KR20130090369A - Mbs based graft copolymer and polycarbonate resin composition - Google Patents

Abstract

PURPOSE: An MBS-based graft copolymer is provided to prevent the loss of an impact strength and whiteness under a waterproof and heatproof condition when applied to a polycarbonate resin. CONSTITUTION: An MBS-based graft copolymer has a core-shell type structure. The core and the shell is obtained by a polymerization under the presence of a carboxyl emulsifier, a sulfonate emulsifier, and a phosphate emulsifier. The carboxyl emulsifier is either or both potassium salt and/or sodium salt of an oleic acid. The reinforcing agent for a polycarbonate resin consists of the MBS-based graft copolymer. A polycarbonate resin composition includes 4-10 wt% of the reinforcing agent and 90-96 wt% of the polycarbonate resin.

Description

MBS based graft copolymer and polycarbonate resin composition

The present invention relates to a MBS graft copolymer and a polycarbonate resin composition, and more particularly, when applied to a polycarbonate resin by providing a core-shell type graft copolymer obtained by polymerization under a specific emulsifier combination. The present invention relates to an MBS-based graft copolymer and a polycarbonate resin composition including the same, in which impact resistance and whitening degree are not lowered under heat and humidity conditions.

Polycarbonate (PC) is known as a resin having excellent impact resistance, electrical properties, and heat resistance, and is widely used as an interior and exterior material throughout the industry, such as widely used in the manufacture of molded articles for electric and electronic products including automobiles. However, polycarbonate has high melt viscosity and poor moldability, and has disadvantages such as impact resistance and thickness dependency.

In order to compensate for these shortcomings and to improve impact resistance, JPA S56-45946, JPA S56-45947, and EP465792 prepared and mixed acrylic impact modifiers. However, acrylic impact modifiers have a higher glass transition temperature than butadiene-based or silicone-based impact modifiers, resulting in a lack of an effect of improving low-temperature impact strength and a decrease in colorability.

Korean Patent Laid-Open Publication No. 2006-0036523 proposes a method for improving low-temperature impact strength and colorability by providing a silicone-acrylic impact modifier, but the effect of improving colorability is insignificant.

In addition, JPB S36-14035 and JPA S48-54160 mixed polyester resins such as polyethylene terephthalate or polybutylene terephthalate in order to supplement the chemical resistance of the polycarbonate, but the impact resistance is low. It was necessary.

JPB H1-34463 discloses a method of improving the impact strength and colorability by adding an acrylic impact modifier having a multi-layered structure to a polycarbonate and polyester resin mixture. However, the effect of improving the coloring properties, particularly low temperature impact strength, is insufficient.

In addition, Korean Patent Publication No. 2001-0070975 discloses a resin composition having excellent impact resistance and molding appearance through controlling the particle size distribution and rubber content of the impact modifier.

On the other hand, in many of the above-described prior art, the effect that the impact resistance and the degree of whitening does not decrease under the high temperature and high humidity humidity heat conditions have not been disclosed.

Accordingly, an object of the present invention is to provide an MBS-based graft copolymer and a polycarbonate resin composition including the same, in which impact resistance and whitening degree are not lowered even under damp heat conditions.

In order to achieve the above object, according to the present invention,

As a core-shell type graft copolymer,

The core and the shell are obtained by polymerizing under a carboxyl emulsifier, a sulfonate emulsifier and a phosphate emulsifier, to provide an MBS graft copolymer.

In addition, according to the present invention, there is provided an impact modifier for polycarbonate resin, characterized in that consisting of the above-described MBS graft copolymer.

Furthermore, according to the present invention, there is provided a polycarbonate resin composition comprising 4 to 10% by weight of the above-described impact modifier and 90 to 96% by weight of a polycarbonate resin.

Hereinafter, the present invention will be described in detail.

In the present invention, by providing a core-shell type graft copolymer obtained by polymerizing under a specific emulsifier combination, the impact resistance and the degree of whitening of the MBS-based graft copolymer are not lowered even when applied to a polycarbonate resin even under damp-heat conditions. It provides technical features.

Specifically, in the present invention, the MBS-based graft copolymer is composed of a core-shell type, and the core and the shell are each obtained by polymerization under three emulsifiers of a carboxyl emulsifier, a sulfonate emulsifier, and a phosphate emulsifier. It features.

For example, the core may be a diene rubber polymer latex obtained by adding a carboxyl emulsifier and a sulfonate emulsifier at a point of polymerization conversion of less than 60% and a phosphate emulsifier at a point of polymerization conversion of 60 to 75%. . In another example, the core is a diene rubber polymer latex obtained by adding a carboxyl emulsifier and a sulfonate emulsifier at a polymerization conversion rate of 45% or less and a phosphate emulsifier at a polymerization conversion point of 60 to 70%. Can be.

