KR20070047464A - Impact modifier having multi-layered structure, method for preparing the same, and thermoplastic resin composition comprising the same - Google Patents

Abstract

The present invention relates to an acrylic impact modifier having a multilayer structure, a method of manufacturing the same, and a thermoplastic resin composition comprising the same, and more particularly, a) a sheath, b) a core surrounding the sheath, and c) the core. Wherein the a) seed comprises a copolymer polymerized from i) an aromatic vinylic monomer, ii) a hydrophilic vinylic monomer, and iii) a crosslinkable vinylic monomer, wherein b) the core is i) Alkyl acrylates having 2 to 8 carbon atoms of alkyl groups, and ii) copolymers polymerized from crosslinker monomers, wherein c) the shell comprises: i) aromatic vinyl monomers, ii) hydrophilic vinyl monomers, iii) crosslinkable vinyl A monomer, and iv) a multi-layered acrylic impact modifier comprising a copolymer polymerized from a functional group-containing vinyl monomer, a method for preparing the same, and a thermoplastic resin composition comprising the same. One will.

Impact modifier, multi-layer structure, seed, glass transition temperature, functional monomer vinyl monomer

Description

Acrylic impact modifier of multi-layered structure, a method for manufacturing the same, and a thermoplastic resin composition comprising the same.

[Industrial use]

The present invention relates to an acrylic impact modifier having a multilayer structure, and a thermoplastic resin composition comprising the same, and more particularly, an acrylic impact modifier having a multilayer structure for reinforcing impact resistance, chemical resistance, processability, weather resistance, and the like of a thermoplastic resin, and the like. It relates to a thermoplastic resin composition comprising.

[Private Technology]

Core-shell structured impact modifiers have been used to reinforce the impact resistance, chemical resistance, processability and weather resistance of thermoplastics. Methyl methacrylate-butadiene-styrene (MBS) resins, acrylic resins, ethylene chloride (CPE) resins, silicone resins and the like are used depending on the application.

Although the use of impact modifiers was mostly limited to impact reinforcement of polyvinyl chloride, engineering plastics such as polyalkylene terephthalate resins, polyamide resins, polyacetal resins, polycarbonate resins, and two or more of these alloys, etc. The area of use is widening with resin.

Korean Laid-Open Patent Publication No. 2004-0057069 is a multilayer acrylic impact modifier comprising a sheath prepared from a vinyl aromatic monomer and a hydrophilic monomer, an alkylacrylate rubber core, and an alkyl methacrylate shell. It has been shown to reinforce impact resistance and colorability.

U.S. Pat.No. 5242982 discloses reinforcing the low temperature impact strength of an engineering plastic that is reactive with an epoxy group by polymerizing an epoxy group monomer on the surface of an acrylic rubber core.

Korean Patent Laid-Open Publication No. 1994-0000519 discloses a core-shell polymer comprising a core layer polymerized from a diene monomer and a vinyl aromatic monomer and a shell of a styrene copolymer such as a copolymer of styryl or hydroxyalkyl acrylate. The polyester resin composition which improved the impact resistance, containing a polymer and maintaining transparency is shown.

However, these core-shell structured impact modifiers have sufficient low temperature impact strength reinforcement and various pigments for engineering plastic resins such as polyalkylene terephthalate resins, polyamide resins, polyacetal resins, polycarbonate resins, or alloys thereof. Does not have high colorability to

The present invention is to solve the above problems, it is an object of the present invention to provide an acrylic impact modifier that is added to the engineering plastic resin to impart excellent impact resistance and colorability.

Another object of the present invention is to provide a method for producing the impact modifier.

Still another object of the present invention is to provide a thermoplastic resin composition comprising the impact modifier.

The present invention to achieve the above object, a) 0.5 to 40 parts by weight of the seed (based on the composition weight); b) 50 to 89.5 parts by weight of the core surrounding the sheath, based on the weight of the composition; And c) 10.0 to 49.5 parts by weight of the shell surrounding the core, based on the weight of the composition, wherein a) the seed comprises i) an aromatic vinyl monomer, ii) a hydrophilic vinyl monomer, and iii) a crosslinkable vinyl monomer. Copolymers polymerized from a polymer comprising; i) an alkyl acrylate having 2 to 8 carbon atoms of an alkyl group, and ii) a copolymer polymerized from a crosslinker monomer, wherein c) the shell is i) aromatic It provides a vinyl-based monomer, ii) a hydrophilic vinyl monomer, iii) a crosslinkable vinyl monomer, and iv) a copolymer polymerized from a functional group-containing vinyl monomer.

