KR101868800B1 - A method for manufacturing acrylic graft copolymer having improved impact strength, coloring properties and weather resistance - Google Patents
A method for manufacturing acrylic graft copolymer having improved impact strength, coloring properties and weather resistance Download PDFInfo
- Publication number
- KR101868800B1 KR101868800B1 KR1020160182562A KR20160182562A KR101868800B1 KR 101868800 B1 KR101868800 B1 KR 101868800B1 KR 1020160182562 A KR1020160182562 A KR 1020160182562A KR 20160182562 A KR20160182562 A KR 20160182562A KR 101868800 B1 KR101868800 B1 KR 101868800B1
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- parts
- rubber
- acrylic
- graft copolymer
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/22—Coagulation
Abstract
Description
The present invention relates to a process for producing an acrylic graft copolymer, and more particularly, to a process for producing an acrylic graft copolymer having excellent impact resistance and colorability.
Generally, ABS resin obtained by graft copolymerizing styrene and acrylonitrile monomer in a butadiene rubber-like polymer has excellent impact resistance and processability, excellent mechanical strength and heat distortion temperature, and good coloring property. Thus, Devices and the like.
However, since ABS resin contains chemically unstable double bonds in the rubber component used, there is a problem that the rubber component is easily aged by the ultraviolet rays and is very vulnerable to weatherability.
On the other hand, a method using a chemically stable acrylic rubber instead of the butadiene rubber, a method using a rubbery polymer obtained by polymerizing butadiene and an acrylic polymerizable monomer, and the like have been used.
Particularly, an ASA (acrylate-styrene-acrylonitrile) graft copolymer resin in which styrene and acrylonitrile monomer are graft-copolymerized with an acrylic rubber-like polymer is used for interior and exterior parts such as automobiles and agricultural equipments, It is widely used for electric and electronic goods.
Since the ASA resin does not have a chemically unstable double bond, a special effect can be obtained in weatherability, but there is a problem that the impact resistance and the coloring property are low as compared with the ABS resin.
On the contrary, a method of increasing the particle diameter of the acrylic rubber or lowering the gel content of the rubbery polymer has been suggested. However, these methods are not only difficult to control the physical properties of the graft copolymer, have. Further, in order to improve the impact resistance, attempts have been made to improve the physical properties such as impact resistance and gloss by preparing and mixing acrylic rubbers having different particle diameters, respectively, but have failed to obtain sufficiently satisfactory results.
Korean Patent Laid-Open Publication No. 2014-0147655 attempts to simultaneously improve colorability, weatherability, and impact strength through the use of a multi-layer alkyl acrylate rubber containing a diene rubber therein. However, in order to form a plurality of shells It is difficult to control the reaction and the rigidity of the surface of the diene rubber which is the core part is low so that the alkyl acrylate rubber can not be effectively laminated thereon and thus it is difficult to achieve the required level of weatherability .
Therefore, there is a need for a manufacturing method capable of improving the weather resistance, impact resistance and coloring property of the ASA resin and realizing them in a balanced manner in order to expand the application range of the ASA resin.
SUMMARY OF THE INVENTION The present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to provide an acrylic graft copolymer which is capable of improving impact resistance and coloring property while balancing the weatherability of the acrylic graft copolymer, And a method for producing the same.
(A) 20 to 60 parts by weight of a rubber-modified graft copolymer, 50 to 150 parts by weight of an acrylic monomer, 0.1 to 5 parts by weight of an initiator, 0.1 to 5 parts by weight of a crosslinking agent, and 0.1 to 5 parts by weight of an emulsifier Reacting the rubber-modified graft copolymer to prepare a structure comprising a layer of acrylic rubber on the surface of the rubber-modified graft copolymer; And (b) 30 to 120 parts by weight of an aromatic vinyl monomer and 20 to 60 parts by weight of an unsaturated nitrile monomer to the structure.
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 the conjugated diene rubber.
In one embodiment, the conjugated diene rubber is selected from the group consisting of 1,3-butadiene, 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene and 2,3- One or more polymers or copolymers selected from the group consisting of
In one embodiment, the aromatic vinyl monomer is selected from the group consisting of styrene,? -Methylstyrene, vinyltoluene, t-butylstyrene, halogen substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, And mixtures of two or more.
In one embodiment, the unsaturated nitrile monomer is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and mixtures of two or more thereof .
In one embodiment, the acrylic monomer may be selected from the group consisting of (meth) acrylic acid, an alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms, and a mixture of two or more thereof.
In one embodiment, the initiator may be a water-soluble initiator.
