KR101351735B1 - Mbs resin impact modifier, polycarbonate resin composition containing the same with excellent impact resistance under high temperature and humidity, and their preparation method - Google Patents

Abstract

The present invention relates to a MBS-based resin for impact modifiers, a polycarbonate resin composition having excellent moisture resistance and low temperature impact resistance, including the same, and a method for manufacturing the same, and more particularly, in the method of manufacturing an MBS-based impact modifier, a) Preparing a butadiene-based rubber polymer core by emulsion polymerization; b) emulsion-grafted copolymerization of the prepared butadiene-based rubber polymer core, alkyl methacrylate-based monomer and styrene-based monomer to prepare a core-shell structured MBS-based resin latex; And c) preparing the MBS-based resin having a powdery core-shell structure by salt coagulation, dehydration and drying process, or spray drying process of the prepared MBS-based resin latex; At least one selected from the group consisting of sulfonate-based emulsifiers, sulfate-based emulsifiers, fatty acid soaps, and alkali salts of rosin acid, as an emulsifier in the steps of preparing the core and b) preparing the graft shell. The present invention relates to a method of manufacturing an MBS-based resin for an impact modifier, an MBS-based resin for an impact modifier prepared therefrom, a polycarbonate resin composition comprising the same, and a method for manufacturing the same.
According to the present invention, MBS-based resin for impact reinforcing agent of the core-shell structure manufactured using a predetermined emulsifier, and the effect of providing a polycarbonate resin composition and a method for producing the same, which does not lower the impact resistance even under moist heat conditions by adding it There is.

Description

MBS resin for impact modifiers, polycarbonate resin compositions having excellent moisture and heat resistance and low temperature impact resistance, including the same, and methods for preparing the same THEIR PREPARATION METHOD}

The present invention relates to a MBS-based resin for impact modifiers, a polycarbonate resin composition having excellent moisture resistance and low temperature impact resistance, including the same, and a method for preparing the same, and more particularly, a core-shell structure manufactured using a predetermined emulsifier. MBS-based resin for impact modifiers, and polycarbonate resin compositions and methods for producing the same, in which impact resistance is not lowered even under moist heat conditions.

In general, polycarbonate (PC) is widely used as an interior and exterior agent throughout the industry due to its excellent impact resistance, electrical properties and heat resistance, but there is a problem in that processability, chemical resistance and heat and humidity resistance are inferior.

PC / ABS blend resin is excellent in processability and mechanical strength, and widely used in electric and electronic parts, including automobiles, but there is a problem in that room temperature and low temperature impact resistance are severely degraded under high temperature and high humidity humidity test conditions.

Therefore, it is a situation that the development of the polycarbonate resin composition which impact resistance does not fall also in damp-heat conditions.

In order to solve the problems of the prior art as described above, the present invention is a core-shell structured impact modifier MBS-based resin prepared by using a predetermined emulsifier, polycarbonate resin composition that does not lower the impact resistance even under moist heat conditions by adding it And it aims at providing these manufacturing methods.

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 provides a method for producing an impact modifier MBS resin, a) preparing a butadiene-based rubber polymer core by emulsion polymerization; b) emulsion-grafted copolymerization of the prepared butadiene-based rubber polymer core, alkyl methacrylate-based monomer and styrene-based monomer to prepare a core-shell structured MBS-based resin latex; And c) preparing the MBS-based resin having a powdery core-shell structure by salt coagulation, dehydration and drying process, or spray drying process of the prepared MBS-based resin latex; At least one selected from the group consisting of sulfonate-based emulsifiers, sulfate-based emulsifiers, soaps of fatty acids, alkali salts of rosin acid, and oleic acid alkali salts as an emulsifier in the step of preparing the core and b) preparing the graft shell. It provides a method for producing an impact modifier MBS resin, characterized in that used.

In addition, the present invention provides a MBS-based resin for impact modifiers prepared according to the above method, a polycarbonate resin composition comprising the same, and a method of manufacturing the same.

As described above, according to the present invention MBS-based resin for the impact modifier of the core-shell structure prepared using a predetermined emulsifier, polycarbonate resin composition and its preparation that does not lower the impact resistance even under moist heat conditions by adding it It has the effect of providing a method.

Hereinafter, the present invention will be described in detail.

Method for producing an impact modifier MBS-based resin of the present invention, the method of manufacturing an impact modifier MBS-based resin, a) preparing a butadiene-based rubber polymer core by emulsion polymerization; b) emulsion-grafted copolymerization of the prepared butadiene-based rubber polymer core, alkyl methacrylate-based monomer and styrene-based monomer to prepare a core-shell structured MBS-based resin latex; And c) preparing a MBS-based resin having a powdery core-shell structure by using the prepared MBS-based resin latex by salt coagulation, dehydration and drying, or spray drying. at least one selected from the group consisting of sulfonate-based emulsifiers, sulfate-based emulsifiers, fatty acid soaps, and alkali salts of rosin acid as emulsifiers in a) preparing a rubber polymer core and b) preparing a graft shell. It is characterized by using.