The invention also comprises the steps of a) manufacturing the seed, b) polymerizing 50 to 89.5 parts by weight of the core on the surface of the prepared 0.5 to 40 parts by weight of the seed, and c) 10.0 to the surface of the prepared core It provides a method for producing a multi-layer acrylic impact modifier comprising the step of polymerizing 49.5 parts by weight of the shell.

The present invention also provides a thermoplastic resin composition comprising a) 80 to 99.5 parts by weight of the thermoplastic matrix resin, and b) 0.5 to 20 parts by weight of the acrylic impact modifier.

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

MEANS TO SOLVE THE PROBLEM The present inventors added the acrylic polymer of the multilayered structure manufactured by multistage superposition | polymerization to engineering plastic resins, such as a polyalkylene terephthalate resin, a polyamide resin, a polyacetal resin, a polycarbonate resin, or these alloys, and provides impact resistance. The invention was found to improve and show excellent colorability.

Acrylic impact modifier of the multi-layer structure of the present invention comprises a high glass transition temperature of the sheath, a) 0.5 to 40 parts by weight (based on the weight of the impact modifier), b) 50 to 89.5 weight of the core surrounding the sheath Parts (based on the weight of the impact modifier), and c) 10.0 to 49.5 parts by weight (based on the weight of the impact modifier) surrounding the core.

If the sheath is less than 0.5 parts by weight, the stability of the latex may be lowered. If it is more than 40 parts by weight, the mechanical properties may be reduced. In addition, when the core is less than 50 parts by weight, properties deterioration including low temperature impact characteristics may occur. When the core is more than 89.5 parts by weight, the stability of the latex may be reduced due to the excess rubber component. In addition, when the shell is less than 10 parts by weight, it is difficult for the shell to be effectively grafted to the core portion, and when the shell is more than 49.5 parts by weight, property degradation including low temperature shock characteristics may occur.

The a) seed is polymerized from an aromatic vinyl monomer having a high glass transition temperature, a hydrophilic vinyl monomer, and a crosslinkable vinyl monomer, and more preferably i) 65 to 99.4 parts by weight of the aromatic vinyl monomer (the seed monomer weight). Basis), ii) 0.5 to 30 parts by weight of hydrophilic vinyl monomer (based on the weight of the seed monomer), and iii) 0.1 to 5 parts by weight of crosslinkable vinyl monomer (based on the weight of the monomer).

In the polymerization of the seed, when the content of the aromatic vinyl monomer is less than 65 parts by weight, it is not desirable to form a copolymer with the hydrophilic vinyl monomer, and when it exceeds 99.4 parts by weight due to the aromatic vinyl monomer having a slow polymerization rate. The reaction time is long. In addition, when the content of the hydrophilic vinyl monomer is less than 0.5 parts by weight, the polymerization rate is slowed down, and the polymerization conversion rate is lowered under a certain polymerization time, and when the content of the hydrophilic vinyl monomer exceeds 30 parts by weight, the copolymer with the aromatic vinyl monomer is not well formed. This does not cause physical properties and color degradation. In addition, when the content of the crosslinkable vinyl monomer is less than 0.1 part by weight, the crosslinking point decreases, and thus the grafting property with the core layer of the next step is lowered. Can be.

The sheath of the acrylic impact modifier has a glass transition temperature of 60 to 100 ℃, preferably having an average particle diameter of 100 to 200 nm. If the glass transition temperature of the seed is less than 60 ℃ can not play the role of a hard seed, if it exceeds 100 ℃ may cause a decrease in impact strength. In addition, when the average particle diameter of the seed is less than 100 nm, the latex final particle size becomes small, and when it exceeds 200 nm, the latex final particle diameter is too large, so that the stability of the impact modifier particles may be lowered.

In addition, b) the core surrounds the outside of the sheath, i) 95.0 to 99.9 parts by weight of alkyl acrylate having 2 to 8 carbon atoms of the alkyl group (based on the weight of the core monomer), and ii) 0.1 to 5.0 weight of the crosslinking monomer. It is preferable to include a copolymer polymerized from a part (based on the weight of the core monomer).

In the polymerization of the core, when the content of the alkyl acrylate is less than 95.0 parts by weight, the degree of crosslinking is too high, and the impact strength reinforcing effect of the alkyl acrylate as the rubber may be lowered. The grafting efficiency of the shell may be reduced.

