.

US Patent Publication No. 2011-0160338, "FUNCTIONALIZED BIMODAL IMPACT MODIFIERS" U.S. Patent Registration No. 7,524,898, "Thermoplastic molding composition having improved toughness at low temperatures and surface appearance"

As a result of various studies to solve the above problems, the present inventors used a mixture of small-diameter acrylate-based crosslinked nanoparticles with large-diameter MBS-based nanoparticles at a low temperature that occurs in conventional polycarbonate-based resins. The present invention was completed by confirming that the impact strength reduction problem can be solved.

Accordingly, an object of the present invention is to provide an MBS-based impact modifier that can improve the impact resistance of a PC-based resin.

In addition, another object of the present invention is to provide a method of manufacturing the MBS-based impact modifier.

In addition, another object of the present invention is to provide a composition for a polycarbonate-based resin comprising the MBS-based impact modifier.

In order to achieve the above object, the present invention is an MBS system comprising 3 to 8 parts by weight of acrylate-based crosslinked nanoparticles having an average particle diameter of 1 to 150 nm, relative to 100 parts by weight of MBS-based nanoparticles having an average particle diameter of 300 to 350 nm. Provide impact modifiers.

In addition, the present invention

Preparing an MBS-based nanoparticle latex having an average particle diameter of 300 to 350 nm;

Preparing an acrylate-based crosslinked nanoparticle latex having an average particle diameter of 1 to 150 nm;

Adding an acrylate-based crosslinked nanoparticle latex to the MBS-based nanoparticle latex, mixing and aggregating to prepare a slurry; And

Drying step,

At this time, it provides a method for manufacturing an MBS-based impact modifier that mixes 3 to 8 parts by weight of acrylate-based crosslinked nanoparticles with respect to 100 parts by weight of MBS-based nanoparticles.

In addition, the present invention provides a polycarbonate-based resin composition comprising the MBS-based impact modifier.

At this time, the polycarbonate-based resin is characterized in that the polycarbonate alone resin, PC / ABS or PC / SAN blend resin.

MBS-based impact modifier according to the present invention exhibits excellent impact resistance at low and normal temperatures in both polycarbonate-only resins, PC / ABS or PC / SAN blend resins.

Hereinafter, the present invention will be described in more detail.

The polycarbonate (hereinafter referred to as "PC")-based resins provided in this specification include all PC resins, PC / ABS, and PC / SAN blend resins unless otherwise specified.

MBS impact modifier

When an impact modifier having a large particle size is used to improve the impact resistance of the PC-based resin, the impact resistance is improved, but the impact strength at low temperature is greatly reduced. Accordingly, in the present invention, acrylic crosslinked nanoparticles are added to the MBS-based nanoparticles during the aggregation process, thereby improving bulk density and caking properties of the MBS-based nanoparticles. The acrylic cross-linked nanoparticles have excellent compatibility with PC-based resins, and are quickly and evenly dispersed in the PC-based resin matrix, thereby dispersing the impact with the MBS-based nanoparticles with a high specific surface area, thereby improving the impact strength.

The impact modifier presented in the present invention is a mixture of MBS-based nanoparticles and acrylate-based crosslinked nanoparticles, wherein the MBS-based impact modifier has an average particle diameter of 300 to 350 nm, and the acrylate-based crosslinked nanoparticles have an average particle diameter. 1 to 150 nm.

As suggested in the above range, the acrylic nanoparticles have a smaller size compared to the MBS nanoparticles, thereby reducing the distance between the MBS nanoparticles. In other words, if the MBS-based nanoparticles are large, the distance between the particles is far and the impact dispersing effect is lowered, but the acrylic nanoparticles are well dispersed therebetween to shorten the distance between the particles, thereby making it possible to use it as an impact modifier. Do.

That is, the MBS-based nanoparticles have excellent dispersibility between particles by the composition (ie, MMA) introduced in the MBS graft step, which is also well mixed with the acrylic crosslinked nanoparticles, due to the excellent compatibility with PC resin Overall, the specific surface area can be improved to disperse the impact, thereby improving the low-temperature impact strength.