For example, the shell may be a graft polymer obtained by adding a carboxyl emulsifier and a sulfonate emulsifier at a point of less than 65% polymerization conversion and a phosphate emulsifier at a point of 65 to 75% polymerization conversion. In addition, the shell may be a graft polymer obtained by adding a carboxyl emulsifier and a sulfonate emulsifier at a point of less than 60% polymerization conversion, and a phosphate emulsifier at a point of 65 to 70% polymerization conversion.

Here, the carboxyl emulsifier may be, for example, at least one selected from potassium salts and sodium salts of oleic acid, and due to the use of the carboxyl emulsifier, a large amount of carboxylic acid is generated when the acid is aggregated after preparing the graft copolymer. When considering the mechanism for promoting hydrolysis of the resin when applied to the polycarbonate resin may be in the range of 0.1 to 0.5 parts by weight, or 0.2 to 0.3 parts by weight based on 100 parts by weight of the conjugated diene compound constituting the core.

The sulfonate-based emulsifier may be, for example, at least one selected from sodium salts, calcium salts, and amine salts of alkali phenyl disulfonate alkali phenyl, and minimizes the carboxyl emulsifier content to prevent decomposition of polycarbonate chains. Considering the role, it may be in the range of 0.1 to 0.5 parts by weight, or 0.2 to 0.3 parts by weight based on 100 parts by weight of the conjugated diene-based compound constituting the core.

The phosphate-based emulsifier may be, for example, at least one selected from sodium diethylhexyl phosphate , phosphonated polyoxyethylene alcohol, and phosphonated polyoxyethylene phenol. As a specific example, the polyoxyethylene-containing compound may be used in the form of a product prepared in the form of a free acid, sodium salt, or amine salt. As another example, it may be a polyoxyethylene alkylether phosphate type including a polyoxyethylene alkyl ether having a chemical formula of RO (C ₂ H ₄ O) n H (R: C 12 to C 14, n: 2 to 18).

The phosphate-based emulsifier is 0.1 to 0.5 parts by weight based on 100 parts by weight of the conjugated diene-based compound constituting the core, in consideration of the fact that the acid is difficult to aggregate by the use of the sulfonate-based emulsifier and requires an excessive flocculant It may be in the range of 0.3 to 0.5 parts by weight.

In the present invention, the conjugated diene-based compound constituting the diene-based rubbery polymer latex may be used alone or copolymerized with other compounds, for example, 1,3-butadiene, isoprene, chloroprene, and pyrrylene. As the other compounds, aromatic vinyl compounds such as styrene and α-methylstyrene, and vinyl cyan compounds such as acrylonitrile, methacrylonitrile, and ethacrylonitrile may be used, based on 100 parts by weight of the conjugated diene-based compound. 20 parts by weight or less can be used.

The method of dosing the compound may be a batch dose or a multistage dose.

An initiator may be added to the core during manufacture. For example, the initiator may be a water-soluble persulfate initiator such as potassium persulfate, sodium persulfate or ammonium persulfate, and may be used within a range of 0.2 to 1 part by weight based on 100 parts by weight of the conjugated diene compound.

Molecular weight regulators may be added when the core is manufactured. For example, the molecular weight regulator may be mercaptans, it can be used within the range of 0.2 to 1 parts by weight based on 100 parts by weight of the conjugated diene-based compound constituting the core.

An electrolyte may be added when the core is manufactured. For example, the electrolyte may include KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , Na ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO _4, or Na ₂ HPO ₄ may be used alone or in combination of two or more thereof. The electrolyte may be used within the range of 0.2 to 2 parts by weight based on 100 parts by weight of the conjugated diene-based compound constituting the core.

In addition, ion-exchanged water may be used when preparing the core. For example, the ion-exchanged water may be used within the range of 65 to 100 parts by weight based on 100 parts by weight of the conjugated diene-based compound constituting the core.

The polymerization temperature for preparing the core may be adjusted according to the gel content and swelling degree of the diene rubbery polymer latex, and the selection time and the timing of administration of the polymerization initiator should also be considered. For example, it can be carried out within a temperature range of 40 to 85 ℃.

Specifically, the core may provide a rubbery polymer latex having a particle size or an average particle diameter of 2500 to 3500 Pa, or 2800 to 3300 Pa, and a gel content in the range of 65 to 85% under non-agglomeration after the coagulation step after emulsion polymerization. .