In one embodiment, the water-soluble initiator may be selected from the group consisting of potassium persulfate, sodium persulfate, ammonium persulfate, silver persulfate, and mixtures of two or more thereof.
In one embodiment, the crosslinking agent is selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, But are not limited to, acrylate, acrylate, acrylate, acrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, aryl methacrylate, triarylamine, diarylamine, triarylisocyanurate, Rate, and a mixture of two or more thereof.
In one embodiment, the emulsifier is selected from the group consisting of fatty acid soap, rosin acid, oleic acid, or an alkali salt of succinic acid; Alkyl aryl sulfonates; Alkaline methyl alkyl sulfates; Alkali alkyl sulfonates; Sulfonated alkyl esters; And mixtures of two or more thereof.
According to an aspect of the present invention, there is provided a rubber-modified graft copolymer which is obtained by reacting a rubber-modified graft copolymer having a surface grafted with a monomer to the periphery of a rubber component and an acrylic monomer in the presence of a water- It is possible to stably produce a structure including a layer made of acrylic rubber on the surface of the assembly.
The acrylic graft copolymer in which the aromatic vinyl monomer and the unsaturated nitrile monomer are grafted to the above structure can be balanced in impact resistance and coloring property while maintaining weatherability.
It should be understood that the effects of the present invention are not limited to the effects described above, but include all effects that can be deduced from the description of the invention or the composition of the invention set forth in the claims.
Hereinafter, the present invention will be described in detail. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Throughout the specification, when a part is referred to as being "connected" to another part, it includes not only "directly connected" but also "indirectly connected" . Also, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.
(A) 20 to 60 parts by weight of a rubber-modified graft copolymer, 50 to 150 parts by weight of an acrylic monomer, 0.1 to 5 parts by weight of an initiator, 0.1 to 5 parts by weight of a crosslinking agent, and 0.1 to 5 parts by weight of an emulsifier Reacting the rubber-modified graft copolymer to prepare a structure comprising a layer of acrylic rubber on the surface of the rubber-modified graft copolymer; And (b) 30 to 120 parts by weight of an aromatic vinyl monomer and 20 to 60 parts by weight of an unsaturated nitrile monomer to the structure.
In the step (a), a structure may be prepared by reacting a rubber-modified graft copolymer and an acrylic monomer in the presence of an initiator, a crosslinking agent, and an emulsifier to thereby form a layer comprising an acrylic rubber on the surface of the rubber-modified graft copolymer have. The reaction may be a conventional emulsion polymerization reaction.
The rubber-modified graft copolymer may be a copolymer in which an aromatic vinyl monomer and an unsaturated nitrile monomer are grafted to the conjugated diene rubber.
In order to improve the colorability, weatherability, and impact strength of the conventional acrylic graft copolymer, there has been proposed a method of using a multi-layer acrylate rubber polymer containing a diene rubber polymer therein. However, in order to form a plurality of shells It is difficult to control the reaction and the rigidity of the surface of the diene rubber which is the core part is low so that the acrylate rubber can not be effectively stacked thereon and it is difficult to achieve the required level of weatherability.
On the other hand, the rubber-modified graft copolymer is obtained by grafting an aromatic vinyl monomer and an unsaturated nitrile monomer onto the surface of the conjugated diene rubber and has a higher surface rigidity than the ungrafted conjugated diene rubber, The formed acrylic rubber can be stably separated without infiltrating into the conjugated diene rubber.
Further, the rubber-modified graft copolymer prepared at a conversion rate of 99% or more can be used to simplify the process and improve the reproducibility, without considering the conversion rate between the reaction as in the prior art.
The conjugated diene rubber contributes to impact resistance and coloring property and the acrylic rubber contributes to weatherability and trade-off exists in the action effect of each rubber component. Therefore, when they are arbitrarily mixed, The action and effect that the rubber component can realize may be lowered together. For example, if the acrylic rubber formed on the surface is impregnated in the conjugated diene rubber in the inside, the weather resistance derived from the acrylic rubber in the final product is lowered, and the impact resistance and the coloring property derived from the conjugated diene rubber also deteriorate .
Since the structure is obtained by reacting and polymerizing an acrylic monomer on the surface of the above-mentioned conjugated copolymer in which an aromatic vinyl monomer and an unsaturated nitrile monomer are grafted on the surface of the conjugated diene rubber as a seed, A diene rubber, a monomer grafted on the surface thereof, and an acrylic rubber.
That is, in the structure, the conjugated diene rubber and the acrylic rubber are independently separated from each other by the monomers grafted to the surface of the conjugated diene rubber, and thus the weather resistance derived from the acrylic rubber and the conjugate Impact resistance and coloring property derived from a diene rubber can be balancedly realized.
