KR102049869B1 - Graft copolymers based on acrylonitrile-styrene-acrylate and thermoplastic resin composition comprising the same - Google Patents
Graft copolymers based on acrylonitrile-styrene-acrylate and thermoplastic resin composition comprising the same Download PDFInfo
- Publication number
- KR102049869B1 KR102049869B1 KR1020160030752A KR20160030752A KR102049869B1 KR 102049869 B1 KR102049869 B1 KR 102049869B1 KR 1020160030752 A KR1020160030752 A KR 1020160030752A KR 20160030752 A KR20160030752 A KR 20160030752A KR 102049869 B1 KR102049869 B1 KR 102049869B1
- Authority
- KR
- South Korea
- Prior art keywords
- styrene
- acrylonitrile
- graft copolymer
- acrylate
- weight
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
- C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
Abstract
The graft copolymer of the present invention is an acrylate-styrene-acrylonitrile graft copolymer, comprising: a core containing an acrylic rubbery polymer; And a grafting shell positioned on the surface of the core and containing a styrene-acrylonitrile copolymer, wherein the acrylic rubber polymer has a crosslinking degree of 93 to 99, a swelling index of 4 to 10, and a crosslinking degree. The ratio of the swelling index to is 0.04 to 0.1. The graft copolymer may have excellent drying efficiency as it has excellent weather resistance, and has excellent cohesive properties due to improved bulk density and moisture content, and may have excellent impact strength, appearance characteristics, and thermal stability.
Description
The present invention is excellent in weather resistance, but also improves the cohesive properties, appearance properties and thermal stability, and excellent drying efficiency of the core-shell structure of the acrylate-styrene-acrylonitrile-based graft copolymer and thermoplastic resin composition comprising the same It is about.
Generally, acrylonitrile-butadiene-styrene (ABS) resin is a tertiary copolymer of butadiene, styrene, and acrylonitrile. It has excellent impact resistance and rigidity, and thus has excellent mechanical properties, excellent moldability, and excellent colorability. It is widely used in various applications such as electronic housing, automotive interior materials and lamp housing materials. However, there is a difference in mechanical properties according to the composition and manufacturing method of the raw material, and basically has a rubber component having an unsaturated bond, there is a weak point such as oxygen, ozone and heat or light (ultraviolet) in the air. Therefore, the applicability to the exterior material is somewhat inferior, there is a disadvantage that the coating to be applied to the exterior material.
For example, in order to apply acrylonitrile-butadiene-styrene (ABS) resin to an exterior material, especially a lamp housing, after the primary coating on the injection molded acrylonitrile-butadiene-styrene (ABS) resin surface In order to protect the aluminum film, aluminum is deposited and top coating is performed again. The coating may be a paint failure, and the environmental damage due to the use of excess solvent and the toxicity and scattering of the solvent is being avoided by workers, as well as the productivity and cost increase due to the additional process occurs.
Therefore, research is being carried out to deposit immediately without coating, and in order to increase the deposition property, a method of controlling the rubber content using bimodal or other types of rubber components, a surfactant, etc., and coating properties and coating spreadability A method of improving is proposed.
However, the above method uses acrylonitrile-butadiene-styrene (ABS) resin having a rubber component having an unsaturated bond as a base resin, and thus has a problem of weak weatherability caused by the rubber component having the unsaturated bond, that is, a long-term external condition. When exposed to light, the fundamental problems such as yellowing of the surface color, cracking, and significant drop in impact strength were not solved.
On the other hand, the acrylate-styrene-acrylonitrile (ASA) resin is a resin of acrylonitrile-butadiene-styrene (ABS) resin by using an acrylate rubber component having no unsaturated bond instead of butadiene rubber which is a rubber component having an unsaturated bond. It has excellent mechanical properties and molding processability, and is a material that has remarkably improved weather resistance, which is the biggest drawback, and is widely applied to outdoor applications using painted articles or metal materials. Since the acrylate-styrene-acrylonitrile-based resin has excellent weather resistance even without post-treatment such as coating, there is an advantage in that there is little discoloration even when exposed to light for a long period of time and a decrease in mechanical properties is relatively low.
