KR102016469B1 - A method for manufacturing acrylic graft copolymer having improved impact strength and surface appearance - Google Patents

Abstract

According to an aspect of the present invention, there is provided a structure including a layer of an acrylic rubber on the surface of the rubber-modified graft copolymer (a) by reacting a rubber-modified graft copolymer, an acrylic monomer, a first initiator, a crosslinking agent, and an emulsifier. Manufacturing step; And (b) grafting a copolymer of an aromatic vinyl monomer and an unsaturated nitrile monomer to the structure in the presence of a mercaptan-based molecular weight regulator and a second initiator, wherein the second initiator is a peroxycarbonate-based compound. The amount of the mercaptan-based molecular weight modifier is 0.1 to 0.5 parts by weight based on 100 parts by weight of the copolymer consisting of the aromatic vinyl monomer and unsaturated nitrile monomer provides a method for producing an acrylic graft copolymer.

Description

A method for producing an acrylic graft copolymer having excellent impact resistance and appearance {A METHOD FOR MANUFACTURING ACRYLIC GRAFT COPOLYMER HAVING IMPROVED IMPACT STRENGTH AND SURFACE APPEARANCE}

The present invention relates to an acrylic graft copolymer and a method for producing the same, and more particularly, to a method for producing the acrylic graft copolymer having excellent impact resistance and appearance.

In general, ABS resin obtained by graft copolymerization of styrene and acrylonitrile monomer to butadiene-based rubbery polymer has excellent impact resistance, processability, excellent mechanical strength and heat deformation temperature, and good colorability. It is widely used in equipment and the like.

However, the ABS resin contains a chemically unstable double bond in the rubber component used, so that the rubber component is easily aging due to ultraviolet rays, which is very vulnerable to weather resistance.

On the other hand, the method of using the chemically stable acrylic rubber instead of butadiene rubber, the method using the rubbery polymer which superposed | polymerized butadiene and an acrylic polymerizable monomer, etc. are used.

In particular, the ASA (Acrylate-Styrene-Acrylonitrile) graft copolymer resin obtained by graft copolymerization of styrene and acrylonitrile monomers to an acrylic rubber polymer requires special weather resistance such as automobile and agricultural equipment with high exposure to sunlight, and special weather resistance. It is widely used in electrical and electronic goods.

Since ASA resin does not have a chemically unstable double bond, a special effect can be obtained in weather resistance, but there is a problem of low impact resistance and colorability compared to ABS resin.

On the other hand, a method of increasing the acrylic rubber particle diameter or lowering the gel content of the rubbery polymer has been proposed, but these methods are not only difficult to control the properties of the graft copolymer, but also deteriorate the resin appearance properties such as glossiness. have. In addition, in order to improve the impact resistance, but to improve the physical properties such as impact resistance and gloss by producing and mixing each of the acrylic rubber having a different particle diameter, but has not been sufficiently satisfactory results.

In addition, although the mechanical properties of the thermoplastic ASA resin including these ASA resins are excellent, the gloss and flowability may be low, thereby limiting applications.

 Therefore, there is a demand for technology development for an ASA graft copolymer having excellent appearance and thermal stability as well as impact resistance.

The present invention is to solve the above problems of the prior art, the object of the present invention is to improve the impact resistance and appearance problems of the acrylic graft copolymer, while maintaining the thermal stability, improve the flowability, and balance them It is to provide a method for producing an acrylic graft copolymer that can be implemented.

According to an aspect of the present invention, there is provided a structure including a layer of an acrylic rubber on the surface of the rubber-modified graft copolymer (a) by reacting a rubber-modified graft copolymer, an acrylic monomer, a first initiator, a crosslinking agent, and an emulsifier. Manufacturing step; And (b) grafting a copolymer of an aromatic vinyl monomer and an unsaturated nitrile monomer to the structure in the presence of a mercaptan-based molecular weight regulator and a second initiator, wherein the second initiator is a peroxycarbonate-based compound. The amount of the mercaptan-based molecular weight modifier is 0.1 to 0.5 parts by weight based on 100 parts by weight of the copolymer consisting of the aromatic vinyl monomer and unsaturated nitrile monomer provides a method for producing an acrylic graft copolymer.