The conjugated diene rubber may be 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- Polymers or copolymers, preferably homopolymers of 1,3-butadiene, but are not limited thereto.
The average particle size of the conjugated diene rubber may be 250 to 350 nm, and preferably 280 to 330 nm. When the average particle size of the conjugated diene rubber is less than 250 nm, the effect of imparting impact strength is weak. When the average particle size is more than 350 nm, the gloss and coloring property of the final product may be deteriorated.
The content of the conjugated diene rubber may be 10 to 40% by weight based on the total weight of the rubber component contained in the structure, that is, the conjugated diene rubber and the acrylic rubber. If the content of the conjugated diene rubber is less than 10% by weight, impact resistance and coloring property may be deteriorated. If the content is more than 40% by weight, a layer made of an acrylic rubber may not be formed.
Wherein the aromatic vinyl monomer is at least one selected from the group consisting of styrene,? -Methylstyrene, vinyltoluene, t-butylstyrene, halogen substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, ethylstyrene, And may be, but is not limited to, styrene.
The unsaturated nitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and mixtures of two or more thereof, , Acrylonitrile, but is not limited thereto.
The acrylic monomer for forming a layer made of an acrylic rubber on the surface of the rubber-modified graft copolymer is preferably a (meth) acrylic acid, an alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms, And may be, but is not limited to, butyl acrylate.
Also, by using a water-soluble initiator suitable for emulsion polymerization as an initiator for imparting a radical to the rubber-modified graft copolymer, the acrylic monomer can be polymerized smoothly on the surface of the rubber-modified graft copolymer.
The amount of the initiator may be 0.1 to 5 parts by weight. If the amount of the initiator is less than 0.1 parts by weight, the reaction rate and the conversion of the acrylic monomer may be lowered. If the amount of the initiator is more than 5 parts by weight, the molecular weight and the average particle size of the structure may be decreased.
The water-soluble initiator may be a persulfate-based compound, and may preferably be selected from the group consisting of potassium persulfate, sodium persulfate, ammonium persulfate, silver persulfate, and mixtures of two or more thereof, It is not.
In the structure, the rubber-modified graft copolymer and the acrylic rubber may be bonded by a crosslinking agent. The cross-linking agent is capable of linking a radical generated on the surface or outer periphery of the rubber-modified graft copolymer to the acrylic monomer by the initiator, connecting the acrylic rubber produced by randomly mutual polymerization of the acrylic monomer with the radical have.
The crosslinking agent may form a strong bond between the rubber-modified graft copolymer and the acrylic rubber to stabilize the structure.
The amount of the cross-linking agent may be 0.1 to 5 parts by weight. If the amount of the cross-linking agent is less than 0.1 part by weight, the acrylic rubber is hardly produced on the surface of the rubber-modified graft copolymer, and if it is more than 5 parts by weight, the impact resistance may be lowered.
The crosslinking agent may be selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol Dimethacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, arylmethacrylate, triarylamine, diarylamine, triarylisocyanurate, triarylcyanurate, and 2 of these And mixtures thereof. Preferably, it may be triaryl cyanurate, but is not limited thereto.
The amount of the emulsifier may be 0.1 to 5 parts by weight. If the amount of the emulsifier is less than 0.1 parts by weight, the stability of the latex may deteriorate to increase the amount of the coagulated product. If the amount of the emulsifier is more than 5 parts by weight, the average particle size of the structure may be decreased.
The emulsifier may be selected from the group consisting of fatty acid soap, rosin acid, oleic acid, or an alkali salt of succinic acid; Alkyl aryl sulfonates; Alkaline methyl alkyl sulfates; Alkali alkyl sulfonates; Sulfonated alkyl esters; And a mixture of two or more thereof, preferably dioctyl sulfosuccinate, but is not limited thereto.
Meanwhile, in the step (b), 30 to 120 parts by weight of an aromatic vinyl monomer and 20 to 60 parts by weight of an unsaturated nitrile monomer may be copolymerized with the structure to prepare an acrylic graft copolymer.
The copolymerization in the step (b) may be carried out by a conventional emulsion polymerization reaction. After the reaction, the latex-phase product is agglomerated and dried to obtain a powdery acrylic graft copolymer.
Hereinafter, embodiments of the present invention will be described in detail.