The MBS graft copolymer, for example, may be composed of 40 to 80% by weight of the core and 20 to 60% by weight of the shell. As another example, it may consist of 50 to 75% by weight of the core and 25 to 50% by weight of the shell. Within the above range, the latex constituting the core sufficiently increases the graft rate and improves dispersibility in the resin when used in the polycarbonate resin and improves the impact strength as well as prevents agglomeration at the end of the polymerization and aggregation.

The shell may be a polymer of 40 to 80% by weight of the core, and 19 to 40% by weight of the alkyl methacrylate compound and 1 to 20% by weight of the aromatic vinyl compound surrounding the core. As another example, the shell may be a polymer of 50 to 75% by weight of the core, and 22 to 40% by weight of the alkyl methacrylate compound and 3 to 10% by weight of the aromatic vinyl compound surrounding the core.

The alkyl methacrylate compound is not specified as long as it gives a compatibility with the matrix resin to increase the impact strength, for example, selected from the group consisting of methyl methacrylate, ethyl methacrylate, and butyl methacrylate. It may be one or more.

In addition, the amount used may be 19 to 40% by weight, or 22 to 40% by weight to appropriately transmit the impact from the outside to the core layer by reducing the colorability and thickness of the shell layer.

The aromatic vinyl compound is not specific as long as it has a high refractive index and improves colorability. For example, the aromatic vinyl compound may be at least one selected from the group consisting of styrene, alphamethylstyrene, vinyltoluene, and 3-4-dichlorostyrene.

In addition, the amount used may be 1 to 20% by weight, or 3 to 10% by weight in consideration of improving colorability and compatibility with the matrix resin.

Furthermore, the shell may further include a vinyl cyan compound, an alkyl acrylate or a mixture thereof. For example, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, acrylonitrile, and the like may be used, and the amount of use thereof may be The total amount of the latex and the compound constituting the shell may be 2 parts by weight or less based on 100 parts by weight.

The method of adding the compound can be either batch or multi-stage addition, for example, it can be continuously administered for 2 to 5 hours to minimize the generation of coagulum and to improve the graft reaction, such as to control the heat and increase the reproducibility of the reaction. have.

The polymerization initiator used in the preparation of the shell is, for example, peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide and sodium formaldehyde sulfoxylate, ethylenediamine tetrasodium acetate, and sulfuric acid. It may be selected from oxidation-reduction catalysts such as iron, sodium pyrophosphate, dextrose and the like. The amount used may be in the range of 0.1 to 1 parts by weight based on 100 parts by weight of the total amount of latex and the compound constituting the shell.

The shell preparation may be performed including ion-exchanged water. As an example Ion-exchanged water may be used within the range of 10 to 40 parts by weight based on a total of 100 parts by weight of the latex and the compound constituting the shell.

Polymerization conditions for producing the shell may vary depending on the type of initiator, for example, may be carried out for 3 to 6 hours at a temperature of 45 ~ 80 ℃.

The core-shell type MBS graft copolymer thus obtained can be dried by an acid or salt aggregation process or a spray drying process.

Technically, in the present invention, the specific emulsifier input is minimized by using the sulfonate emulsifier in combination with the sulfonate-based emulsifier to minimize the amount of the carboxyl emulsifier used in the initial stage of the emulsion polymerization and the graft polymerization. Problems such as difficulty in coagulation and coagulation can be compensated by the addition of a phosphate-based emulsifier during the reaction. For reference, if the timing of the phosphate-based emulsifier is not appropriate during the reaction, the rubber particle diameter of the target level may not be made or the stability may be reduced.

The MBS graft copolymer may be improved in impact strength and whitening under moisture and heat conditions when used as an impact modifier against a thermoplastic resin such as polycarbonate resin.

For example, it is possible to provide a polycarbonate resin composition comprising 4 to 10 wt% of the impact modifier and 90 to 96 wt% of a polycarbonate resin.

As described above, according to the present invention, when applied to a polycarbonate resin, there is an effect of providing an impact modifier and a polycarbonate resin composition including the same, in which impact resistance and whitening are not lowered even under damp-heat conditions.