If the content of the crosslinker monomer is less than 0.1 part by weight, and the crosslinking of the core is insufficient, the grafting of the latex may not be smooth, and thus, the latex may not grow to a latex of sufficient size, and the physical properties of the final polymer may be reduced. In addition, even when the content of the crosslinker monomer exceeds 5.0 parts by weight and the crosslinking degree is too high, a large amount of hard solids is generated in the polymerization process, thereby lowering the stability of the polymerization, the production efficiency and the impact reinforcing effect of the rubber.

Glass transition temperature of the core of the acrylic impact modifier is preferably -60 ℃ to 0 ℃. When the glass transition temperature of the core is less than -60 ℃, the low temperature impact strength reinforcement effect is improved, but the thermal stability and weather resistance may be lowered.

In addition, the c) the shell surrounds the core, i) 55 to 98.9 parts by weight of the aromatic vinyl monomer (based on the weight of the shell monomer), ii) 0.5 to 30 parts by weight of the hydrophilic vinyl monomer (based on the weight of the shell monomer), iii) 0.1 to 5 parts by weight of the crosslinkable vinyl monomer (based on the weight of the shell monomer), and iv) a copolymer polymerized from 0.5 to 10 parts by weight (based on the weight of the shell monomer) of the functional group-containing vinyl monomer.

When the content of the aromatic vinyl monomer in the polymerization of the shell is less than 55 parts by weight, it is not desirable to form a copolymer with the hydrophilic vinyl monomer, and when it exceeds 98.9 parts by weight, the reaction occurs due to the slow aromatic vinyl monomer. It will take longer. In addition, when the content of the hydrophilic vinyl monomer is less than 0.5 parts by weight, the polymerization rate is slowed down, and the polymerization conversion rate is lowered under a certain polymerization time, and when the content exceeds 30 parts by weight, the copolymer with the aromatic vinyl monomer is not well formed. This does not cause physical properties and color degradation. In addition, when the content of the crosslinkable vinyl monomer is less than 0.1 part by weight, the crosslinking point decreases, and thus the grafting property with the core layer of the next step is lowered. Can be. In addition, when the content of the functional group-containing vinyl monomer is less than 0.5 parts by weight, the number of functional groups present on the surface of the impact modifier particles is small, so that the effect of improving compatibility with the matrix resin is insignificant. There is no additional improvement of impact strength beyond the limit of improvement.

The glass transition temperature of the shell of the acrylic impact modifier is preferably 60 to 100 ℃. When the glass transition temperature of the shell is less than 60 ° C, liquid coagulation is hindered beyond the normal aggregation temperature range, and when the glass transition temperature exceeds 100 ° C, the glass transition ionicity of the final polymer is increased, thereby reducing the effect of impact reinforcement.

The aromatic vinyl monomer used for the polymerization of the seed and the shell is preferably at least one selected from the group consisting of styrene, alphamethylstyrene, 4-methylstyrene, and 3,4-dichlorostyrene, Hydrophilic vinyl monomers used for the polymerization of the shell is a group consisting of acrylonitrile, methacrylonitrile, benzyl methacrylate, aryl methacrylate, alkyl acrylate having 1 to 8 carbon atoms of alkyl group, alkyl methacrylate It is preferably at least one selected from the group, and the crosslinkable vinyl monomers used for polymerization of the seed, core and shell are divinylbenzene, 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate, trimethylolpropane triacrylate, tetrae It is preferable that it is 1 or more types chosen from the group which consists of a styrene glycol diacrylate and tetraethylene glycol dimethacrylate.

The aromatic vinyl monomer has a relatively high glass transition temperature and thus serves to improve the agglomeration characteristics of the latex. In particular, the aromatic vinyl monomer used for the polymerization of the shell is a hard vinyl monomer and has an appropriate amount of hydrophilic vinyl. When copolymerized with the monomer, it is excellent in compatibility with engineering plastics and has a high refractive index to compensate for coloring of a relatively low refractive index acrylic rubber. In addition, the crosslinkable vinyl monomer used for the polymerization of the core not only maintains the polymerization stability of the latex, but also the structure of the impact modifier together with the hard seed in the matrix during processing. It helps to maintain.