The butadiene-based rubber polymer core may be prepared by emulsion polymerization of at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and pyrrylene and the like, based on the total weight of the MBS resin, 60 to 80 wt% It is preferably included in%, there is an effect of improving the impact strength within this range.

The butadiene-based rubber polymer core may further include one or more selected from the group consisting of styrene-based monomers, vinyl cyanide-based monomers, etc. as a comonomer in the polymerization production, and 0 to 20 based on the total weight of the butadiene-based rubber polymer core It may be included in weight percent.

The alkyl methacrylate monomer may be at least one selected from the group consisting of methyl methacrylate, butyl methacrylate, benzyl methacrylate, and the like, preferably methyl methacrylate, and the total weight of the MBS resin It is preferably included in 15 to 30% by weight relative to.

The styrene monomer may be at least one selected from the group consisting of styrene, alpha methyl styrene, vinyl toluene, 3-4-dichloro styrene, and the like, preferably styrene, and 5 to 10 weight based on the total weight of the MBS resin. It is preferably included in%.

The shell graft copolymerization of step b) is an acryl acrylate monomer such as ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate and acryl in addition to the alkyl methacrylate monomer and styrene monomer. It may further include one or more selected from the group consisting of vinyl cyanide monomers such as ronitrile, may be included in 0 to 5% by weight relative to the total weight of the MBS resin.

The MBS resin latex is salt agglomeration, dehydration and drying process; Or it is preferable to be made of a powder-based MBS resin using a spray-drying process, it is easy to aggregate when using these processes, there is an effect that the carboxylic acid that hydrolyzes the PC / ABS blending resin is not produced.

The emulsifier is preferably at least one selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, soaps of fatty acids, alkali salts of rosin acids, and the like, more preferably sulfonates Sulfonate-based emulsifier.

The sulfonate-based emulsifier is preferably used in 0.1 to 4 parts by weight based on a total of 100 parts by weight of the butadiene-based rubber polymer core during the emulsion polymerization of step a), the MBS system in the shell graft copolymerization of step b) It is preferable to use 0.3 to 1.0 parts by weight based on 100 parts by weight of the resin. If the amount of the emulsifier is used in a smaller amount than the above range, latex stability during polymerization is reduced, and an excessive amount of solids is generated, which is unproductive. There is a possibility of excessive gas generation in the appearance of the molded article, which is not preferable.

MBS-based resin for the impact modifier of the present invention is characterized in that it is prepared according to the above production method.

The polycarbonate resin composition excellent in moisture and heat resistance of the present invention is 50 to 80% by weight of the polycarbonate resin, 15 to 30% by weight ABS resin and the MBS-based resin for the impact modifier 5 with respect to the total weight of the polycarbonate, ABS and MBS-based resin To 20 wt%.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example 1

<Preparation of Butadiene Rubber Polymer Core>

75 parts by weight of ion-exchanged water, 60 parts by weight of 1,3-butadiene as monomer, 1.2 parts by weight of sodium dodecylbenzene sulfonate (SDBS) as an emulsifier and potassium carbonate (K ₂₎ as an electrolyte in a nitrogen-substituted polymerization reactor (autoclave) CO ₃ ) 0.9 parts by weight, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as the molecular weight regulator, 0.3 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as the initiator and polymerization conversion rate at a reaction temperature of 70 ℃ 30 After reacting to a time point of 40 to 40%, 0.3 parts by weight of sodium dodecylbenzene sulfonate (SDBS) was first administered, and then 20 parts by weight of 1,3-butadiene was collectively reacted at 70 ° C. to a point of polymerization conversion of 60%, 20 parts by weight of the remaining 1,3-butadiene was 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 prepared rubbery polymer latex was 76%, the average particle diameter was 305 nm.

In the gel content, the rubber latex was coagulated with dilute acid or metal salt, washed, and then dried in a vacuum oven at 60 ° C. for 24 hours. Was added to 100 g of toluene and stored in a dark room at room temperature for 48 hours, and then separated into sol and gel and measured.

<Preparation of MBS-based resin for impact modifier of core-shell structure>

After adding 70 parts by weight of the prepared rubber latex (solid content) to a closed reactor, the temperature was raised to 70 ° C with nitrogen filling, and then 0.1 parts by weight of sodium pyrophosphate, 0.2 parts by weight of dextrose and sulfide in the reactor. 0.002 parts by weight of ferrous iron was added at once.