In one embodiment, the rubber modified graft copolymer may be a copolymer in which an aromatic vinyl monomer and an unsaturated nitrile monomer are grafted to a conjugated diene rubber.

In one embodiment, the conjugated diene rubber is 1,3-butadiene, 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene and 2,3-dimethyl-1,3-butadiene It may be one or more polymers or copolymers selected from the group consisting of.

In one embodiment, the aromatic vinyl monomer is styrene, α-methylstyrenevinyltoluene, t-butylstyrene, halogen-substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, ethylstyrene, and two of them. It may be one selected from the group consisting of the above combination.

In one embodiment, the unsaturated nitrile monomer is one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, and combinations of two or more thereof Can be.

In one embodiment, the acrylic monomer may be one selected from the group consisting of (meth) acrylic acid, alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms, and a combination of two or more thereof.

In one embodiment, the first initiator may be a water-soluble initiator.

In one embodiment, the first initiator may be one selected from the group consisting of potassium persulfate, sodium persulfate, ammonium persulfate, silver persulfate, and combinations of two or more thereof.

In one embodiment, the second initiator is 2,5-dimethyl-2,5-di- (2-ethylhexanonylperoxy) hexane, t-amylperoxy-2-ethylhexanoate, t-butyl Peroxy-2-ethylhexanoate, t-amyl (2-ethylhexyl) monoperoxycarbonate, t-butylisopropyl monoperoxycarbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) Hexane, t-butyl- (2-ethylhexyl) monoperoxycarbonate, t-amylperoxybenzoate, tertiarybutylperoxyacetate, t-butylperoxy-3,5,5-trimethylhexanoate and t -Butyl peroxybenzoate and one selected from the group consisting of two or more thereof.

In one embodiment, the mercaptan-based molecular weight modifier may be one selected from the group consisting of n - decyl mercaptan, n- dodecyl mercaptan , t- dodecyl mercaptan , n-octadecyl mercaptan and combinations of two or more thereof have.

In one embodiment, the crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate Methacrylate, neopentyl glycol dimethacrylate, trimethylolpropanetrimethacrylate, trimethylolmethanetriacrylate, arylmethacrylate, triarylamine, diarylamine, triarylisocyanurate, triarylcyanu Rate, and a combination of two or more thereof.

In one embodiment, the emulsifier is an alkali salt of fatty acid soap, rosin acid, oleic acid, or succinic acid; Alkyl aryl sulfonates; Alkali methyl alkyl sulfates; Alkali alkyl sulfonates; Sulfonated alkyl esters; And it may be one selected from the group consisting of two or more combinations thereof.

In one embodiment, the average particle diameter of the conjugated diene rubber may be 250nm to 350nm.

In one embodiment, the amount of the crosslinking agent may be 0.1 to 0.5 parts by weight based on 100 parts by weight of the copolymer consisting of the aromatic vinyl monomer and the unsaturated nitrile monomer.

According to one aspect of the invention, the monomer is grafted around the rubber component,

Rubber-modified graft copolymer and acrylic type endowed with a certain level of rigidity on cotton

By reacting the monomer in the presence of the second initiator and the molecular weight regulator, a structure including a layer of acrylic rubber on the surface of the rubber-modified graft copolymer can be stably produced.

The acrylic graft copolymer in which the aromatic vinyl monomer and the unsaturated nitrile monomer are grafted to the structure may achieve balanced appearance and flow while maintaining impact resistance and weather resistance.

It is to be understood that the effects of the present invention are not limited to the above effects, and include all effects deduced from the configuration of the invention described in the detailed description or claims of the present invention.