However, the acrylate rubber component having no unsaturated bond has a disadvantage that the impact strength reinforcement effect is lower than the butadiene rubber component and the impact strength reinforcement effect is low at low temperatures. In addition, there is a problem that glossiness is inferior to acrylonitrile-butadiene-styrene (ABS) resin, and furthermore, there is also a problem that the drying efficiency is lowered compared to acrylonitrile-butadiene-styrene (ABS) resin and the drying efficiency is lowered. Have
Accordingly, the development of an acrylate-styrene-acrylonitrile copolymer and a thermoplastic resin composition comprising the same, which have excellent weather resistance, excellent cohesive properties, excellent drying efficiency, and excellent impact strength, appearance characteristics and thermal stability, It is necessary.
An object of the present invention is to provide a thermoplastic resin having excellent weather resistance, improved cohesive properties through improvement of bulk density and wet powder moisture content, and improved appearance properties, impact strength, and thermal stability through control of various parameters. An object of the present invention is to provide an acrylate-styrene-acrylonitrile graft copolymer having a core-shell structure and a thermoplastic resin composition comprising the same.
In order to solve the above problems, the present invention is an acrylate-styrene-acrylonitrile-based graft copolymer, a core containing an acrylic rubber polymer; And a grafting shell positioned on the surface of the core and containing a styrene-acrylonitrile (SAN) -based copolymer, wherein the acrylic rubber polymer has a crosslinking degree of 93 to 99 and a swelling index ( It provides a graft copolymer having a swelling index) of 4 to 10.
In order to solve the above problems, the present invention is 100 parts by weight of acrylate monomers; 0.01 to 1.0 part by weight of a polymerization initiator; And 0.3 to 0.9 parts by weight of a crosslinking agent, a crosslinking degree of 93 to 99, a swelling index of 4 to 10, and a ratio of the swelling index to the crosslinking degree of 0.04 to 0.1.
In order to solve the above problems, the present invention has a crosslinking degree of 93 to 99, the swelling index of 4 to 10, 30 to 70 parts by weight of the acrylic rubber polymer having a ratio of the swelling index to the crosslinking degree of 0.04 to 0.1; 20 to 60 parts by weight of the aromatic vinyl compound; 5 to 25 parts by weight of a vinyl cyan compound; And 0.01 to 0.15 parts by weight of a molecular weight modifier, and provides a composition for copolymerization of an acrylate-styrene-acrylonitrile graft copolymer having a graft ratio of 32 to 60%.
In order to solve the above problems, the present invention provides a thermoplastic resin composition comprising the acrylate-styrene-acrylonitrile-based graft copolymer described above.
According to the present invention, the degree of crosslinking, the swelling index and the ratio of the acrylic rubbery polymer contained in the core of the acrylate-styrene-acrylonitrile-based graft copolymer, and the styrene-acrylonitrile-based air contained in the grafting shell Parameters such as the graft rate of the coalescence can be controlled, thereby improving the bulk density and wet powder moisture content of the thermoplastic resin thus prepared, and on the other hand, improving the cohesive properties of the graft copolymer, and the thermal stability Physical properties such as impact strength and appearance characteristics can be improved at the same time.
Accordingly, the present invention controls acrylate-styrene-acryl with improved cohesiveness, appearance and thermal stability while maintaining weather resistance compared to conventional acrylate-styrene-acrylonitrile-based resins by controlling certain parameters. A ronitrile-based graft copolymer can be provided.
Hereinafter, the present invention will be described in more detail to aid in understanding the present invention. The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
The present invention by controlling the parameters such as the swelling index, the degree of crosslinking, the ratio of the swelling index to the degree of crosslinking, the graft ratio, the weight average molecular weight, while maintaining the excellent weather resistance characteristic of the existing acrylate-styrene-acrylonitrile-based resin, The present invention provides an acrylate-styrene-acrylonitrile-based graft copolymer with improved mechanical properties such as impact strength and appearance characteristics, and excellent bulk density and wet powder moisture content.
A graft copolymer according to an embodiment of the present invention, the core containing an acrylic rubber polymer; And a grafting shell positioned on the surface of the core and containing a styrene-acrylonitrile (SAN) -based copolymer, wherein the acrylic rubber polymer has a crosslinking degree of 93 to 99 and a swelling index ( swelling index) is 4 to 10.
The core may include an acrylic rubber polymer, and the acrylic rubber polymer may be polymerized by mixing an acrylate monomer, a polymerization initiator, and a crosslinking agent.