Specifically, MBS-based nanoparticles are conjugated diene-based rubber polymer core; And surrounding the core, wherein the alkyl (meth) acrylate and the ethylenically unsaturated aromatic monomer have a structure composed of a graft polymerized shell.

The conjugated diene-based rubber polymer core may use a conjugated diene-based monomer alone or, if necessary, further include an ethylenically unsaturated aromatic monomer and a crosslinkable monomer as a comonomer.

The conjugated diene-based monomer is not particularly limited in the present invention, but may be, for example, butadiene, isoprene, chloroisoprene, and the like, preferably butadiene.

The ethylenically unsaturated aromatic monomer may be one selected from the group consisting of styrene, alphamethylstyrene, isopropenylnaphthalene, vinylnaphthalene, styrene substituted with C1 to C3 alkyl groups, halogen substituted styrene, and combinations thereof. In this case, the ethylenically unsaturated aromatic monomer is used in a total amount of up to 32% by weight or less in all the monomers constituting the core.

In addition, the crosslinkable monomer is, for example, divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, arylmeth Acrylate and 1,3-butylene glycol diacrylate, and the like. At this time, the crosslinkable monomer is used at a maximum of 3% by weight or less in all the monomers constituting the core.

The conjugated diene-based rubber polymer core having the above-described composition is wrapped with a shell, wherein the shell is graft polymerized with an alkyl (meth) acrylate and an ethylenically unsaturated aromatic monomer.

Alkyl (meth) acrylates are methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and these It may be one selected from the group consisting of a combination, preferably methyl methacrylate is used.

The ethylenically unsaturated aromatic monomer follows the composition mentioned in the above core, and styrene is preferably used.

The method of manufacturing the core-shell structured MBS-based nanoparticles as described above is not particularly limited in the present invention, and a known emulsion polymerization can be used.

Specifically, the MBS-based nanoparticles include: (a) preparing a conjugated diene-based rubber polymer core; (b) In the presence of 50 to 80% by weight of the prepared core, 20 to 50% by weight of an alkyl (meth) acrylate and 0 to 30% by weight of an ethylenically unsaturated aromatic monomer are added to perform graft polymerization to perform core-shell A graft copolymer having a structure is obtained.

The content of the conjugated diene-based rubber polymer core, alkyl (meth) acrylate, and ethylenically unsaturated aromatic monomer is a content capable of sufficiently satisfying a desired level of impact resistance, particularly impact strength at low temperatures, if the If the content is outside the above range, such an effect cannot be expected, and thus it is appropriately used within the above range.

The graft polymerization reaction is preferably performed for 3 to 5 hours at a temperature of 40 to 80 ℃ by adding an initiator, an emulsifier and various additives necessary for emulsion polymerization. At this time, various compositions and reaction conditions are not particularly limited in the present invention, and follow what is known in this field.

MBS-based nanoparticles are prepared in a slurry form to have a particle size in a range within a range using a coagulant such as an acid or a salt such as sulfuric acid or hydrochloric acid after graft polymerization through emulsion polymerization.

The MBS-based nanoparticles have a particle size of 300 to 350 nm and a large particle size as an impact modifier. If the particle size is less than the above range, the effect of improving the impact strength cannot be expected. On the contrary, if it is outside the above range, it is difficult to secure stability when manufacturing the impact modifier, and a large amount of coagulum occurs during polymerization or the reactor hardens. As it may occur, it is appropriately used within the above range.

The MBS-based nanoparticles described above are mixed with acrylate-based crosslinked nanoparticles for use as an impact modifier.

The term "acrylate-based crosslinked nanoparticles" as used herein means that the crosslinking degree is high as an acrylate-based nanosize particle unless otherwise specified.

The acrylate-based crosslinked nanoparticles have a particle size smaller than that of the MBS-based nanoparticles, and are mixed with the MBS-based nanoparticles and uniformly dispersed in the matrix of the PC-based resin when used as an impact modifier, due to the high specific surface area Excellent impact resistance, especially improves impact strength at low temperatures.