Hereinafter, the present invention will be described in detail. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

Throughout the specification, when a part is "connected" to another part, this includes not only "directly connected" but also "indirectly connected" with another member in between. . In addition, when a part is said to "include" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.

According to an aspect of the present invention, there is provided a structure including a layer of an acrylic rubber on the surface of the rubber-modified graft copolymer (a) by reacting a rubber-modified graft copolymer, an acrylic monomer, a first initiator, a crosslinking agent, and an emulsifier. Manufacturing step; And (b) grafting a copolymer of an aromatic vinyl monomer and an unsaturated nitrile monomer to the structure in the presence of a mercaptan-based molecular weight regulator and a second initiator, wherein the second initiator is a peroxycarbonate-based compound. The amount of the mercaptan-based molecular weight modifier is 0.1 to 0.5 parts by weight based on 100 parts by weight of the copolymer consisting of the aromatic vinyl monomer and unsaturated nitrile monomer provides a method for producing an acrylic graft copolymer.

In the step (a), a rubber-modified graft copolymer and an acrylic monomer are reacted in the presence of a first initiator, a crosslinking agent, and an emulsifier to prepare a structure including a layer of acrylic rubber on the surface of the rubber-modified graft copolymer. can do. The reaction may be a conventional emulsion polymerization reaction.

In addition, an activator may be included in the emulsion polymerization reaction, and the activator may be sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, ferrous sulfate, lactose, dextrose, sodium liroline, sodium sulfate, and the like. It may be one selected from the group consisting of two or more of these, preferably sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate and ferrous sulfate, but is not limited thereto.

The rubber modified graft copolymer may be a copolymer in which an aromatic vinyl monomer and an unsaturated nitrile monomer are grafted to a conjugated diene rubber.

In order to improve the colorability, weather resistance and impact strength of the acrylic graft copolymer, a method of using a multilayer acrylate rubber polymer including a diene rubber polymer therein has been proposed, but for forming a plurality of shells according to a certain conversion rate Since the monomers must be introduced sequentially, it is difficult to control the reaction, and the rigidity of the surface of the diene-based rubber, which is a core part, is low so that acrylate rubber cannot be effectively laminated thereon, thereby achieving a required level of weather resistance.

In contrast, the rubber-modified graft copolymer is obtained by grafting an aromatic vinyl monomer and an unsaturated nitrile monomer on the surface of a conjugated diene-based rubber, and thus has high surface rigidity as compared to the ungrafted conjugated diene-based rubber. The formed acrylic rubber can be stably separated, without arbitrarily penetrating into the conjugated diene rubber therein.

In addition, it is possible to simplify the process and improve reproducibility by using a rubber-modified graft copolymer that is prepared at a conversion rate of 99% or more without considering conversion between reactions as in the prior art.

The conjugated diene rubber contributes to impact resistance and colorability, the acrylic rubber contributes to weather resistance, and there is a trade-off in the action of each rubber component, so that each rubber component when they are arbitrarily mixed This can be accompanied by a deterioration of the effect. For example, when the acrylic rubber formed on the surface is randomly infiltrated into the conjugated diene rubber therein, not only the weather resistance derived from the acrylic rubber in the final product is lowered, but also the impact resistance and colorability derived from the conjugated diene rubber are also reduced. Can be.

Since the structure is a seed having a copolymer in which an aromatic vinyl monomer and an unsaturated nitrile monomer are grafted on the surface of the conjugated diene rubber, and the acrylic monomer is reacted and polymerized on the surface of the seed, the structure is conjugated from the inside. The diene rubber, the monomer grafted on the surface thereof, and the acrylic rubber may be sequentially included.

That is, since the conjugated diene-based rubber and the acrylic rubber in the structure are separated from each other independently by monomers grafted on the surface of the conjugated diene-based rubber, weather resistance derived from acrylic rubber in the final product, and conjugated Both impact resistance and coloring properties derived from diene rubber can be achieved in a balanced manner.