The composition for polymerization according to an embodiment of the present invention is a composition used when polymerizing the acrylic rubber polymer, 100 parts by weight of the acrylate monomer; 0.01 to 1.0 part by weight of a polymerization initiator; And 0.5 to 2.5 parts by weight of a crosslinking agent.
The acrylate monomer may be applied without limitation as long as it is a compound that can be polymerized into an acrylic rubbery polymer, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, 2-chloroethyl vinyl ether, hydroxyethyl meth Acrylate, trimethylolpropane triacrylate (TMPTA) or a mixture of two or more thereof may be applied.
The acrylate monomer is preferably methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-chloroethyl vinyl ether, hydroxyethyl methacryl Latex, trimethylolpropane triacrylate (TMPTA) and the like can be applied.
The acrylate monomer may be included in 30 to 70% by weight relative to the total weight of the acrylate-styrene-acrylonitrile graft copolymer. When the content of the acrylate monomer is less than 30% by weight, the rubber content is low, the impact strength may be lowered. When the content of the acrylate monomer is greater than 70% by weight, the shell formed on the core including the acrylate monomer may not be sufficiently wrapped therein, thereby acryl-based to the outside. The rubbery polymer may be exposed, and therefore, due to the aggregation phenomenon of other copolymer particles with the acrylic rubbery polymers, the wet powder moisture content or the bulk density may be lowered, and thus there is a concern that the aggregation property is lowered.
The polymerization initiator is a compound that plays a role to cause the reaction to occur in the initiation step of the polymerization reaction, it may be included in about 0.01 to 1.0 parts by weight, based on 100 parts by weight of the acrylate monomer, it may be applied if the initiator of the general polymerization reaction For example, water-soluble initiators such as sodium persulfate, potassium persulfate, ammonium persulfate, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide, paramethane hydride Oil-soluble initiators such as loperoxide and benzoyl peroxide, or redox-based polymerization initiators in which an oxidation-reducing agent is combined may be used.
An activator may be used to promote the initiation reaction of the peroxide together with the initiator, and the activator may be sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate or sodium sulfite. It is preferable to use individually or in mixture of 2 or more types.
Examples of the crosslinking agent capable of determining the degree of crosslinking include divinylbenzene, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, and 1,4-butanediol dimethacrylate. Crylate, aryl acrylate, aryl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neo Pentyl glycol dimethacrylate, triallyl isocyanurate, triarylamine, diallylamine, a compound represented by the following formula (1), or a mixture of two or more thereof may be applied.
[Formula 1]
Wherein A may independently be a substituent having a vinyl group or a (meth) acrylate group, and A ′ is a hydrogen group, a substituent having a vinyl group, an alkyl group having 1 to 30 carbon atoms, an aryl alkyl group having 5 to 24 carbon atoms, and 5 to C carbon atoms. It may be an aryl amine group of 24, or an aryl group having 6 to 30 carbon atoms, R may be independently an ethyl group or a propyl group, n may be an integer of 0 to 15.
The crosslinking agent is an additive material that can directly control the degree of crosslinking of the acrylic rubber polymer and can have an indirect effect on the crosslinking density, and it may be important to control the amount of the crosslinking agent added to the composition used during polymerization. The crosslinking agent may be included in an amount of 0.3 to 0.9 parts by weight, based on 100 parts by weight of the acrylate monomer, and this range is a content range that can control the ratio of the swelling index to the degree of crosslinking, swelling index, and crosslinking degree of the acrylic rubbery polymer. If less than 0.3 parts by weight or more than 0.9 parts by weight, the acrylic rubber polymer having a degree of crosslinking desired in the present invention may not be prepared.
In addition, the method of administering the crosslinking agent may be applied in a batch, divided administration, etc., but divided into two or more divided administration, it may be more advantageous in controlling the degree of polymerization or crosslinking degree of the acrylic rubber polymer.
The acrylic rubber polymer prepared by adjusting the content of the crosslinking agent in the composition may have a crosslinking degree of 93 to 99, preferably 94 to 98, and more preferably 95 to 98. The degree of crosslinking may be affected to some extent depending on the conditions of various polymerization reactions, but may be mainly determined by the content of the crosslinking agent.
If the crosslinking degree of the acrylic rubber polymer is less than 93 due to the failure of control of the content of the crosslinking agent or other reaction conditions, the cohesiveness decreases due to the decrease in the bulk density and the wet powder moisture content, the glossiness decreases, and the impact strength decreases. And thermal stability may be lowered. When the crosslinking degree exceeds 99, impact strength may be lowered and mechanical properties of the graft copolymer may be lowered.