The acrylate-based crosslinked nanoparticles are copolymers of alkyl methacrylate, alkyl acrylate, and vinyl-based monomers having an alkylene oxide group.

Preferably, the acrylate-based crosslinked nanoparticles are 80 to 95% by weight of alkyl methacrylate, 1 to 15% by weight of alkyl acrylate; And 1 to 10% by weight of a vinyl-based monomer having an alkylene oxide group.

The content of the vinyl-based monomer having the alkyl methacrylate, the alkyl acrylate, and the alkylene oxide group is a content capable of sufficiently satisfying a desired level of impact resistance, particularly impact strength at low temperatures, if the content is If it is outside the above range, such an effect cannot be expected, and thus it is appropriately used within the above range. According to a preferred experimental example of the present invention, when the content of the vinyl monomer having an alkylene oxide group is outside the above range (Comparative Examples 7 and 8), it was not possible to achieve a sufficient level of impact strength at low temperature.

The alkyl methacrylate is one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate and combinations thereof. It is possible, preferably methyl methacrylate.

In addition, the alkyl acrylate may be one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, and combinations thereof, preferably butyl Acrylate.

And, the vinyl monomer having an alkylene oxide group is ethylene glycol monoacrylate, ethylene glycol monomethacrylate, propylene glycol monoacrylate, propylene glycol monomethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, One type selected from the group consisting of propylene glycol diacrylate, propylene glycol dimethacrylate, and combinations thereof is possible, and preferably, ethylene glycol dimethacrylate is used.

The production of the acrylate-based crosslinked nanoparticles according to the present invention is not particularly limited in the present invention, and can be polymerized by applying various methods such as emulsion polymerization, bulk polymerization, suspension polymerization, solution polymerization, etc., preferably performed by emulsion polymerization. do.

During the emulsion polymerization, the monomer may further include an initiator, an emulsifier, and additives such as molecular weight regulators, activators, redox catalysts, and ionic water commonly known in the art. At this time, the specific composition and reaction conditions required for the polymerization are not particularly limited in the present invention, and follow what is known in this field.

These acrylate-based crosslinked nanoparticles have a small particle size range of 1 to 150 nm, preferably 10 to 100 nm, more preferably 30 to 60 nm, and have an average particle diameter of MBS-based nanoparticles having a large diameter of 300 nm or more. Mix.

If the particle size is less than the above range, there is a possibility that aggregation occurs between acrylate-based crosslinked nanoparticles. Conversely, if the particle size is outside the above range, it is not expected to improve impact resistance at a low temperature.

The MBS-based impact modifier according to the present invention is used by mixing MBS-based nanoparticles and acrylate-based crosslinked nanoparticles as described above in a constant content ratio. Specifically, acrylate-based crosslinked nanoparticles are mixed in an amount ratio of 3 to 8 parts by weight with respect to 100 parts by weight of the MBS-based nanoparticles. According to a preferred experimental example of the present invention, if the content of the acrylate-based crosslinked nanoparticles is less than the above range, the problem of lowering the impact strength at low temperature cannot be solved (see Comparative Example 5), and if it exceeds the above range, the impact modifier It has low bulk density and low caking properties, which also has low impact strength at low temperatures.

MBS impact modifier manufacturing method

The manufacture of the MBS-based impact modifier is not particularly limited in the present invention, and the powder is prepared through each polymerization process and manufactured through a conventional mixing process.

In one example, the MBS-based impact modifier according to the present invention

(S1) preparing MBS-based nanoparticle latex having an average particle diameter of 300 to 350 nm;

(S2) preparing an acrylate-based crosslinked nanoparticle latex having an average particle diameter of 1 to 150 nm;

(S3) adding an acrylate-based crosslinked nanoparticle latex to the MBS-based nanoparticle latex, mixing and aggregating to prepare a slurry; And

(S4) It is manufactured through a step of drying.

The steps S1 to S3 follow the above.