< Example  1>

i) Manufacture of rubber polymer latex

a) polymerization stage:

75 parts by weight of ion-exchanged water, 60 parts by weight of 1,3-butadiene as a compound, 0.2 parts by weight of potassium oleate salt as an emulsifier, 0.2 parts by weight of an alkali phenyl disulfonate salt (product name: Dofafax) in a nitrogen-substituted polymerization reactor (autoclave). part, 0.9 parts by weight of potassium carbonate (K ₂ CO ₃ ) as an electrolyte, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, and 0.3 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as an initiator After the reaction was carried out at a temperature of 70 ° C. to the point of polymerization conversion of 30 to 40%, 20 parts by weight of 1,3-butadiene was collectively administered, and the reaction was carried out at 70 ° C. to the point of polymerization conversion of 60%.

b) Additional polymerization stages:

20 parts by weight of the remaining 1,3-butadiene and 0.5 parts by weight of sodium diethylhexyl phosphate (product name: RHODAFAC) were collectively heated to 80 ° C, and the reaction was terminated when the polymerization conversion was 95%. The polymerization time was 23 hours, the gel content of the obtained rubbery polymer latex was 76%, and the particle size or average particle diameter was 3050 mm 3.

For reference, the gel content of the rubber latex solidified with dilute acid or metal salt, washed, dried in a vacuum oven at 60 ℃ for 24 hours, and then chopped the rubber mass with scissors, 1 g of rubber sections To 100 g of toluene was stored in a dark room at room temperature for 48 hours, and then measured by separating the sol and gel.

ii ) Graft  Copolymer production

A) polymerization step:

After adding 70 parts by weight (solid content) of the rubbery polymer latex to a closed reactor, the temperature was raised and maintained at 70 ° C with nitrogen filling. 0.1 parts by weight of sodium pyrophosphate, 0.2 parts by weight of dextrose, and 0.002 parts by weight of ferrous sulfide were introduced into the reactor at once. In a separate mixing device, 25.5 parts by weight of methyl methacrylate, 4.5 parts by weight of styrene, 0.1 parts by weight of potassium oleate, 0.1 parts by weight of alkali phenyl disulfonate sodium salt (trade name: Dofax), 0.1 parts by weight of cumene hydroperoxide, ions Compound emulsion was prepared by mixing 20 parts by weight of exchanged water. The compound emulsion was continuously added to the reactor over 2.5 hours.

B) add Graft  Copolymer Preparation Steps:

Immediately after the addition of the emulsion (at a polymerization conversion rate of 70%), 0.04 part by weight of cumene hydroperoxide and 0.2 part by weight of sodium diethylhexyl phosphate (product name: RHODAFAC) were added and aged at the same temperature for 1 hour to terminate the reaction. . After the completion of the polymerization, the particle diameter or the average particle diameter was 3200 mm 3, the polymerization conversion rate was 98%, and the solid content was 42%.

Flocculation stage:

An antioxidant was added to the obtained latex, coagulated with an aqueous sulfuric acid solution, and then dehydrated and spray dried to obtain an impact modifier resin powder.

< Example  2>

In Example 1, ii ) in the step of A) polymerization in the graft copolymer preparation step , in each of 0.1 parts by weight of potassium oleate and alkali phenyl disulfonate sodium salt (product name: Dowfax) in each of 0.2 parts by weight, and B) added The procedure of Example 1 was repeated except that 0.2 parts by weight of sodium diethylhexyl phosphate (product name: RHODAFAC) was replaced with 2.0 parts by weight in the graft copolymer preparation step to obtain an impact modifier resin powder.

< Example  3>

In Example 2, i) replacing 0.2 parts by weight of potassium oleate and alkali phenyl disulfonate sodium salt (product name: Dowfax) in each of a) the polymerization step in the step of preparing a rubber polymer latex with 0.3 parts by weight, respectively, and b) further polymerization. In step, the process of Example 2 was repeated except that 0.5 parts by weight of sodium diethylhexyl phosphate (product name: RHODAFAC) was replaced with 4.5 parts by weight to obtain an impact modifier resin powder.

< Comparative example  1>

In Example 1, i) the preparation of the rubber polymer latex , a) 0.2 parts by weight of potassium oleate salt during the polymerization step of 0.4 parts by weight, alkali phenyl disulfonate salt (trade name: Dofax) is not used, b) additional polymerization step 0.5 parts by weight of sodium diethylhexyl phosphate (trade name: RHODAFAC) was replaced with 0.9 parts by weight of potassium oleate, ii ) replacing 0.1 parts by weight of potassium oleate salt with 0.2 parts by weight in the step A) polymerization in the step of preparing the graft copolymer , and without using the alkali phenyl disulfonate sodium salt (product name: Dofafax) and B) further graft copolymer The procedure of Example 1 was repeated except that 0.2 parts by weight of sodium diethylhexyl phosphate (product name: RHODAFAC) was replaced with 2.0 parts by weight of potassium oleate, to thereby obtain an impact modifier resin powder.