The acrylic rubber polymer may be a parameter having a primary crosslinking degree, but it is also necessary to control the swelling index. The swelling index can be obtained 4 to 10, preferably 5 to 9 acrylic rubbery polymer, when the acrylic rubbery polymer has a swelling index of the same range, the bulk density and wet powder moisture content of the final graft polymer It can be improved so that the flocculation property is excellent. That is, the swelling index may be a main parameter that may be organically related to the bulk density and the wet powder moisture content of the graft copolymer along with the degree of crosslinking and may influence the cohesive properties of the graft copolymer.
It may be important to control the degree of crosslinking and the swelling index of the acrylic rubber polymer, and furthermore, it is necessary to control the parameter values by paying attention to the relationship between them, and satisfy the following relationship.
0.04 ≤ [swelling index] / [crosslinking degree] ≤ 0.1
As described above, when the ratio of the swelling index to the degree of crosslinking of the acrylic rubber polymer and the swelling index has a value of 0.04 to 0.1, preferably a value of 0.06 to 0.09, the graft copolymer The various properties of can be improved and can have an optimal value among the properties in the trade-off relationship.
Acrylic rubber polymer polymerized using the composition for polymerization according to an embodiment of the present invention, may be contained in the core of the graft copolymer according to an embodiment of the present invention, the core has a diameter of 50 to 600 nm, preferably 100 to 400 nm.
When the diameter of the core is smaller than 50 nm, it may be difficult to maintain the mechanical properties such as impact strength and tensile strength of the final graft copolymer at an excellent level, and there are relatively few grafting sites on which a grafting shell may be formed. As a result, the graft ratio is inevitably lowered, and as a result, the physical properties of the graft copolymer may be reduced.
In addition, when the diameter of the core exceeds 600 nm, when the finally prepared acrylate-styrene-acrylonitrile-based graft copolymer of the core-shell structure is applied as an additive resin of a specific matrix resin, There is a fear that it may not be achieved, and accordingly, properties such as excellent weather resistance and thermal stability of the acrylate-styrene-acrylonitrile graft copolymer of the present invention may not be effectively expressed.
The grafting shell may include a graft copolymer that may be graft copolymerized to an acrylic rubber polymer contained in the core, and may include a styrene-acrylonitrile copolymer.
The styrene-acrylonitrile-based copolymer may be graft copolymerized at a grafting site in which an aromatic vinyl compound and a vinyl cyan compound are present on the surface of the acrylic rubbery polymer.
That is, the aromatic vinyl compound as the styrene-based monomer and the vinyl cyan compound as the acrylonitrile-based monomer may be graft copolymerized to an acrylic rubber polymer of a preformed core, and a shell may be formed by such graft copolymerization. Finally, the acrylate-styrene-acrylonitrile-based graft copolymer may be formed.
The composition for copolymerization according to an embodiment of the present invention may be a composition for preparing a grafting shell formed on the core surface of the acrylate-styrene-acrylonitrile-based graft copolymer, the degree of crosslinking is 93 to 99 30 to 70 parts by weight of an acrylic rubber polymer having a swelling index of 4 to 10 and a ratio of swelling index to a degree of crosslinking of 0.04 to 0.1; 20 to 60 parts by weight of the aromatic vinyl compound; 5 to 25 parts by weight of a vinyl cyan compound; And 0.01 to 1.5 parts by weight of a molecular weight modifier.
The acrylic rubber polymer having a crosslinking degree of 93 to 99 included in the composition, a swelling index of 4 to 10, and a ratio of swelling index to a crosslinking degree of 0.04 to 0.1 is polymerized by the composition for polymerization of an acrylic rubbery polymer according to the present invention. The crosslinking degree of the acrylic rubber polymer is 93 to 99, the swelling index is 4 to 10, and the ratio of the swelling index to the crosslinking degree is 0.04 to 0.1, but may be applied without particular limitation. .
The composition for copolymerization of the acrylate-styrene-acrylonitrile graft copolymer may include a molecular weight modifier in an amount of 0.01 to 1.5 parts by weight based on 100 parts by weight of the acrylic rubber polymer.