The conjugated diene rubber is at least one selected from the group consisting of 1,3-butadiene, 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene and 2,3-dimethyl-1,3-butadiene It may be a polymer or a copolymer, and preferably, it may be a homopolymer of 1,3-butadiene, but is not limited thereto.

An average particle size of the conjugated diene rubber may be 250 to 350 nm, and preferably, 280 to 330 nm. If the average particle size of the conjugated diene rubber is less than 250nm, the impact strength imparting effect is insignificant, and if it is more than 350nm, the gloss and colorability of the final product may be lowered.

The content of the conjugated diene rubber may be 10 to 40% by weight based on the total weight of the rubber component included in the structure, that is, the conjugated diene rubber and the acrylic rubber.

have. When the content of the conjugated diene rubber is less than 10% by weight, impact resistance and colorability may be lowered, and when the content of the conjugated diene rubber is greater than 40% by weight, it is difficult to form a layer made of acrylic rubber, and thus weather resistance may be lowered.

In the group wherein the aromatic vinyl monomer is styrene, α-methylstyrene vinyltoluene, t-butylstyrene, halogen-substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, ethyl styrene, and combinations of two or more thereof It may be one selected, preferably styrene, but is not limited thereto.

The unsaturated nitrile monomer may be one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, and combinations of two or more thereof, and preferably And may be acrylonitrile, but is not limited thereto.

The acrylic monomer may be one selected from the group consisting of (meth) acrylic acid, alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms, and a combination of two or more thereof, and preferably, may be butyl acrylate. It is not limited to this.

In addition, by adding a water-soluble initiator suitable for the emulsion polymerization reaction as an initiator for imparting a radical to the rubber-modified graft copolymer, the acrylic monomer can be smoothly polymerized on the surface of the rubber-modified graft copolymer.

The input amount of the first initiator may be 0.1 to 5 parts by weight. When the amount of the first initiator is less than 0.1 part by weight, the reaction rate and the conversion rate of the acrylic monomer may be lowered. When the amount of the first initiator is more than 5 parts by weight, the molecular weight and the average particle size of the structure may be reduced, thereby reducing the impact resistance of the final product. .

The first initiator is a water-soluble initiator, may be a persulfate compound, preferably, one selected from the group consisting of potassium persulfate, sodium persulfate, ammonium persulfate, silver persulfate, and combinations of two or more thereof It may be, but is not limited thereto.

In the structure, the rubber modified graft copolymer and the acrylic rubber may be bonded by a crosslinking agent. The crosslinking agent may link the radicals generated on the surface or the outer surface of the rubber-modified graft copolymer with the acrylic monomer by the first initiator, and the acrylic rubber and the radicals generated by random polymerization of the acrylic monomers. You can also connect.

The crosslinking agent may stabilize the structure by forming a strong bond between the rubber modified graft copolymer and the acrylic rubber.

The amount of the crosslinking agent may be 0.1 to 5 parts by weight. When the amount of the crosslinking agent is less than 0.1 part by weight, the acrylic rubber may hardly be formed on the surface of the rubber-modified graft copolymer, and when the amount of the crosslinking agent is greater than 5 parts by weight, impact resistance may be lowered.

The crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanoic diol dimethacrylate, neopentyl glycol Dimethacrylate, trimethylolpropanetrimethacrylate, trimethylolmethanetriacrylate, arylmethacrylate, triarylamine, diarylamine, triarylisocyanurate, triarylcyanurate, and two of these It may be one selected from the group consisting of the above combination, preferably triaryl cyanurate, but is not limited thereto.

The amount of the emulsifier may be 0.1 to 5 parts by weight. When the amount of the emulsifier is less than 0.1 part by weight, the stability of the latex may be reduced, and the coagulum may be increased. When the amount of the emulsifier is greater than 5 parts by weight, the average particle size of the structure may be decreased, thereby reducing the impact resistance of the final product.