< Comparative example  2>

In Example 1, i) replacing 0.2 parts by weight of potassium oleate salt with 0.4 parts by weight, and 0.2 parts by weight of alkali phenyl disulfonate salt (product name: Dofafax) during the polymerization step of i) preparing a rubber polymer latex , and 0.1 parts by weight, b) sodium diethylhexyl phosphate (product name: RHODAFAC) during the further polymerization step is replaced with potassium oleate, ii ) 0.1 part by weight of potassium oleate salt in 0.4) by weight in the polymerization step A) during the graft copolymer preparation step; , B) The process of Example 1 was repeated except that 0.2 parts by weight of sodium diethylhexyl phosphate (trade name: RHODAFAC) was replaced with 0.7 parts by weight of potassium oleate in the step of preparing the graft copolymer, and the impact modifier resin powder was replaced. Got it.

< Comparative example  3>

In Example 1, i) 0.2 parts by weight of an alkali phenyl disulfonate salt (product name: Dofafax) during the polymerization step of i) preparing a rubber polymer latex is replaced with 0.3 parts by weight, and b) sodium diethylhexyl phosphate ( Product name: RHODAFAC) is replaced with potassium oleate, ii ) 0.1 parts by weight of alkali phenyl disulfonate sodium salt (product name: Dowfax) in the polymerization step A ) in the graft copolymer preparation step, 0.2 parts by weight, B) The procedure of Example 1 was repeated except that 0.2 parts by weight of sodium diethylhexyl phosphate (product name: RHODAFAC) was replaced with 0.6 parts by weight of potassium oleate salt in the step of preparing a further graft copolymer to obtain an impact modifier resin powder.

< Comparative example  4>

In Example 1, i) replacing 0.2 parts by weight of an alkali phenyl disulfonate salt (trade name: Dofafax) during the polymerization step of i) preparing a rubber polymer latex , 0.4 parts by weight, and b) sodium diethylhexyl phosphate ( Product name: RHODAFAC) replaced with potassium oleate, ii) a graft copolymer prepared A) a polymerization step, the alkali-phenyl di-sulfonate salts in one step (product name: Dowfax) 0.1 parts by weight of a further alternative, and, B) portion of 0.6 parts by weight graft copolymer manufacturing step, sodium diethyl from hexyl The procedure of Example 1 was repeated except that phosphate (product name: RHODAFAC) was replaced with potassium oleate salt to obtain an impact modifier resin powder.

< Comparative example  5>

In Example 1, i) preparing a rubber polymer latex , a) using no potassium oleate salt during the polymerization step , using 0.5 parts by weight of an alkali phenyl disulfonate sodium salt (trade name: Dofax), and b) an additional polymerization step. Replace sodium diethylhexyl phosphate (product name: RHODAFAC) with alkali phenyl disulfonate sodium salt (product name: Dofafax), ii ) a potassium oleate salt is not used in the polymerization step A) of the graft copolymer preparation step, 0.3 parts by weight of an alkali phenyl disulfonate sodium salt (trade name: Dofax), and B) an additional graft copolymer preparation step, The process of Example 1 was repeated except that sodium diethylhexyl phosphate (product name: RHODAFAC) was replaced with alkali phenyl disulfonate sodium salt (product name: Dofax) to obtain an impact modifier resin powder.

< Comparative example  6>

In Example 1, i) preparation of rubber polymer latex , 0.9 parts by weight of sodium diethylhexyl phosphate (product name: RHODAFAC) instead of potassium oleate and alkali phenyl disulfonate sodium salt (product name: Dofafax) during the polymerization step ii ) except that 0.9 parts by weight of sodium diethylhexyl phosphate (product name: RHODAFAC) was used instead of potassium oleate and alkali phenyl disulfonate sodium salt (product name: Dowfax) in the polymerization step, A ) in the graft copolymer preparation step. The process of Example 1 was repeated and the impact modifier resin powder was obtained.

< Comparative example  7>

In Example 1, i) preparation of rubber polymer latex , a) potassium oleate salt is not used during the polymerization step , 0.2 parts by weight of alkali phenyl disulfonate salt (product name: Dofax) is replaced by 0.4 parts by weight, and b) an additional polymerization step. 0.5 parts by weight of sodium diethylhexyl phosphate (trade name: RHODAFAC) was replaced with 0.3 parts by weight, ii ) 0.1 parts by weight of potassium oleate salt and 0.1 parts by weight of alkali phenyl disulfonate salt (product name: Dowfax) in A) polymerization step in the graft copolymer preparation step to 0.6 parts by weight of alkali phenyl disulfonate sodium salt (product name: Dowfax) Except for replacing, the process of Example 1 was repeated to obtain an impact modifier resin powder.