In addition, the mixing of (S3) is not particularly limited in the present invention, and a mixing method using a conventional mixer may be used.

The drying of (S4) is performed at a temperature at which the dispersion can be sufficiently removed, and if necessary, it is performed under reduced pressure. For example, it is performed at 30 to 80 ° C for 2 to 72 hours.

PC resin composition

In particular, the MBS-based impact modifier of the present invention can be used as an impact modifier for PC-based resins.

Preferably, the PC-based resin composition according to the present invention comprises 90 to 98% by weight of PC-based resin, and 2 to 10% by weight of impact modifier. At this time, the PC-based resin includes all of PC resin, PC / ABS, and PC / SAN blend resin.

The PC-based resin composition is a flame retardant, lubricant, antioxidant, light stabilizer, reaction catalyst, release agent, pigment, antistatic agent, conductivity imparting agent, EMI shielding agent, magnetic imparting agent, crosslinking agent, antibacterial agent, processing aid, metal deactivator , Inhibitors, fluorine-based anti-loading agents, inorganic fillers, glass fibers, anti-friction wear-resistant agent and coupling agent may further include at least one selected from the group consisting of.

The method of melt-kneading and processing the PC-based resin and the impact modifier and other additives is not particularly limited, but as a specific example, after primary mixing in a supermixer, a twin screw extruder, a single screw extruder, a roll mill, a kneader or a chestnut mixer, etc. It can be melt-kneaded using one of the compounding processing machines, pellets are obtained with a pelletizer, and then dried sufficiently with a dehumidifying dryer or a hot air dryer, followed by injection processing to obtain a final molded product.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely illustrative of the present invention, and it is apparent to those skilled in the art that various changes and modifications can be made within the scope and technical scope of the present invention. It is natural that changes and modifications fall within the scope of the appended claims.

[Example]

Examples 1-3 and Comparative Examples 1-8: Preparation of MBS impact modifier

(1) Preparation of MBS-based nanoparticles

<Production of conjugated diene-based rubber polymer core>

75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor (autoclave), 75 parts by weight of 1,3-butadiene as a monomer, 2.0 parts by weight of potassium oleate as an emulsifier, 1.2 parts by weight of sodium sulfate as an electrolyte, and 3 as a molecular weight regulator 0.3 parts by weight of dodecyl mercaptan (TDDM), 0.4 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as an initiator, reacted at a reaction temperature of 70 ° C. to a polymerization conversion rate of 30 to 40%, and 1, 25 parts by weight of 3-butadiene and 0.4 parts by weight of potassium oleate were added and the reaction was terminated when the polymerization conversion was 95%. The time required for polymerization was 23 hours, and the average particle diameter was 300 nm.

<Core-shell manufacturing>

After 70 parts by weight (solid content) of the rubber latex prepared above was introduced into a closed reactor, the temperature was increased to 70 ° C. with nitrogen filling and maintained. Sodium pyrophosphate 0.1 part by weight dextrose 0.2 part by weight, ferrous sulfide 0.002 part by weight was charged to the reactor.

A monomer emulsion was prepared by mixing 25.5 parts by weight of methyl methacrylate, 4.5 parts by weight of styrene, 0.3 parts by weight of potassium oleate, 0.1 parts by weight of cumene hydroperoxide, and 20 parts by weight of ion-exchanged water in a separate mixing device. The monomer emulsion was continuously added to the reactor over 2.5 hours and aged at the same temperature for 1 hour to complete the reaction. After the polymerization was completed, a latex having a particle size of 315 nm, a polymerization conversion rate of 98%, and a solid content of 42% was obtained.

(2) Preparation of acrylic crosslinked nanoparticle latex

The weight percentages of the following compounds are based on 100% by weight of the total monomer used for the preparation of acrylate-based crosslinked nanoparticles.