Example One
300 parts by weight of ion-exchanged water and 50 parts by weight (based on solid content) of ABS latex were heated to 70 占 폚 in an atmosphere substituted with nitrogen, and then 1 part by weight of potassium persulfate as an initiator was added thereto and stirred for 10 minutes. Then, a mixture of 100 parts by weight of butyl acrylate and 1 part by weight of triarylcyanurate as a crosslinking agent and 1 part by weight of dioctylsulfosuccinate as an emulsifier was continuously added for 4 hours to polymerize. The polymerized product was further agitated at a temperature of 70 캜 for 1 hour and aged to obtain rubber particles.
Example 2
Rubber particles were obtained in the same manner as in Example 1 except that sodium persulfate was used instead of potassium persulfate as an initiator.
Example 3
Rubber particles were obtained in the same manner as in Example 1 except that ammonium persulfate was used in place of potassium persulfate as an initiator.
Comparative Example One
Rubber particles were obtained in the same manner as in Example 1 except that cumene hydroperoxide was used instead of potassium persulfate as an initiator.
Comparative Example 2
Rubber particles were obtained in the same manner as in Example 1 except that benzoyl peroxide was used instead of potassium persulfate as an initiator.
Comparative Example 3
Rubber particles were obtained in the same manner as in Example 1 except that ABS latex was omitted and 0.3 parts by weight of dioctylsulfosuccinate as an emulsifier was used in order to maintain the same rubber particle size.
Comparative Example 4
Rubber particles were obtained in the same manner as in Example 1 except that polybutadiene latex was used instead of ABS latex.
The rubber particles prepared in Examples and Comparative Examples were copolymerized with 70 parts by weight of styrene and 30 parts by weight of acrylonitrile based on 100 parts by weight of butyl acrylate to prepare a grafted ASA latex and then coagulated and dried to obtain ASA powder .
The ASA powder was then mixed with a conventional SAN resin. At this time, 20 parts by weight of ASA powder, 0.2 part by weight of antioxidant, 0.7 part by weight of lubricant and 2 parts by weight of black colorant were mixed with 100 parts by weight of SAN resin, and the specimen was extruded at 230 캜 using a twin- .
The physical properties of the specimens were measured by the following methods, and the results are shown in Table 1 below.
Impact strength (kg · cm / cm): measured according to ASTM D256 at a thickness of 3.2 mm.
- Coloring degree: The L value was measured using a spectrocolorimeter (Datacolor 650). Here, the lower the L value, the better the coloring property.
Weatherability: The degree of discoloration (ΔE) in the colorimetric system was measured after a 4,500 KJ / m 2 exposure according to SAEJ2527 with a weatherometer. Here, the closer to 0 the ΔE value means the better the weatherability.
Referring to Table 1, Examples 1 to 3 using a water-soluble peroxide-based initiator showed improved impact strength, colorability, and weatherability as compared with Comparative Examples 1 and 2 using an oil-soluble peroxide initiator. In Examples 1 to 3 using ABS latex containing a certain amount of butadiene rubber, the impact strength and coloring property were improved as compared with Comparative Example 3. Further, in Examples 1 to 3 using core particles having a hard surface as compared with Comparative Example 4, weather resistance was improved.
As described above, by using the ABS latex containing a certain amount of butadiene rubber and the water soluble persulfate-based initiator in the production of the rubber particles, the impact strength, coloring property and coloring property of the ASA powder and SAN resin prepared from the rubber particles are balanced It can be implemented as an implementation.
It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.
The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.
Claims (10)
(b) copolymerizing 30 to 120 parts by weight of an aromatic vinyl monomer and 20 to 60 parts by weight of an unsaturated nitrile monomer in the structure,
Wherein the rubber-modified graft copolymer is a copolymer obtained by grafting an aromatic vinyl monomer and an unsaturated nitrile monomer onto a conjugated diene rubber.
Wherein 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- A method for producing an acrylic graft copolymer, which is a polymer or a copolymer.
Wherein the aromatic vinyl monomer is selected from the group consisting of styrene,? -Methylstyrene, vinyltoluene, t-butylstyrene, halogen-substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, ethylstyrene, Wherein the graft copolymer is one selected from the group consisting of acrylic acid, methacrylic acid, and methacrylic acid.
Wherein the unsaturated nitrile monomer is one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and a mixture of two or more thereof. ≪ / RTI >
Wherein the acrylic monomer is one selected from the group consisting of (meth) acrylic acid, an alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms, and a mixture of two or more thereof.
Wherein the initiator is a water-soluble initiator.
Wherein the water-soluble initiator is one selected from the group consisting of potassium persulfate, sodium persulfate, ammonium persulfate, silver persulfate, and a mixture of two or more thereof.