The emulsifiers include alkali salts of fatty acid soaps, rosin acids, oleic acids, or succinic acids; Alkyl aryl sulfonates; Alkali methyl alkyl sulfates; Alkali alkyl sulfonates; Sulfonated alkyl esters; And it may be one selected from the group consisting of two or more of these, preferably, it may be dioctylsulfursulfate, but is not limited thereto.

On the other hand, in the step (b), the acrylic graft copolymer may be prepared by copolymerizing 30 to 120 parts by weight of aromatic vinyl monomer and 20 to 60 parts by weight of unsaturated nitrile monomer in the structure.

The copolymerization in step (b) may be performed by a conventional emulsion polymerization reaction, and after the reaction, the latex product may be aggregated and dried to obtain an acryl-based graft copolymer.

The second initiator is 2,5-dimethyl-2,5-di- (2-ethylhexanoylperoxy) hexane, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethyl Hexanoate, t-amyl (2-ethylhexyl) monoperoxycarbonate, t-butylisopropyl monoperoxycarbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl- (2-ethylhexyl) monoperoxy carbonate, t-amyl peroxy benzoate, tertiary butyl peroxy acetate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy benzoate And it may be one selected from the group consisting of two or more combinations thereof, preferably t-butyl isopropyl monoperoxy carbonate or t-butyl- (2-ethylhexyl) monoperoxy carbonate, but is not limited thereto It is not.

The mercaptan-based molecular weight modifier may be one selected from the group consisting of n -decylmercaptan , n -dodecylmercaptan , t -dodecylmercaptan , n-octadecylmercaptan, and combinations of two or more thereof, and preferably 3 -Dodecyl mercaptan, but is not limited thereto.

The mercaptan-based molecular weight modifier may be included in an amount of 0.1 to 0.5 parts by weight, preferably 0.2 to 0.4 parts by weight, and 0.1 part by weight of mercaptan-based molecular weight modifier based on 100 parts by weight of the copolymer comprising the aromatic vinyl monomer and the unsaturated nitrile monomer. If the amount is less than the effect of improving the gloss is insufficient, if it is more than 0.5 parts by weight mechanical properties can be greatly reduced.

Hereinafter, embodiments of the present invention will be described in detail.

Example 1

300 parts by weight of ion-exchanged water and 50 parts by weight of ABS latex (based on solids) were heated to 70 ° C. under a nitrogen-substituted atmosphere, and then 1 part by weight of potassium persulfate as the first initiator was added and stirred for 10 minutes. Then, 100 parts by weight of butyl acrylate, a mixture of 1 part by weight of triarylcyanurate as a crosslinking agent, and 1 part by weight of an aqueous solution of dioctylsulfursulfate as an emulsifier were continuously added for 4 hours to polymerize. The polymerized product was aged by further stirring at a temperature of 70 ° C. for 1 hour to obtain rubber particles.

50 parts by weight of ion-exchanged water and an activator are added to 50 parts by weight of the rubber particles (based on a solid content) and then mixed, and then 50 parts by weight of a styrene-acrylonitrile compound copolymer and a molecular weight modifier tertiary dodecyl mercaptan (TDDM) 0.1 parts by weight was continuously added for 4 hours to perform graft polymerization. At the same time, 1.5 parts by weight of an emulsifier, 0.2 parts by weight of a peroxycarbonate-based t-butyl isopropyl monoperoxycarbonate as a second initiator, and 10 parts by weight of ion-exchanged water were charged for 4 hours 30 minutes. After further stirring for 1 hour for aging process to obtain acrylate-styrene-acrylonitrile latex.

Example 2

A graft copolymer latex was obtained in the same manner as in Example 1, except that the amount of the molecular weight modifier 3-dodecyl mercaptan was changed to 0.2 part by weight.

Example 3

A graft copolymer latex was obtained in the same manner as in Example 1, except that t-butyl (2-ethylhexyl) monoperoxycarbonate was replaced with t-butyl isopropyl monoperoxycarbonate as the second initiator. .