In a separate mixing device, 25.5 parts by weight of methyl methacrylate, 4.5 parts by weight of styrene, 0.5 parts by weight of sodium dodecylbenzene sulfonate (SDBS) as an emulsifier, 0.1 part by weight of cumene hydroperoxide, and 20 parts by weight of ion-exchanged water were mixed. An emulsion was prepared.

After the monomer emulsion was continuously added to the reactor for 2.5 hours, 0.03 parts by weight of cumene hydroperoxide was added after 30 minutes and aged at the same temperature for 1 hour to terminate the reaction at the point of polymerization conversion of 98%. The prepared MBS resin latex had a particle diameter of 3200 mm 3 and a solid content of 42%.

An antioxidant was added to the MBS-based resin latex, aggregated with magnesium sulfate (MgSO ₄ ), dehydrated and dried to prepare a powdery MBS-based impact modifier.

<Production of Polycarbonate Resin Composition>

Polycarbonate (300-15, LG-Dow) 65% by weight, ABS resin (DP270, LG Chem.) 25% by weight and a total of 100 parts by weight of the resin mixture consisting of 10% by weight of the MBS impact modifier, and other processing additives After mixing 0.5 parts by weight and 0.02 parts by weight of pigment, it was extruded using a twin screw extruder manufactured by Leistritz at 200 rpm, a metering speed of 60 kg / hr and 250 to 320 ° C., to pellet polycarbonate resin composition ( pellets) were prepared. The pellets were injected at 250 to 320 ° C. using ENGEL's EC100 φ30 injection machine to produce 1/4 ”and 1/8” specimens for measuring impact strength and moisture resistance.

Example 2

In Example 1, except that the spray drying process was used instead of the flocculation, dehydration, and drying processes in the preparation of the MBS-based impact modifier, the same method as in Example 1 was performed.

Comparative Example 1

Except that the MBS-based impact modifier was used in the preparation of the polycarbonate resin composition in Example 1 was carried out in the same manner as in Example 1.

Comparative Example 2

Except for using potassium oleate as an emulsifier in the preparation of the butadiene-based rubber polymer core and MBS impact modifier in Example 1, sulfuric acid (H ₂ SO ₄ ) as a flocculant in the manufacture of the MBS impact modifier It carried out in the same manner as in Example 1.

Comparative Example 3

Except for using the potassium oleate as an emulsifier in the preparation of the butadiene-based rubber polymer core and MBS impact modifier in Example 1 was carried out in the same manner as in Example 1.

 [Test Example]

The properties of the 1/4 "and 1/8" specimens of the polycarbonate resin compositions prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 1 below. .

* IZOD impact strength (IMP)-The prepared specimens were measured at room temperature and -40 ℃ according to ASTM D-256 standard.

* Moisture-resistant heat test- The prepared specimens were left at 90 ° C. and 95% RH chamber for 1000 hr, and then the IZOD impact strength (IMP) was measured at room temperature and −40 ° C. according to ASTM D-256.

As shown in Table 1, the polycarbonate resin composition (Examples 1 and 2) containing the MBS-based impact modifier of the present invention does not include an MBS-based impact modifier (Comparative Example 1) and oleic acid as an emulsifier during manufacture. Compared to the polycarbonate resin composition (Comparative Examples 2 and 3) containing the MBS-based impact modifier using potassium, the impact strength at room temperature and low temperature is excellent, and furthermore, at room temperature and low temperature after exposure to harsh high temperature and high humidity environments. Impact strength (heat resistance test) was confirmed to be more remarkable.

Claims (5)

In the manufacturing method of the MBS resin for impact modifiers,
a) preparing a butadiene-based rubber polymer core by emulsion polymerization, using the amount of the emulsifier in an amount within the range of 0.5 to 2.0 parts by weight based on 100 parts by weight of the total butadiene-based rubber polymer core;
b) emulsion-grafted copolymerization of the prepared butadiene-based rubber polymer core, alkyl methacrylate-based monomer and styrene-based monomer to prepare core-shell structured MBS-based resin latex, and the amount of emulsifier used in the MBS-based resin latex total 100 Preparing by using an amount within the range of 0.3 to 1.0 parts by weight based on parts by weight; And
c) preparing a MBS-based resin having a powdery core-shell structure by salt coagulation, dehydration and drying process, or spray drying process of the prepared MBS-based resin latex;
In the step a) preparing a rubber polymer core and b) preparing a graft shell, an alkyl aryl sulfonate or a sulfonate-based emulsifier, which is a sulfonated alkyl ester, is used as an emulsifier.
Method for producing MBS resin for impact modifiers. delete delete Manufactured according to the method of claim 1
MBS resin for impact modifiers. 5 to 20% by weight of the MBS-based resin, 50 to 80% by weight of the polycarbonate resin, and 15 to 30% by weight of the ABS resin, based on the total weight of the MBS resin, the polycarbonate and the ABS resin. doing
Polycarbonate resin composition excellent in moisture and heat resistance.