In addition, the alkyl acrylate used for the polymerization of the core is selected from the group consisting of ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate. It is preferable that it is 1 or more types, and the functional group containing vinyl monomer used for superposition | polymerization of the said shell is preferably a vinyl monomer containing functional groups, such as a hydroxyl group, a carboxyl group, an epoxy group, glycidyl methacrylate, methacryl It is more preferable that it is at least 1 type selected from the group which consists of an acid, methylol acrylamide, and hydroxymethyl methacrylate.

At this time, the functional group-containing vinyl monomer used for the polymerization of the shell is an engineering plastic containing an ester group, a carboxyl group, or an epoxy group, the acrylic impact modifier of the present invention including a functional group such as hydroxyl group, carboxyl group, epoxy group, etc. Or it helps to effectively disperse in their alloys serves to maximize the impact resistance of the core, in particular low temperature impact resistance. Therefore, the acrylic impact modifier having a shell polymerized from the functional group-containing monomer is better dispersed in the engineering plastic resin than the acrylic impact modifier, which is particularly excellent in low temperature impact strength below 0 ° C.

At this time, the aromatic vinyl monomer, the hydrophilic vinyl monomer, and the crosslinkable vinyl monomer used in the polymerization of the shell are aromatic vinyl monomer, the hydrophilic vinyl monomer, and the crosslinkable vinyl monomer used in the polymerization of the seed. The same thing as a monomer may be used, or a different thing may be selected and used.

The acrylic impact modifier of the multilayer structure of the present invention preferably has an average particle diameter of 200 to 600 nm. When the average particle diameter of the acrylic impact modifier is less than 200 nm, the impact reinforcing effect is lowered, and when it exceeds 600 nm, the colorability is inferior.

The acrylic impact modifier of a multilayer structure including a sheath and a shell having such a characteristic shows high colorability to improve impact resistance of the engineering plastic resin and to realize various colors.

The acrylic impact modifier of the present invention may be prepared by mixing a) a thermoplastic resin composition having excellent low temperature impact strength and colorability by mixing 0.5 to 20 parts by weight with respect to 80 to 99.5 parts by weight of the thermoplastic matrix resin.

In this case, the thermoplastic matrix resin is preferably an engineering plastic resin selected from the group consisting of polyester resins, polyamide resins, polyacetal resins, polycarbonate resins, and two or more alloys thereof.

The thermoplastic resin composition including the acrylic impact modifier of the present invention may be molded into a desired type of product at a suitable temperature by using conventional molding methods such as extrusion molding, injection molding, and the like. It can be applied to housing parts of automation devices, electrical and electronic devices, and the like.

Acrylic impact modifier of the multi-layer structure of the present invention is a) a step of producing a seed, b) polymerizing 50 to 89.5 parts by weight of the core on the surface of the prepared 0.5 to 40 parts by weight of the seed, and c) the core prepared Polymerizing 10.0 to 49.5 parts by weight of the shell on the surface of the. In addition, if necessary, the method may further include d) drying the acrylic impact modifier latex obtained in step c).

The step of polymerization of the seed and the core may be prepared by emulsion polymerization by mixing the above-described polymerization monomer with water and an emulsifier in the above content, and the polymerization step of the shell emulsifies the monomer for shell polymerization described above. It can be prepared by graft polymerization. In this case, in the emulsion polymerization or emulsion graft polymerization, a conventional initiator for emulsion polymerization, an emulsifier, an electrolyte, or the like may be used.

Emulsifiers used in each step of the present invention may be used alone or mixed with a variety of well-known emulsifiers, in consideration of the properties of the thermoplastic matrix resin to be used as an impact modifier, oleic acid salts that are deteriorated in the acidic flocculant, Preference is given to using alkaline emulsifiers of weak acids, such as rosin acid salts or fatty acid salts.

In addition, engineering plastic resins such as polycarbonate may have the decomposition of chains by metal salts under high temperature during processing such as extrusion, so the amount of emulsifier should be minimized, and the content of emulsifier is 0.1 to 10 relative to the total monomer weight. It is preferable to use by weight part.

The polymerization initiator used in each step of the present invention may be any compound that can cause a reaction. Preferred examples of the polymerization initiator are one selected from the group consisting of ammonium persulfate, potassium persulfate, benzoyl peroxide, azobisisobutyronitrile, butyl hydroperoxide, cumin hydroperoxide, and dodecylbenzenesulfonic acid. The above can be used, and depending on the monomer properties of the selected seed, core, and shell, or the stability of the polymerization system, it is more preferable to use an initiator such as persulfate and hydroperoxide or dodecylbenzenesulfonic acid. desirable.