< Comparative example  8>

In Example 1, i) preparing a rubbery polymer latex , a) during the polymerization step , a potassium oleate salt was not used, 0.2 parts by weight of an alkali phenyl disulfonate salt (trade name: Dofax) was replaced with 0.4 parts by weight, ii ) 0.1 parts by weight of potassium oleate salt and 0.1 parts by weight of alkali phenyl disulfonate salt (product name: Dowfax) in A) polymerization step in the graft copolymer preparation step to 0.6 parts by weight of alkali phenyl disulfonate sodium salt (product name: Dowfax) Subsequently, B) The procedure of Example 1 was repeated except that 0.2 parts by weight of sodium diethylhexyl phosphate (product name: RHODAFAC) was replaced with 0.5 parts by weight in the step of preparing a further graft copolymer, thereby obtaining an impact modifier resin powder. .

< Comparative example  9>

In Example 1, i) 0.2 parts by weight of oleic acid potassium salt and alkali phenyl disulfonate salt (product name: Dowfax) during the polymerization step of i) rubber polymer latex preparation , 0.2 parts by weight of alkali phenyl disulfonate salt (product name: Dowfax) 0.3 parts by weight, ii ) during the graft copolymer preparation step, A) in the polymerization step, the potassium oleate salt is not used, 0.1 parts by weight of the alkali phenyl disulfonate salt (trade name: Dofax) is replaced by 0.2 parts by weight, and B) additional graft copolymer production step The procedure of Example 1 was repeated except that 0.2 parts by weight of sodium diethylhexyl phosphate (product name: RHODAFAC) was replaced by 1.5 parts by weight to obtain an impact modifier resin powder.

Processing based on 100 parts by weight of 4% by weight of the impact modifier resin powder obtained in Examples 1 to 3 and Comparative Examples 1 to 9 and 96% by weight of polycarbonate (product name: PC 200-1 of LG-Dow) After mixing 0.5 parts by weight of the additive and 0.02 parts by weight of the pigment, the pellet was extruded at 200 rpm using a twin screw extruder manufactured by Leistritz at a measuring speed of 60 kg / hr and a temperature of 250 to 320 ° C. . This pellet was injected into a temperature of 250 ~ 320 ℃ using an Eng100 EC100 φ 30 injection machine was prepared as a specimen for evaluating the impact strength, colorability.

As the physical properties of the specimens, the impact strength and the whiteness were measured in the following manner, respectively, under the initial impact strength and the moist heat resistance conditions, and summarized together in Table 1 below.

[Property evaluation]

Initial impact strength: Impact specimens were prepared in accordance with ASTM D-256. Izod impact strengths of 1 / 8-inch and 1 / 4-inch specimens were measured at -40 ° C and room temperature, respectively.

Impact strength under heat-and-moisture conditions: 1 / 8-inch and 1 / 4-inch specimens were placed in a 90 ° C., 95% chamber for 1000 hr and impacted at room temperature, respectively. Intensity was measured.

Initial whiteness ( WT ): The WI value of the color measurement specimens was measured using a color difference meter (X-rite Color-Eye 7000A). The larger the WI value, the more white the specimen.

Whiteness ( WT ) under humidity and heat conditions : The color measurement specimens were placed in 90 ° C, 95% chamber for 1000 hr, and the WI value of the color measurement specimens was measured using a colorimeter (X-rite Color-Eye 7000A) at room temperature. It was. The larger the WI value, the better the heat and moisture resistance.

As a comparative example, the physical properties were evaluated in the manner described above for 100% by weight of polycarbonate alone, the initial impact strength (1/8 ") was 28.6, and the initial impact strength (1/4") was 28.3, 100hr moisture resistant shock Strength (1/8 ") is 8.6, 1000hr Moisture Heat Impact Strength (1/4") is 7.4, Initial Color (Whiteness) is 72.0, 1000 hr Moisture Resistance Color (Whiteness) is 10.3. It can be seen that the impact strength is considerably poor under all conditions.