Content control of the molecular weight modifier is contained in the grafting shell in the process of forming the grafting shell when the acrylate-styrene-acrylonitrile-based graft copolymer is prepared using the composition for copolymerization according to an embodiment of the present invention. It may also serve to control the molecular weight of the acrylate-styrene-acrylonitrile-based copolymer, and may also serve as a grafting agent that may partially affect the graft rate, the content range is 100 weight of the acrylic rubber polymer 0.01 parts by weight to 1.5 parts by weight may be included. When the molecular weight modifier is included in the composition in the above range, it has the molecular weight of the styrene-acrylonitrile-based copolymer to be obtained in the present invention, thereby providing excellent physical properties such as impact strength, agglomeration characteristics, drying efficiency, and appearance characteristics. Graft copolymers can be obtained.
Examples of the molecular weight regulator include alkyl mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-dodecyl thiol acetate, pentaerythritol tetrakis (β-mercaptopropionate), and limonene dimercaptan. Etc. can be mentioned. In addition, an organic mercapto compound containing two or more mercapto groups in the molecule, for example, pentaerythritol tetrakis (β-mercaptopropionate), limonene dimercaptan and the like can be applied.
In addition, the molecular weight modifier may be applied to alpha methyl styrene duplex, terpinolene, dipentene, gamma terpinene, alpha terpinene or a combination thereof.
The graft copolymer polymerized using the composition of which the content of the graft agent is controlled may have a graft ratio of 32 to 60%, preferably 35 to 55%. In this case, the graft rate may mean a ratio at which the styrene monomer and the acrylonitrile monomer are graft copolymerized at the grafting site of the acrylic rubber polymer contained in the core.
The graft rate may be determined by the molecular weight of the styrene-acrylonitrile copolymer copolymerized with the number of grafting sites of the acrylic rubber polymer, and may be controlled by the grafting agent added during the graft copolymerization as a primary factor. Indirect control may be possible by a molecular weight modifier, and may be controlled by increasing the grafting site by adjusting the molecular weight of the acrylic rubbery polymer.
If the graft rate is less than 32% due to inability to properly control the graft rate, the bulk density and the wet powder moisture content may be remarkably lowered, which may not improve the cohesive properties, and the physical properties such as impact strength, glossiness, and thermal stability may be deteriorated. There is concern. In addition, although the graft ratio is up to 60%, the impact strength is increased to obtain a graft copolymer having excellent mechanical properties. However, when the graft ratio is exceeded, the impact strength is decreased again to decrease the physical properties.
The acrylate-styrene-acrylonitrile-based graft copolymer finally prepared using the composition of which the content of the molecular weight modifier is controlled is the weight average molecular weight of the styrene-acrylonitrile-based graft copolymer portion as the graft shell portion. May be 90,000 to 150,000, preferably 100,000 to 130,000. The weight average molecular weight, in addition to the molecular weight modifier, may also be partially controlled by various methods such as control of reaction time, control of monomer amount, and the like.
When the weight average molecular weight is less than 90,000, physical properties that influence flocculation characteristics such as bulk density and wet powder moisture content may be deteriorated, impact strength and thermal stability may also be deteriorated, and the weight average molecular weight is greater than 150,000. The wet powder moisture content and bulk density for determining the coagulation property may be lowered again, and unlike the case where the molecular weight is less than that, there is a fear that appearance characteristics such as glossiness may be deteriorated.
The copolymer composition may include an aromatic vinyl compound of a styrene-based monomer system and a vinyl cyan compound of an acrylonitrile-based monomer system, which may be a skeleton of the styrene-acrylonitrile-based copolymer.
The aromatic vinyl compound may be included in an amount of 20 to 60 parts by weight based on 100 parts by weight of the acrylate-styrene-acrylonitrile graft copolymer, but is not limited thereto. For example, styrene, α-methylstyrene, p-styrene and vinyl toluene, or a combination thereof may be applied. The vinyl cyan compound may be included in an amount of 5 to 25 parts by weight based on 100 parts by weight of the acrylate-styrene-acrylonitrile graft copolymer, for example, acrylonitrile, methacrylonitrile, or a combination thereof. This can be applied.