In addition, a molecular weight modifier may be used, and preferred examples of the molecular weight modifier may include n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptopropioic acid, methyl mercaptopropionate, isopropanol, acetaldehyde, or the like. have.

 The emulsion polymerization conditions of the above steps are not significantly different from the emulsion polymerization conditions of the conventional vinyl polymer, and those skilled in the art to which the present invention pertains can carry out without any difficulty from the description of the present invention. As such, detailed description is omitted.

The polarity and glass transition temperature of the seed can be controlled by the content of the aromatic vinyl monomer having a relatively high glass transition temperature and the hydrophilic vinyl monomer having a polar group, and the crosslinking degree, gel content, particle size, etc. Amount, amount of emulsifier, and amount of electrolyte. However, the adjustment of the amount of the emulsifier and the electrolyte can be appropriately selected by those skilled in the art as needed, and therefore, the present invention is not particularly limited.

However, the seed is preferably polymerized to have an average particle diameter of 100 to 200 nm, and is preferably polymerized to have a solid concentration of 8 to 15 wt% in the seed latex after polymerization of the seed is completed. If the concentration of the solid content is less than 8% by weight, the productivity is lowered, and when the concentration of the solid content is more than 15% by weight, the latex concentration is increased, which may cause stability.

In addition, the polymerization step of the core includes 50 to 89.5 parts by weight (based on the weight of the impact modifier) of the monomer mixture for core polymerization in the seed latex containing 0.5 to 40 parts by weight of the prepared sheath (impact enhancer weight). It is preferable to add the emulsion, and to polymerize the core latex by emulsion polymerization.

In this case, a variety of methods may be used as the input method of the monomer for the core polymerization, i) as a power feeding method to be introduced into the reactor while gradually increasing the content of the monomer having a relatively high glass transition temperature in the emulsion. It is preferred to add, ii) at a time, iii) continuously, or iv) continuously into the prepared latex for 1 to 2 hours with a solvent dissolving the monomer.

In addition, the step of polymerization of the shell is a monomer for shell polymerization in the core latex containing 0.5 to 40 parts by weight of the prepared sheath (based on the weight of the impact modifier) and 50 to 89.5 parts by weight (based on the weight of the impact modifier). It is preferable to add an emulsion containing 49.5 parts by weight and to emulsion graft polymerize it.

At this time, it is preferable that the finally produced acrylic impact modifier of the multilayer structure has an average particle size of 200 to 600 nm, the solid content concentration in the final latex is 30 to 50% by weight after the polymerization is completed. When the concentration of the solid content is less than 30% by weight, the productivity decreases, and when the concentration of the solid content exceeds 50% by weight, the stability of the latex drops rapidly.

The acrylic impact modifier latex having a multilayer structure obtained by polymerizing the seed, the core, and the shell may be obtained in powder form through a drying process. That is, the prepared impact modifier latex is diluted with ion-exchanged water so that the solid content is 10 to 15% by weight, and then aggregated by adding an acid or a basic solution, and the aggregated mixed solution is heated to 90 ° C. or more and aged. After cooling, washing, filtration, and drying, it can be obtained as an impact modifier in powder form. At this time, the drying process is preferably dried so that the moisture content is less than 0.1% by weight.

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

EXAMPLE

Example 1

(Polymerization of Seed Latex)

970.60 g of ion-exchanged water was introduced into the reactor, and the inside of the reactor was made into a nitrogen atmosphere, and then the temperature was raised to 75 ° C.

When the temperature of the ion-exchanged water reached 75 ° C, 84.4 g of styrene (ST), acrylonitrile (11.25 g (8 wt% solution) of fatty acid potassium salt solution, 50 g (5 wt% solution) of sodium bicarbonate solution) AN) 12.6 g, allyl methacrylate (AMA) 1.0 g, and divinylbenzene (DVB) 2.0 g were added at a time and stirred to prepare an emulsion.

After the temperature in the reactor was stabilized at 70 ° C., 22 g (3 wt% solution) of potassium persulfate solution was added thereto, and the reaction was continued for 2 hours.

The particle size of the polymerized seed latex was measured using a laser light scattering device, NICOMP, and found to be 150 nm with a conversion of 98%.

(Core Latex Polymerization Step)

280 g of ion-exchanged water, 80 g of fatty acid solution (8 wt% solution), 546.7 g of butyl acrylate (BA) and 3.3 g of allyl methacrylate were added to a separate container, and the mixture was stirred vigorously to prepare an emulsion.