88% by weight of methyl methacrylate, 7% by weight of butyl acrylate, and 5% by weight of ethylene glycol dimethacrylate, 0.03 parts by weight of ethylenediaminetetrasodium acetate, 0.002 parts by weight of ferrous sulfate, and sodium formaldehyde sulfoxyl Rate 0.2 parts by weight, sodium lauryl sulfate 2 parts by weight, alkenyl succinic acid potassium salt (alkenyl succinic acid potassium salt) 2.5 parts by weight, ion-exchanged water 160 parts by weight and 0.2 parts by weight of t-butyl hydroperoxide 60 Polymerization was carried out at 6 ° C for 6 hours to obtain an acrylate-based crosslinked nanoparticle latex having a polymerization conversion rate of 99% and an average particle size of 45 nm.

(3) MBS impact modifier powder production

0.5 parts by weight of an antioxidant (Irganox-245) emulsified in 100 parts by weight of the MBS-based nanoparticle latex prepared in (1) was added, and after adding acrylate-based crosslinked nanoparticle latex prepared in (2), sulfuric acid was stirred. The aqueous solution was added and aggregated to obtain a slurry. After aging at 80 ° C., the copolymer and water were separated, followed by dehydration drying to obtain an impact modifier powder.

MBS-based impact modifiers were prepared through the steps of (1) to (3), wherein the content of each composition and the obtained particles and physical properties are shown in Table 1 below. At this time, the particle size was measured using DLS (Dynamic Light Scattering).

Furtherance
(Parts by weight) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative example
7 Comparative Example 8 A BD 70 70 70 - 70 70 70 70 70 70 70 MMA 25.5 25.5 25.5 - 25.5 25.5 25.5 25.5 25.5 25.5 25.5 SM 4.5 4.5 4.5 - 4.5 4.5 4.5 4.5 4.5 4.5 4.5 B MMA 88 86 91 - - 88 88 88 88 91 80 EA - 9 - - - - - - - - - BA 7 - 7 - - 7 7 7 7 9 5 EGDMA 5 5 2 - - 5 5 5 5 - 15 Average particle diameter
(nm) A 315 315 315 - 315 100 200 315 315 315 315 B 45 45 45 - - 45 45 45 45 47 45 A / B mixing ratio 100: 5 100: 5 100: 5 - - 100: 5 100: 5 100: 2 100: 10 100: 5 100: 5 week)
A: MBS nanoparticles
B: acrylate-based nanoparticles
BD: Butadiene
MMA: methyl methacrylate
SM: Styrene
EA: ethyl acrylate
EDGMA: Ethylene glycol dimethacrylate

(4) Properties of impact modifier

Aggregation properties for the impact modifier powders of Examples 1 to 3 and Comparative Examples 1 to 8 were prepared in the following manner, and are summarized in Table 2 below.

-Bulk density (g / ml): measured according to ASTMD1895.

-Caking characteristics (sec): 20 g of dried powder is placed in a self-made cylindrical container, left for 2 hours under a load of 40 kg, and then the obtained cake is shaken while vibrating using an vibrator. The time for this collapse was measured. At this time, the caking property is excellent as the collapse time is short.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Bulk density
(g / ml) 0.411 0.402 0.414 - 0.345 0.431 0.424 0.371 0.422 0.410 0.396 Caking
Test (sec) 25 29 28 - 581 23 25 122 22 38 22

Looking at Table 2, in the case of Comparative Example 2 in which acrylate-based crosslinked nanoparticles were not included or Comparative Example 5 having a low content, bulk density and caking properties were deteriorated.

In the case of the powder of Comparative Example 7, the bulk density and the caking test showed excellent results, but the impact strength at a low temperature was very low, which was an alkylene oxide group in the composition constituting the acrylate-based nanoparticles. It is attributable to the absence of the vinyl monomer to have.

Experimental Example: Preparation of polycarbonate resin and measurement of physical properties

(1) Preparation of polycarbonate resin composition

The impact modifiers of Examples 1 to 3 and Comparative Examples 1 to 8 prepared above were respectively prepared according to the input amounts shown in Tables 3 and 4 below, and polycarbonate resins and PC / SAN resins, respectively.