When the aromatic vinyl compound and the vinyl cyan compound are included in an amount less than the above range, the weight average molecular weight and graft ratio of the styrene-acrylonitrile copolymer may be excessively lowered, and as described above, the weight average molecular weight or graft ratio may be set. There is a concern that the lower the lower limit of the numerical range, there is a problem occurs, and if the amount is included in the amount greater than the above range, the weight average molecular weight and graft ratio of the styrene-acrylonitrile-based copolymer may be excessively high, as described above There may be a problem that the weight average molecular weight or the graft ratio is higher than the upper limit of the set numerical range.
At this time, the aromatic vinyl compound and the vinyl cyan compound may be mixed in a ratio of 97: 3 to 60:40 by weight, and the weight ratio is not particularly limited, but acrylate-styrene-acrylonitrile having excellent weather resistance, durability, etc. In order to have basic characteristics of the graft copolymer, it may be preferable that the two compounds are included in the composition for copolymerization in the above weight ratio range.
The copolymer composition may further include a polymerization initiator, an emulsifier, and the like, and may be included in an amount of about 10 parts by weight or less relative to 100 parts by weight of the acrylic rubber polymer in the case of the polymerization initiator and the emulsifier. Additives such as emulsifiers, polymerization initiators may be as follows.
The emulsifier uses a derivative of an alkyl sulfo succinate metal salt of C12 to C18, an alkyl sulfate ester or a sulfonic acid metal salt of C12 to C20. Examples of the C12-C18 alkyl sulfo succinate metal salt derivative include dicyclohexylsulfonate, dihexylsulfosuccinate sodium or potassium salt, and C12-C20 sulfate ester or sulfonic acid metal salt. Alkyl sulfate metal salts, such as ric sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate, potassium octadecyl sulfate, etc. can be used. The emulsifier has a pH of 9 to 13 in its aqueous solution, and is preferably a derivative of carboxylic acid metal salts such as C12 to C20 fatty acid metal salts and rosin acid metal salts, and examples of fatty acid metal salts are sodium or oleic acid of fetic acid, lauryl acid and oleic acid. There are potassium of Iksan, and the metal salt of rosin is sodium rosin or potassium rosin. The said emulsifier can be used individually or in mixture of 2 or more types.
The polymerization initiator is a water-soluble initiator such as sodium persulfate, potassium persulfate, ammonium persulfate, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobisisobutylnitrile, tertiary butyl hydroperoxide, paramethane hydride Oil-soluble initiators, such as a loperoxide and benzoyl peroxide, or the redox type polymerization initiator which combined the oxidation-reduction agent, etc. can be used.
An activator may be used to promote the initiation reaction of the peroxide together with the polymerization initiator, and the activator may be sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, Or it is preferable to use sodium sulfite etc. individually or in mixture of 2 or more types.
The graft copolymer according to an embodiment of the present invention may further include any one or two or more selected from alkyl methacrylate having 1 to 4 carbon atoms of alkyl in the grafting shell formed on the surface of the core. . Preferably, methyl methacrylate or ethyl methacrylate having 1 or 2 carbon atoms can be used. When such a compound is further included in the grafting shell, physical properties such as impact strength, thermal stability or glossiness may be further improved.
The grafting shell may have a thickness of 6 to 200 nm. The above-described thickness range of the grafting shell is a numerical range which appears when the graft ratio and / or the weight average molecular weight are properly controlled through the content adjustment of the molecular weight modifier, etc., if so, the impact strength, as described above, There exists a possibility that physical properties, such as thermal stability, may fall.
As described above, the parameters presented in the present invention, such as the degree of crosslinking, swelling index, ratio of swelling index to crosslinking degree, graft rate and weight average molecular weight of the graft copolymer, improve and improve the cohesive properties of the graft copolymer. It may be a kind of criteria to improve the drying efficiency and at the same time provide a property improvement effect such as weather resistance, impact strength, appearance characteristics and thermal stability, and if any one of the parameters is satisfied, the graft properties are improved Copolymers can be provided. However, if two or more of the parameters are satisfied, the graft copolymer may have improved properties. If all of the parameters are satisfied, the graft copolymer may have more improved properties.
In addition, as described above, as the means for controlling the above parameters, the content of a crosslinking agent or a molecular weight modifier may be important, but is not limited to only such means and is not controlled uniformly. It does not exclude the possibility of being affected by the content of monomers, the type of additives, and the like.
According to another embodiment of the present invention, a method of preparing a graft copolymer may include forming a core including an acrylic rubber polymer by mixing and polymerizing an acrylate monomer, a polymerization initiator, and a crosslinking agent; And grafting copolymerizing the core, the aromatic vinyl compound, and the vinyl cyan compound to form a shell including a styrene-acrylate copolymer on the core.