The prepared monomer emulsion was introduced into the reactor containing the previously prepared seed latex at 70 ° C. nitrogen atmosphere three times at an interval of 1 hour, and the reaction proceeded.

At this time, 0.008 g of FES (ferrous sulfate) and 0.143 g of EDTA (disodiumethylenediaminetetraacetate) were added into the reactor before the monomer emulsion was added, and 10 minutes after each monomer emulsion was added, SFS ( 12 g of formaldehyde sodium sulfoxylate (3 wt% solution) solution and 3 g of t-BHP (t-butylhydroperoxide) solution (10 wt% solution) were added thereto.

After completion of the reaction, the aging step was performed for 1 hour. The particle size of the polymerized core latex was measured using a laser light scattering device, NICOMP, and was 255 nm, and the conversion rate was 99%.

(Shell latex polymerization stage)

The polymerization of the shell latex was carried out by preparing a monomer emulsion for shell polymerization in advance and introducing the reactor into the reactor continuously for 2 hours.

135.43 g of ion-exchanged water, 70 g of fatty acid solution (8 wt% solution), styrene 297.97 g, acrylonitrile 43.03 g, 10 g glycidyl methacrylate (GMA), 3 g allyl methacrylate and divinyl 6 g of benzene was added thereto, followed by vigorous stirring to prepare a monomer emulsion.

The prepared monomer emulsion was continuously added to the reactor containing the core latex prepared in a nitrogen atmosphere at 70 ° C. for 2 hours, and 30 g of SFS solution and 10 g of t-BHP solution were continuously added for the same time. .

After the reaction was terminated, a small amount of initiator (t-BHP) was added to increase the conversion rate to undergo a aging step for 1 hour.

The particle size of the polymerized final latex was 330 nm using a laser light scattering device NICOMP and the conversion was 99%.

(Production of impact modifier powder)

Ion-exchanged water was added to the final latex prepared above to lower the final solid content to 10% by weight or less, and then 2% by weight of hydrochloric acid was slowly added thereto.

The slurry mixture thus prepared was heated to 90 ° C. or higher, aged, and cooled to room temperature.

It was washed with ion-exchanged water, filtered and dried to give a powdered impact modifier with a water content of less than 0.1% by weight.

(Production of polycarbonate / polybutylene terephthalate (PC / PBT) alloy thermoplastic resin)

95 parts by weight of PC / PBT alloy resin (30 parts by weight of LUPOX GP-2000, 65 parts by weight of Caliber PC 200-3), 5 parts by weight of the multilayered impact modifier, 0.5 parts by weight of antioxidant and lubricant, and 0.02 parts by weight of the pigment was mixed and extruded using a twin screw extruder manufactured by Leistritz at 200 rpm at a metering speed of 60 kg / hr and a temperature of 200 ° C. to 250 ° C. to obtain pellets. The pellets were injected at a temperature of 220 ° C. to 250 ° C. using an EC100 Φ 30 injection machine manufactured by ENGEL.

Example 2

Example 1 except that the weight of styrene (ST), acrylonitrile (AN), and glycidyl methacrylate was changed to 270.56 g, 40.43 g, and 30 g, respectively, in the preparation of the shell latex. An impact modifier and an alloy thermoplastic resin were produced by the method.

Example 3

Except for changing the weight of styrene (ST), acrylonitrile (AN), and glycidyl methacrylate to 209.67 g, 31.33 g, and 100 g, respectively, in the manufacture of shell latex, An impact modifier and an alloy thermoplastic resin were produced by the method.

Examples 4-6

When prepared at the time of preparation of the shell latex, the impact modifier and alloy thermoplastic in the same manner as in Examples 1, 2, and 3, except that glycidyl methacrylate was changed to methylacrylic acid (MAA), respectively. Resin was prepared.

Comparative Example 1

An impact modifier and an alloy thermoplastic resin were prepared in the same manner as in Example 1, except that acrylonitrile was increased to 53.03 g without using glycidyl methacrylate (GMA) in preparing the shell latex. It was.

Comparative Example 2

An impact modifier and an alloy thermoplastic resin were prepared in the same manner as in Example 1 except that 97.0 g of butyl acrylate (BA) was used alone in the preparation of the seed latex.

Comparative Example 3

An impact modifier and an alloy thermoplastic resin were manufactured in the same manner as in Example 1, except that 97.0 g of 1,2-butadiene (BD) was used alone to prepare the seed latex.