<Polycarbonate resin>

As shown in Table 3, polycarbonate PC1300-15 (manufactured by LG Chem) and MBS-based impact modifier powders prepared in Examples and Comparative Examples were added 0.1 parts by weight of lubricant and 0.05 parts by weight of antioxidant per 100 parts by weight in total. And mixed. This was prepared in pellet form using a 40-pie extrusion kneader at a cylinder temperature of 300 ° C., and injected into the pellet to prepare a physical property specimen, and the following physical properties were measured and shown in Table 3. At this time, the content of the polycarbonate and MBS-based impact modifier powder is shown in Table 3.

<PC / SAN blend resin>

Polycarbonate PC1300-22 (manufactured by LG Chem), MBS-based impact modifier powder prepared in Examples and Comparative Examples, styrene-acrylonitrile copolymer 92HR (manufactured by LG Chem), and flame retardant in total weight of 100 0.5 parts by weight of lubricant and 0.3 parts by weight of antioxidant were added to the parts and mixed. It was prepared in pellet form using a 40-pie extrusion kneader at a cylinder temperature of 250 ° C., and injected into the pellet to prepare a physical property specimen, and the following physical properties were measured and shown in Table 4. At this time, the content of the polycarbonate and MBS-based impact modifier powder is shown in Table 4.

<Measurement of properties>

-Izod impact strength: 1/8 inch and 1/4 inch notched specimens were evaluated by ASTM D256 test method. At this time, the measurement was performed in both chambers maintaining room temperature and -40 ° C. After aging 1 / 8-inch and 1 / 4-inch notched specimens at -40 ° C in each chamber for 6 hours, the specimens were taken out and ASTM D256 tested. It was evaluated by the method.

PC resin Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 PC 96 96 96 100 96 96 96 96 96 96 96 Impact modifier 4 4 4 4 4 4 4 4 4 4 Impact strength at room temperature (23 ℃, kgfcm / cm) 1/8 " 81.5 80.9 80.7 89.1 82.0 79.7 81.2 80.8 77.9 79.7 78.2 1/4 " 72.6 73.5 71.3 N.B. 70.3 71.8 71.6 72.2 71.2 70.7 71.1 Low temperature impact strength (-40 ℃, kgf · cm / cm) 1/8 " 42.5 40.2 41.3 7.5 22.6 28.8 48.7 27.5 32.0 32.6 29.1 1/4 " 18.3 18.0 18.0 6.7 15.1 15.7 19.2 15.6 16.2 16.0 14.7

PC / SAN blend resin Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 PC 63 63 63 70 63 63 63 63 63 63 63 SAN 14 14 14 15 14 14 14 14 14 14 14 Flame retardant 14 14 14 15 14 14 14 14 14 14 14 Impact modifier 9 9 9 - 9 9 9 9 9 9 9 Impact strength at room temperature (23 ℃, kgfcm / cm) 1/8 " 65.1 64.0 64.3 6.1 63.8 13.9 44.8 63.0 45.5 59.5 54.4 1/4 " 23.3 25.1 24.6 4.0 13.9 13.0 20.3 18.2 28.8 20.3 18.8

Referring to Table 3 and Table 4, it can be seen that the impact strength is improved in both the PC and PC / SAN resin to which the impact modifiers of Examples 1 to 3 according to the present invention are applied. In particular, looking at the results of Table 3, it can be seen that the problem of lowering the impact strength at low temperatures, which occurred in the conventional PC sole resin, is solved by the use of the impact modifier according to the present invention.

In comparison, when the acrylate nanoparticles were not used (Comparative Example 2) or used less (Comparative Example 5) and the impact modifier was used, the impact strength at low temperature was very poor, which did not use EDGMA (Comparative Example 7). ), When used in excess (Comparative Example 8), similar results were obtained.

MBS-based impact modifier according to the present invention can be used as an additive in a polycarbonate-based resin composition to produce molded articles having excellent impact resistance at low and normal temperatures.