division MBS polymerization emulsifier
(Total amount-weight part)             Impact strength color
(Whiteness) Initial (kfg-m / m) 1000hr Moisture Resistance Heat (kfg-m / m) OKL
(phr) Dowfax
(phr) RHODAFAC
(phr)  1/8 1/4  1/8 1/4 Early Wet heat
(1000hr) Example 1 0.3 0.3 0.7 60.3 43.1 56.5 41.3 70.3  28.6 Example 2 0.4 0.4 2.5 59.8 42.3 57.3 40.5 71.0  27.5 Example 3 0.5 0.5 5.0 58.2 40.7 54.1 37.8 70.6 28.1 Comparative Example 1 3.5 - - 37.5 30.5 10.4 9.3 69.5  6.9 Comparative Example 2 2.0 0.2 - 40.3 27.5 34.8 18.9 70.1  12.5 Comparative Example 3 1.5 0.5 - 42.5 33.6 36.2 20.3 70.2  13.9 Comparative Example 4 1.0 1.0 - 48.1 31.7 39.0 25.4 70.5  12.6 Comparative Example 5 - 1.5 - 44.4 34.0 38.4 26.0 69.9  13.0 Comparative Example 6 - - 3.0 55.1 35.1 43.4 29.6 71.2  18.7 Comparative Example 7 - 1.0 0.5 49.2 34.6 37.5 28.9 70.6  19.3 Comparative Example 8 - 1.0 1.0 48.4 32.0 38.3 27.1 70.1  17.5 Comparative Example 9 - 0.5 2.0 49.0 31.8 39.1 25.4 70.4  18.9

(PC: polycarbonate, OLK: potassium oleate, Dowfax: product name of alkali phenyl disulfonate sodium salt, RHODAFAC: product name of sodium diethylhexyl phosphate)

As shown in Examples 1 to 3 in Table 1, when the contents of the carboxyl emulsifier and the sulfonate emulsifier are changed, the Izod impact strength of the polycarbonate resin composition is not lowered relatively under moist heat conditions. White also improved.

Meanwhile, in Comparative Example 1 of the carboxyl emulsifier alone or Comparative Example 5 of the sulfonate emulsifier alone, both the impact strength and the color were improved compared to the control example described above, but the MBS graft copolymer was included as the impact modifier. Compared with Examples 1 to 3, the effect of preventing the impact strength from lowering in impact strength, in particular, under damp-heat conditions was not large.

Further, in Comparative Example 6 of the phosphate-based emulsifier alone, the impact strength was remarkably poor under wet and heat conditions.

In addition, in the case of Comparative Examples 2,3,4,7,8,9 in which the content of each emulsifier was used in combination of two kinds of emulsifiers, the effect of preventing the impact strength drop was not great.

In addition, in order to examine the effect of the content of the emulsifier for MBS-based graft copolymer polymerization, the following additional experimental example was performed.

<Add Experimental Example  1>

In Example 3, B) additional graft copolymer manufacturing step, the process of Example 3 was repeated except that 4.5 parts by weight of sodium diethylhexyl phosphate (product name: RHODAFAC) was replaced by 5.5 parts by weight of the impact modifier resin powder Obtained.

As a result of measuring the same physical properties for the specimen made of the impact modifier resin powder, the initial impact strength (1/8 ") is 57.9, the initial impact strength (1/4") is 36.4, 100hr moisture resistance thermal shock strength (1 / 8 ") showed 47.1, 1000hr Moisture Heat Impact Strength (1/4") of 30.3, initial color (whiteness) of 70.1 and 1000hr Moisture Heat of Humidity (whiteness) of 24.1.

In other words, when the phosphate-based emulsifier exceeds the appropriate amount, it was found that the effect of reducing the impact strength is seen but not excellent.

Furthermore, in order to examine the effect on the content change between the polycarbonate resin and the MBS graft copolymer, the following additional experimental example was performed.

<Add Experimental Example  2>

0.5 weight part of a processing additive and 0.02 weight of a pigment with respect to 100 weight part which mix | blended 10 weight% of impact modifier resin powder obtained by the said Example 1, and 90 weight% of polycarbonate (The product name of LG-Dow company: PC 200-1). After mixing the parts, using a twin screw extruder (Leistritz) company extruded at 200 rpm at a metering speed of 60 kg / hr, a temperature of 250 ~ 320 ℃ to obtain a pellet (pellet). This pellet was injected into a temperature of 250 ~ 320 ℃ using an Eng100 EC100 φ 30 injection machine was prepared as a specimen for evaluating the impact strength, colorability.

The same physical properties were measured for the specimens. As a result, the initial impact strength (1/8 ") was 40.1, the initial impact strength (1/4") was 26.43, and the 100hr moisture resistant thermal impact strength (1/8 ") was 26.3, The 1000hr Moisture Heat Impact Strength (1/4 ") was 19.5, the initial color (whiteness) was 71.6, and the 1000hr Moisture Heat Humidity Heat (whiteness) was 5.9.