Comparative Example 4

An impact modifier and an alloy thermoplastic resin were prepared in the same manner as in Example 13 except that methyl methacrylate was increased to 197 g without using glycidyl methacrylate (GMA) in the preparation of the shell latex. It was.

Comparative Example 5

An impact modifier and an alloy thermoplastic resin were prepared in the same manner as in Example 1, except that 99.4 g of butyl acrylate (BA) and 0.6 g of allyl methacrylate were used to prepare the seed latex.

Comparative Example 6

Only 82.75 g of styrene and 14.25 g of acrylonitrile are used as monomers in the preparation of the seed latex, and only 48.52 g of butylacrylate, 0.2 g of allyl methacrylate, and 4.98 g of methyl methacrylate are used as monomers in the preparation of the core. In the same manner as in Example 1, except that only 29.898 g of methyl methacrylate, 0.0195 g of allyl methacrylate, and 0.054 g of divinylbenzene were used as monomers in the preparation of the shell, Roy thermoplastic resin was prepared.

The impact strength of the alloy thermoplastic resin including the acrylic impact modifier of the multilayer structure prepared according to Examples 1 to 15, and Comparative Examples 1 to 5 is made of impact specimens according to ASTM D-256 standard 1/8 inch specimen After measuring the Izod impact strength at room temperature and -30 ℃, respectively, the results are shown in Table 1 below.

Colorability was evaluated by measuring the CIE Lab color value using a spectrophotometer Color-eye 3100 to the specimens processed using a colorant and the results are shown in Table 1 below. The colorability can be judged by ΔE = (ΔL * ² + Δa * ² + Δb * ² ) ^1/2 , which represents the difference in color values based on the specimen with the best coloration. This means high, and when ΔE is large, the colorability is low.

TABLE 1

Izod impact strength (25 ℃, kgcm / cm) Izod impact strength (-30 ℃, kgcm / cm) Colorability (△ E) Example 1 72 22 - Example 2 77 24 One Example 3 68 20 3 Example 4 75 22 2 Example 5 70 19 2 Example 6 70 20 5 Comparative Example 1 75 15 2 Comparative Example 2 68 16 11 Comparative Example 3 66 19 4 Comparative Example 4 72 17 14 Comparative Example 5 67 19 8 Comparative Example 6 68 19 13

As shown in Table 1, the acrylic impact modifier of the multi-layered structure of the present invention is excellent in the effect of reinforcing the impact resistance of the engineering plastic resin, in particular excellent in impact resistance at low temperatures, and at the same time excellent in colorability. have.

 The acrylic impact modifier of the present invention is a multilayered acrylic polymer in which a copolymer of an aromatic vinyl monomer and a hydrophilic vinyl monomer is used as a seed to form a rubber core and a functional shell containing a functional group, and include a PC / PBT alloy, It is added to engineering plastic resins such as PBT, PC, and PA to impart excellent impact resistance and colorability. In addition, the thermoplastic resin including the impact modifier of the multilayer structure shows excellent impact resistance and colorability.

Claims (13)