Comparative Example 1

A graft copolymer latex was obtained in the same manner as in Example 1, except that the molecular weight modifier 3-dodecyl mercaptan was omitted.

Comparative Example 2

A graft copolymer latex was obtained in the same manner as in Example 1, except that the amount of the molecular weight modifier 3-dodecyl mercaptan was changed to 0.3 part by weight.

Comparative Example 3

A graft copolymer latex was obtained in the same manner as in Example 1, except that cumene hydroperoxide was substituted for t-butyl isopropyl monoperoxycarbonate as the second initiator.

Comparative Example 4

A graft copolymer latex was obtained in the same manner as in Example 1, except that ASA latex (Kumho ASA latex, rubber size: 300), which is a single rubber containing no diene rubber instead of ABS latex, was obtained.

Experimental Example

The latex prepared in the examples and the comparative was ASA powder obtained through the aggregation and drying process.

Each prepared ASA dry powder was then kneaded with normal styrene-acrylonitrile (SAN). At this time, 22 parts by weight of ASA powder rubber was added to 100 parts by weight of the SAN resin composition, and 0.2 parts by weight of antioxidant, 0.7 parts by weight of lubricant, and 2 parts by weight of black colorant were mixed. The specimen was then prepared using a twin extruder and an injection machine at a temperature of 230 ℃.

Evaluation of physical properties and the evaluation method for the specimen is as follows.

Impact strength (kgfcm / cm): The specimen thickness is 3.2 mm and measured according to ASTM D256.

Coloring: L value was measured using a spectrophotometer (Datacolor 650). The lower the L value, the better the color book.

Surface gloss: measured using a Micro Haze Plus at an angle of 60 degrees.

Flowability (MI): measured at 220 ° C. and 10 kg condition according to ASTM D1238.

-Flow mark: The presence or absence of a flow mark was visually checked using three color specimens with height deviations. (Yes: ○, none X).

-Thermal stability (△ gloss): After 10 minutes of resin stay in the injection machine screw set to 240 ℃, it showed a change in glossiness (△ Gloss) before and after staying for the molded specimens, the closer to 0 the thermal stability This is excellent.

Weatherability: The degree of discoloration (ΔE) was measured with a colorimeter after 4,500 KJ / m2 exposure based on SAEJ2527 using a weatherometer. ΔE is the arithmetic mean value of the CIE Lab values before and after the stay, and the closer to 0, the better the thermal stability. The color difference meter was measured using Datacolor 650.

-Graft rate (%): After adding tetrahydrofuran (THF) to 0.5 g of acrylic graft copolymer powder, stirring at room temperature for 24hr, centrifuging to collect only the part which is insoluble in THF, and measuring the weight before and after drying. It measured by the following formula.

Graft Rate (%) = (Weight of Grafted Monomer / Weight of Core Polymer) ⅹ100

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Impact strength 23 21 22 23 12 22 15 Degree of coloring 27.5 27.6 27.5 27.5 27.8 27.6 29.5 Surface polished 93 94 93 87 84 90 93 Flow 16 21 15 9 27 15 15 Flow mark X X X O X X X Thermal stability 9 11 8 8 23 19 10 Weather resistance 15.6 16.2 15.9 15.3 18.2 17.4 15.5 Graft rate 43 35 44 51 20 28 45

Referring to Table 1, the amount of the molecular weight mercaptan-based molecular weight regulator is added 0.1 to 0.5 parts by weight based on 100 parts by weight of the copolymer consisting of the aromatic vinyl monomer and unsaturated nitrile monomer and the peroxycarbonate-based as the second initiator Examples 1 to 3 were all improved in impact strength, surface gloss, flowability, flow mark, thermal stability and graft ratio compared to Comparative Examples 1 to 3 that are not. In addition, in the case of Comparative Example 4 using ASA latex instead of ABS latex it was possible to obtain a significantly lower value in the impact strength.

The foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the invention is indicated by the following claims, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the invention.

Claims (14)

(a) reacting a rubber modified graft copolymer, an acrylic monomer, a first initiator, a crosslinking agent, and an emulsifier to prepare a structure including a layer of acrylic rubber on the surface of the rubber modified graft copolymer; And
(b) grafting a copolymer of an aromatic vinyl monomer and an unsaturated nitrile monomer to the structure in the presence of a mercaptan-based molecular weight modifier and a second initiator;
The second initiator is a peroxycarbonate-based compound,
The amount of the mercaptan-based molecular weight regulator is 0.1 to 0.2 parts by weight based on 100 parts by weight of the copolymer composed of the aromatic vinyl monomer and the unsaturated nitrile monomer,
The rubber modified graft copolymer is a copolymer in which an aromatic vinyl monomer and an unsaturated nitrile monomer are grafted to a conjugated diene rubber,
The content of the conjugated diene rubber is 10 to 40% by weight based on the total weight of the rubber component contained in the structure, a method for producing an acrylic graft copolymer. delete The method of claim 1,
The conjugated diene rubber is at least one selected from the group consisting of 1,3-butadiene, 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene and 2,3-dimethyl-1,3-butadiene A method for producing an acrylic graft copolymer, which is a polymer or copolymer. The method of claim 1,
In the group wherein the aromatic vinyl monomer is styrene, α-methylstyrene vinyltoluene, t-butylstyrene, halogen-substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, ethyl styrene, and combinations of two or more thereof Selected one, the manufacturing method of the acrylic graft copolymer. The method of claim 1,
Acrylic graft copolymer, wherein the unsaturated nitrile monomer is one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, and combinations of two or more thereof. Manufacturing method. The method of claim 1,
The acrylic monomer is (meth) acrylic acid, alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms, and a method selected from the group consisting of two or more of these, acrylic graft copolymer production method. The method of claim 1,
The first initiator is a water-soluble initiator, a method for producing an acrylic graft copolymer. The method of claim 7, wherein
Wherein the first initiator is one selected from the group consisting of potassium persulfate, sodium persulfate, ammonium persulfate, silver persulfate, and combinations of two or more thereof, an acrylic graft copolymer. The method of claim 1,
The second initiator is t-amyl (2-ethylhexyl) monooxyoxycarbonate, t-butyl isopropyl monoperoxycarbonate, t-butyl- (2-ethylhexyl) monoperoxycarbonate and combinations of two or more thereof One selected from the group consisting of, acrylic graft copolymer production method. The method of claim 1,
The mercaptan-based molecular weight modifier is n-decyl mercaptan, n- dodecyl mercaptan , t- dodecyl mercaptan , n- octadecyl mercaptan and one selected from the group consisting of two or more thereof, acrylic graft copolymer of Manufacturing method. The method of claim 1,
The crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol Dimethacrylate, trimethylolpropanetrimethacrylate, trimethylolmethanetriacrylate, arylmethacrylate, triarylamine, diarylamine, triarylisocyanurate, triarylcyanurate, and two of these Method for producing an acrylic graft copolymer which is one selected from the group consisting of the above combination. The method of claim 1,
The emulsifier may be an alkali salt of fatty acid soap, rosin acid, oleic acid, or succinic acid; Alkyl aryl sulfonates; Alkali methyl alkyl sulfates; Alkali alkyl sulfonates; Sulfonated alkyl esters; And it is one selected from the group consisting of two or more of these, a method for producing an acrylic graft copolymer. The method of claim 3,
The manufacturing method of the acryl-type graft copolymer whose average particle diameter of the said conjugated diene rubber is 250 nm-350 nm. The method of claim 11,
A method for producing an acrylic graft copolymer, wherein the amount of the crosslinking agent is 0.1 to 0.5 parts by weight based on 100 parts by weight of the copolymer made of the aromatic vinyl monomer and the unsaturated nitrile monomer.