That is, when the polycarbonate resin is used at 90 parts by weight, it showed an effect of preventing the impact strength decrease and was not excellent.

<Add Experimental Example  3>

Except for replacing the impact modifier resin powder 20% by weight, and 80% by weight of the polycarbonate resin in Experimental Example 2, the physical properties of the same specimens were measured, and thus the initial impact strength (1/8 "). ) Is 25.3, initial Impact Strength (1/4 ") is 19.4, 100hr Moisture Heat Impact Strength (1/8") is 19.4, 1000hr Moisture Heat Impact Strength (1/4 ") is 12.7, Initial Color (Whiteness) is 69.9, 1000hr Humid heat color (whiteness) is 3.1.

That is, when the polycarbonate resin was used at 80 parts by weight, the initial impact strength and the whiteness of the impact strength as well as the initial impact strength and the whiteness were significantly poor.

Claims (18)

As a core-shell type MBS-based graft copolymer,
MBS-based graft copolymer, characterized in that the core and the shell is obtained by polymerization under a carboxyl emulsifier, a sulfonate emulsifier and a phosphate emulsifier.
The method of claim 1,
The core is a diene rubber polymer latex obtained by adding a carboxyl emulsifier and a sulfonate emulsifier to a polymerization conversion rate of 60% or less, and a phosphate emulsifier added to a polymerization conversion rate of 60 to 75%. MBS graft copolymer.
The method of claim 1,
The carboxyl emulsifier is MBS graft copolymer, characterized in that at least one selected from potassium salt and sodium salt of oleic acid.
The method of claim 1,
The sulfonate-based emulsifier is MBS graft copolymer, characterized in that at least one selected from sodium salt, calcium salt, and amine salt of alkali phenyl disulfonate alkali phenyl.
The method of claim 1,
The phosphate-based emulsifier is MBS graft copolymer, characterized in that at least one selected from sodium diethylhexyl phosphate , phosphonated polyoxyethylene alcohol and phosphonated polyoxyethylene phenol.
The method of claim 1,
The carboxyl emulsifier is MBS graft copolymer, characterized in that in the range of 0.1 to 0.5 parts by weight based on 100 parts by weight of the conjugated diene compound constituting the core.
The method of claim 1,
The sulfonate-based emulsifier MBS-based graft copolymer, characterized in that in the range of 0.1 to 0.5 parts by weight based on 100 parts by weight of the conjugated diene compound constituting the core.
The method of claim 1,
MBS-based graft copolymer, characterized in that the phosphate-based emulsifier is in the range of 0.1 to 0.5 parts by weight based on 100 parts by weight of the conjugated diene compound constituting the core.
The method of claim 1,
MBS-based graft copolymer, characterized in that the core has a particle size or an average particle diameter of 2500 to 3500 mm 3 under non-aggregation.
The method of claim 1,
MBS graft, characterized in that the shell is a polymer obtained by adding a carboxyl emulsifier and a sulfonate emulsifier at a point of less than 65% polymerization conversion, phosphate-based emulsifier is introduced at a point of 65 to 75% polymerization conversion. Copolymer.
The method of claim 10,
The carboxyl emulsifier is based on a total of 100 parts by weight of the latex and the compound constituting the shell, MBS-based graft copolymer, characterized in that in the range.
The method of claim 10,
The sulfonate-based emulsifier MBS-based graft copolymer, characterized in that in the range of 0.1 to 0.5 parts by weight based on a total of 100 parts by weight of the latex and the compound constituting the shell.
The method of claim 10,
The phosphate-based emulsifier MBS-based graft copolymer, characterized in that in the range of 0.1 to 4.5 parts by weight based on a total of 100 parts by weight of the latex and the compound constituting the shell.
The method of claim 1,
The MBS-based graft copolymer, MBS-based graft copolymer, characterized in that composed of 40 to 80% by weight of the core and 20 to 60% by weight of the shell.
The method of claim 1,
The shell is MBS graft copolymer, characterized in that the polymer of 40 to 80% by weight of the core, 19 to 40% by weight of the alkyl methacrylate compound surrounding the core, and 1 to 20% by weight of the aromatic vinyl compound. .
16. The method of claim 15,
The alkyl methacrylate compound is MBS graft copolymer, characterized in that at least one selected from methyl methacrylate, ethyl methacrylate and butyl methacrylate.
The impact modifier for polycarbonate resin, characterized in that the MBS graft copolymer according to any one of claims 1 to 16.
A polycarbonate resin composition comprising 4 to 10% by weight of the impact modifier of claim 17 and 90 to 96% by weight of a polycarbonate resin.