a) 0.5 to 40 parts by weight of the seed, based on the weight of the composition; b) 50 to 89.5 parts by weight of the core surrounding the sheath, based on the weight of the composition; And c) 10.0 to 49.5 parts by weight of the shell surrounding the core, based on the weight of the composition Including; A) the seed is i) 65 to 99.4 parts by weight of aromatic vinyl monomer (based on the weight of the seed monomer); ii) 0.5 to 30 parts by weight of the hydrophilic vinyl monomer (based on the weight of the seed monomer); And iii) 0.1 to 5 parts by weight of the crosslinkable vinyl monomer (based on the weight of the seed monomer) Comprising a copolymer polymerized from B) the core is i) 95.0 to 99.9 parts by weight of an alkyl acrylate having 2 to 8 carbon atoms of the alkyl group (based on the weight of the core monomer), and ii) 0.1 to 5.0 parts by weight of the crosslinker monomer (based on the weight of the core monomer) Comprising a copolymer polymerized from C) the shell is i) 55 to 98.9 parts by weight of an aromatic vinyl monomer (based on the weight of the shell monomer), ii) 0.5 to 30 parts by weight of the hydrophilic vinyl monomer (based on the weight of the shell monomer), iii) 0.1 to 5 parts by weight of the crosslinkable vinyl monomer (based on the weight of the shell monomer), and iv) 0.5 to 10 parts by weight of the functional group-containing vinyl monomer (based on the weight of the shell monomer) Acrylic impact modifier of a multilayer structure comprising a copolymer polymerized from. According to claim 1, wherein the a) i), and the aromatic vinyl monomer of c) i) is at least one member selected from the group consisting of styrene, alphamethylstyrene, 4-methylstyrene, and 3,4-dichlorostyrene. Acrylic impact modifier of multilayer structure. The method of claim 1, wherein the a) ii), and the hydrophilic vinyl monomer of c) ii) is acrylonitrile, methacrylonitrile, benzyl methacrylate, aryl methacrylate, and alkyl group of 1 to 8 carbon atoms An acrylic impact modifier of at least one type of multilayer structure selected from the group consisting of phosphorus alkyl acrylate and alkyl methacrylate. The method of claim 1, wherein the crosslinkable vinyl monomers of a) iii), b) ii), and c) iii) are divinylbenzene, 3-butanedioldiacrylate, 1,3-butanedioldimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol dimethacrylate Acrylic impact modifier of at least one type selected from the group consisting of a multilayer structure. The method of claim 1, wherein b) i) alkyl acrylate is composed of ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate. Acrylic impact modifier of a multilayer structure of at least one selected from the group. The multilayer monomer according to claim 1, wherein the functional group-containing vinyl monomer of c) iv) is at least one member selected from the group consisting of glycidyl methacrylate, methacrylic acid, methylol acrylamide, and hydroxymethyl methacrylate. Acrylic impact modifier of structure. The acrylic impact modifier of claim 1, wherein the size of the seed particles of the acrylic impact modifier is 100 to 200 nm. The acrylic impact modifier of claim 1, wherein the final particle size of the acrylic impact modifier is 200 to 600 nm. The acrylic impact modifier of claim 1, wherein the glass transition temperatures of the sheath, the core, and the shell of the acrylic impact modifier are 60 to 100 ° C., −60 to 0 ° C., and 60 to 100 ° C., respectively. i) 65 to 99.4 parts by weight of an aromatic vinyl monomer (based on the weight of the seed monomer), ii) 0.5 to 30 parts by weight of the hydrophilic vinyl monomer (based on the weight of the seed monomer), and iii) 0.1 to 5 parts by weight of the crosslinkable vinyl monomer (based on the weight of the seed monomer) Preparing a seed latex by reacting the emulsion containing emulsion by emulsion polymerization; b) a seed latex comprising 0.5 to 40 parts by weight of the seed of step a) (based on the weight of the impact modifier). i) 95.0 to 99.9 parts by weight of an alkyl acrylate having 2 to 8 carbon atoms of the alkyl group (based on the weight of the core monomer), and ii) 0.1 to 5.0 parts by weight of the crosslinker monomer (based on the weight of the core monomer) Preparing a core latex by adding an emulsion containing 50 to 89.5 parts by weight (based on the weight of an impact modifier) and a monomer mixture including an emulsion; And c) 50 to 89.5 parts by weight of the core of step b) (based on the weight of the impact modifier) i) 55 to 98.9 parts by weight of an aromatic vinyl monomer (based on the weight of the shell monomer), ii) 0.5 to 30 parts by weight of the hydrophilic vinyl monomer (based on the weight of the shell monomer), iii) 0.1 to 5 parts by weight of the crosslinkable vinyl monomer (based on the weight of the shell monomer), and iv) 0.5 to 10 parts by weight of the functional group-containing vinyl monomer (based on the weight of the shell monomer) Adding an emulsion containing a monomer mixture 10.0 to 49.5 parts by weight (based on the weight of the impact modifier) comprising an emulsion, the step of emulsion graft polymerization to form a shell latex Method of manufacturing an acrylic impact modifier of a multilayer structure comprising a. The method of claim 10, wherein the acrylic impact modifier d) drying the acryl-based impact modifier latex obtained in step c) to powder and further comprising the step of drying. a) 80 to 99.5 parts by weight of the thermoplastic matrix resin, and b) 0.5 to 20 parts by weight of the acrylic impact modifier according to any one of claims 1 to 9 Thermoplastic resin composition comprising a. 13. The thermoplastic resin composition of claim 12, wherein the thermoplastic matrix resin is selected from the group consisting of polyester resins, polyamide resins, polyacetal resins, polycarbonate resins, and alloys of two or more thereof.