Wherein the crosslinking agent is selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexane diol dimethacrylate, neopentyl glycol Dimethacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, arylmethacrylate, triarylamine, diarylamine, triarylisocyanurate, triarylcyanurate, and 2 of these , And mixtures thereof. ≪ Desc / Clms Page number 24 >
Wherein the emulsifier is selected from the group consisting of fatty acid soap, rosin acid, oleic acid, or an alkali salt of succinic acid; Alkyl aryl sulfonates; Alkaline methyl alkyl sulfates; Alkali alkyl sulfonates; Sulfonated alkyl esters; And a mixture of at least two of the foregoing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160182562A KR101868800B1 (en) | 2016-12-29 | 2016-12-29 | A method for manufacturing acrylic graft copolymer having improved impact strength, coloring properties and weather resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160182562A KR101868800B1 (en) | 2016-12-29 | 2016-12-29 | A method for manufacturing acrylic graft copolymer having improved impact strength, coloring properties and weather resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR101868800B1 true KR101868800B1 (en) | 2018-07-23 |
Family
ID=63103035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020160182562A KR101868800B1 (en) | 2016-12-29 | 2016-12-29 | A method for manufacturing acrylic graft copolymer having improved impact strength, coloring properties and weather resistance |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101868800B1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030038366A (en) * | 2001-11-08 | 2003-05-16 | 주식회사 엘지화학 | Acrylate-styrene-acrylonitrile graft copolymer composition and method for preparing thereof |
| KR20150026404A (en) * | 2013-09-03 | 2015-03-11 | 제일모직주식회사 | Acrylic Rubber Modified Graft Copolymer Having Excellent Impact-resistance and Colorability, and Method for Preparing Same |
-
2016
- 2016-12-29 KR KR1020160182562A patent/KR101868800B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030038366A (en) * | 2001-11-08 | 2003-05-16 | 주식회사 엘지화학 | Acrylate-styrene-acrylonitrile graft copolymer composition and method for preparing thereof |
| KR20150026404A (en) * | 2013-09-03 | 2015-03-11 | 제일모직주식회사 | Acrylic Rubber Modified Graft Copolymer Having Excellent Impact-resistance and Colorability, and Method for Preparing Same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102298295B1 (en) | Thermoplastic resin composition | |
| KR101564847B1 (en) | ASA copolymer and thermoplastic resin composition | |
| KR102168348B1 (en) | MBS impact modifier, polyvinyl chloride resin composition comprising the same | |
| KR101404942B1 (en) | Graft copolymer having excellent transparency and impact strength | |
| KR101743816B1 (en) | Heat-resistant styrene copolymer and styrene resin composition comprising the same | |
| KR101743817B1 (en) | Heat-resistant styrene copolymer and styrene resin composition comprising the same | |
| JPH05247148A (en) | Methacrylate-butadiene-styrene graft polymer and its pvc blend having low yellowness, good clarity and improved impact strength | |
| KR20120054163A (en) | Impact modifiers composition having excellent impact strength at low temperature and thermoplastic resin composition comprising the same | |
| KR101827613B1 (en) | Rubber-modified vinyl-based graft copolymer and thermoplastic resin composition comprising the same | |
| KR101868800B1 (en) | A method for manufacturing acrylic graft copolymer having improved impact strength, coloring properties and weather resistance | |
| JPS60104112A (en) | Impact-resistant polystyrene resin and its production | |
| KR100967124B1 (en) | An acrylic impact modifier and a manufacturing method thereof | |
| KR101094176B1 (en) | A method of manufacturing a thermoplastic risin wiht an excellent wetherability, high impact, and thermal resistance | |
| EP1312641B1 (en) | Transparent impact-resistant thermoplastic resin composition | |
| KR101913741B1 (en) | A method for manufacturing acrylic graft copolymer having improved impact strength, coloring properties and weather resistance | |
| KR100727235B1 (en) | Acrylic impact modifier and method for preparing thereof | |
| KR102016469B1 (en) | A method for manufacturing acrylic graft copolymer having improved impact strength and surface appearance | |
| US20040063814A1 (en) | Impact modifier for thermoplastic resin and resin composition containing the same | |
| JP7066228B2 (en) | Thermoplastic resin composition | |
| JP3472308B2 (en) | Impact resistant methacrylic resin | |
| KR101396697B1 (en) | Thermoplastic resin composition having low gloss surface | |
| JPH0414688B2 (en) | ||
| KR20190080263A (en) | An acrylic graft copolymer and a method for prepairng the same | |
| KR101656798B1 (en) | Method for preparing acrylate-styrene-acrylonitrile latex | |
| KR20190043404A (en) | Thermoplastic resin composition and thermoplastic resin molded article prepared by using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GRNT | Written decision to grant |