Forming the core may be a step of preparing an acrylic rubber polymer included therein.
The method of the polymerization reaction in which the acrylic rubber polymer is prepared is not particularly limited and may be carried out by a method commonly known in the art, for example, a mixture is introduced into a polymerization reactor in bulk, or may be carried out several times during the polymerization reaction. It can be carried out by divided or continuous feeding. In addition to the acrylate monomer, the polymerization initiator and the crosslinking agent in the polymerization reaction, in addition to the content of 10% by weight or less relative to the total weight of the acrylic rubber polymer, other additives such as an emulsifier or a molecular weight modifier may be further included.
Description of the acrylate-based monomer, polymerization initiator and crosslinking agent is duplicated as described above, so the description thereof is omitted.
The polymerization reaction for preparing the acrylic rubber polymer may be carried out at a temperature of about 40 to 90 ℃, it may be carried out continuously or intermittently for 0.5 to 6 hours. There is no particular limitation on these reaction conditions, and as described above, any of the conditions of the polymerization reaction generally applied in the art may be applied to the present invention.
The forming of the shell may include preparing an acrylic rubber polymer included therein.
That is, the styrene monomer and acrylonitrile monomer are grafted to the acrylic rubber polymer by mixing the aromatic vinyl compound as the styrene monomer, the vinyl cyan compound as the acrylonitrile monomer, and the acrylic rubber polymer of the preformed core. It may be a step of performing a reaction to copolymerize.
The graft copolymer to be provided in the present invention can be applied without limitation if the graft polymerization method generally known in the art, in addition to the above production method, for example, there may be an emulsion polymerization, suspension polymerization, etc. If prepared to satisfy the parameters, it is possible to provide a graft copolymer according to an embodiment of the present invention.
The prepared acrylate-styrene-acrylonitrile graft copolymer is preferably a latex that is stable even at a solid content of 40% by weight or more.
When the acrylate-styrene-acrylonitrile-based graft copolymer satisfies the relationship between crosslinking degree, swelling index, and swelling index and crosslinking degree, the bulk density may be 0.4 or more, and thus physical properties such as thermal stability and impact strength This improved graft copolymer can be provided.
In addition, the acrylate-styrene-acrylonitrile-based graft copolymer may have a wet powder moisture content of about 35% or less. When the wet powder moisture content is about 35% or less, physical properties such as thermal stability and impact strength of the graft copolymer may be improved, and when the range is satisfied at the same time as the bulk density, more optimal physical properties may be achieved. .
The acrylate-styrene-acrylonitrile graft copolymer prepared above may be prepared into acrylate-styrene-acrylonitrile-based graft copolymer powder particles by coagulation with a flocculant, followed by aging, dehydration and washing. As the flocculant, for example, an aqueous solution of an inorganic salt such as aluminum chloride, sodium sulfate, sodium nitrate, calcium chloride, magnesium sulfate, aluminum sulfate or an aqueous solution of a flocculant such as sulfuric acid or hydrochloric acid can be used.
The thermoplastic resin composition of the present invention comprises 5 to 60 parts by weight of the acrylate-styrene-acrylonitrile-based graft copolymer powder obtained above and 40 to 95 parts by weight of styrene-acrylonitrile-based resin in a hard matrix.
The styrene-acrylonitrile resin is a hard matrix capable of melt kneading with the acrylate-styrene-acrylonitrile-based graft copolymer dry powder prepared above, and is composed of a hard polymer-forming monomer having a glass transition temperature of at least 60. It is preferable that a vinyl compound, a vinyl cyan compound, a compound containing a unit derived from methyl methacrylate, a compound capable of forming a polycarbonate polymer, or the like is prepared alone or by mixing two or more kinds thereof.
It will be apparent to those skilled in the art that the thermoplastic resin composition may further include dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, and plasticizers that are commonly used according to use. .
Example
Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. 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.
EXAMPLE One
1) Acrylic Gum Preparation of Polymer
In the first step, 5 parts by weight of butyl acrylate, 0.2 parts by weight of sodium dodecyl sulfate, 0.025 parts by weight of triethylene glycol dimethacrylate, 0.025 parts by weight of aryl methacrylate, 0.1 part by weight of potassium persulfate and water The reaction temperature was raised to 70, and then reacted for 1 hour to prepare a polymer seed.