Claims (15)

With respect to 100 parts by weight of MBS-based nanoparticles having an average particle diameter of 300 to 350 nm,
A polycarbonate-based resin composition comprising an MBS-based impact modifier comprising 3 to 8 parts by weight of acrylate-based crosslinked nanoparticles having an average particle diameter of 1 to 150 nm. According to claim 1,
The MBS-based nanoparticles are characterized by being graft polymerized by adding 20 to 50% by weight of an alkyl (meth) acrylate and 0 to 30% by weight of an ethylenically unsaturated aromatic monomer to 50 to 80% by weight of a conjugated diene-based rubber polymer core. Polycarbonate-based resin composition. According to claim 2,
The conjugated diene-based rubber polymer core is a polycarbonate-based resin characterized in that it is an emulsion of 65 to 100% by weight of a conjugated diene-based monomer, 0 to 32% by weight of an ethylenically unsaturated aromatic monomer, and 0 to 3% by weight of a crosslinkable monomer. Composition. According to claim 2,
The conjugated diene-based rubber polymer core is a polycarbonate-based resin composition, characterized in that one type selected from the group consisting of butadiene, isoprene, chloroisoprene and combinations thereof. According to claim 2,
The ethylenically unsaturated aromatic monomer includes one selected from the group consisting of styrene, alphamethylstyrene, isopropenylnaphthalene, vinylnaphthalene, styrene substituted with C1 to C3 alkyl groups, styrene substituted with halogen, and combinations thereof. Polycarbonate-based resin composition, characterized in that. According to claim 3,
The ethylenically unsaturated aromatic monomer includes one selected from the group consisting of styrene, alphamethylstyrene, isopropenylnaphthalene, vinylnaphthalene, styrene substituted with C1 to C3 alkyl groups, styrene substituted with halogen, and combinations thereof. Polycarbonate-based resin composition, characterized in that. According to claim 3,
The crosslinkable monomer is divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, arylmethacrylate, 1 , 3-Butylene glycol diacrylate, and a polycarbonate-based resin composition comprising one selected from the group consisting of these. According to claim 2,
The alkyl (meth) acrylate is methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and A polycarbonate-based resin composition comprising one selected from the group consisting of these. According to claim 1,
The acrylate-based crosslinked nanoparticles are alkyl methacrylate 80 to 95% by weight, alkyl acrylate 1 to 15% by weight; And 1 to 10% by weight of a vinyl monomer having an alkylene oxide group copolymerized therein. The method of claim 9,
The alkyl methacrylate is selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate and combinations thereof. It characterized in that it comprises a polycarbonate-based resin composition. The method of claim 9,
The alkyl acrylate is characterized in that it comprises one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate and combinations thereof. Polycarbonate resin composition. The method of claim 9,
The vinyl monomer having an alkylene oxide group is ethylene glycol monoacrylate, ethylene glycol monomethacrylate, propylene glycol monoacrylate, propylene glycol monomethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene A polycarbonate-based resin composition comprising one selected from the group consisting of glycol diacrylate, propylene glycol dimethacrylate, and combinations thereof. Preparing an MBS-based nanoparticle latex having an average particle diameter of 300 to 350 nm;
Preparing an acrylate-based crosslinked nanoparticle latex having an average particle diameter of 1 to 150 nm;
Adding an acrylate-based crosslinked nanoparticle latex to the MBS-based nanoparticle latex, mixing and aggregating to prepare a slurry;
Drying the slurry to prepare an MBS-based impact modifier; And
Including; mixing by adding a polycarbonate-based resin to the MBS-based impact modifier;
At this time, the method for producing the polycarbonate-based resin composition of claim 1, which is mixed with 3 to 8 parts by weight of acrylate-based crosslinked nanoparticles with respect to 100 parts by weight of MBS-based nanoparticles. The method according to any one of claims 1 to 12,
The polycarbonate-based resin composition
90 to 98% by weight of a polycarbonate resin, and
A polycarbonate-based resin composition comprising 2 to 10% by weight of the MBS-based impact modifier. The method of claim 14,
The polycarbonate-based resin is a polycarbonate-based resin composition, characterized in that the polycarbonate resin, PC / ABS, or PC / SAN blend resin.