In the second step, a mixture of 45 parts by weight of butyl acrylate, 0.4 parts by weight of sodium dodecyl sulfate, 0.3 parts by weight of triethylene glycol dimethacrylate, 0.3 parts by weight of aryl methacrylate, and water were added to the prepared seeds. 0.1 parts by weight of and potassium persulfate were polymerized in succession at 70 to 3 hours, respectively, to obtain an acrylic rubber polymer having a particle size of 150 nm, a crosslinking degree of 96, a swelling index of 7.0, and a ratio of swelling index to a crosslinking degree of 0.073. Prepared.
2) Acrylate -Styrene-acrylonitrile Graft Preparation of Copolymer
50 parts by weight of the acrylic rubber polymer prepared in 1), 35 parts by weight of styrene and 15 parts by weight of acrylonitrile, a mixture of 0.5 parts by weight of sodium dodecyl sulfate and 0.1 parts by weight of t-dodecyl mercaptan, 0.1 parts by weight of potassium persulfate was continuously added at 70 to 3 hours for polymerization, and further reacted at 80 to 1 hour to increase polymerization conversion, and then cooled to 60 to obtain a graft rate of 200 nm of 40%. An acrylate-styrene-acrylonitrile graft copolymer of 120,000 was prepared.
The obtained acrylate-styrene-acrylonitrile graft copolymer was aggregated at 80 using an aqueous calcium chloride solution, then aged at 95, dehydrated and washed, dried for 30 minutes with 90 hot air, and finally acrylate- Styrene-acrylonitrile graft copolymer powder particles were obtained.
3) Preparation of Thermoplastic Specimen
45 parts by weight of the acrylate-styrene-acrylonitrile graft copolymer powder obtained above and 55 parts by weight of styrene-acrylonitrile copolymer (LG Chemical, product name: 92HR) in a hard matrix, 1 part by weight of lubricant, antioxidant 0.5 parts by weight and 0.5 parts by weight of UV stabilizer were added and mixed. This was prepared in pellet form using a 40 pie extrusion kneader at a cylinder temperature of 220, and injected into the pellet to prepare a physical specimen.
EXAMPLE 2
In the preparation of the acrylic rubber polymer of Example 1, the graft was the same as in Example 1 except that ethylene glycol dimethacrylate was added instead of triethylene glycol dimethacrylate in the first and second steps A copolymer was prepared, and the thermoplastic resin specimen including the same was prepared in the same manner as in Example 1.
EXAMPLE 3
In preparing the acrylic rubber polymer of Example 1, 0.05 parts by weight of triethylene glycol dimethacrylate and 0.05 parts by weight of aryl acrylate were added in the first step, and 0.4 parts by weight of triethylene glycol dimethacrylate in the second step. Part Graft copolymer was prepared in the same manner as in Example 1 except that 0.4 parts by weight of aryl acrylate was added, and a thermoplastic resin specimen including the same was prepared in the same manner as in Example 1.
Example 4
In preparing the acrylic rubber polymer of Example 1, the graft copolymer was the same as in Example 1 except that 0.01 parts by weight of sodium dihexylsulfosuccinate was added instead of 0.2 parts by weight of sodium dodecyl sulfate in the first step Was prepared, and the thermoplastic resin specimen including the same was prepared in the same manner as in Example 1.
EXAMPLE 5
In preparing the acrylate-styrene-acrylonitrile graft copolymer of Example 1, except that 0.15 parts by weight of t-dodecyl mercaptan was added, the graft copolymer was prepared in the same manner as in Example 1. And, the thermoplastic resin specimen including the same was prepared in the same manner as in Example 1.
EXAMPLE 6
In preparing the acrylate-styrene-acrylonitrile graft copolymer of Example 1, the graft copolymer was prepared in the same manner as in Example 1 except that 0.05 parts by weight of t-dodecyl mercaptan was added. And, the thermoplastic resin specimen including the same was prepared in the same manner as in Example 1.
Comparative example One
In preparing the acrylic rubber polymer of Example 1, 0.05 parts by weight of triethylene glycol dimethacrylate and 0.005 parts by weight of aryl acrylate were added in the first step, and 0.1 parts by weight of triethylene glycol dimethacrylate in the second step. A graft copolymer was prepared in the same manner as in Example 1, except that 0.1 parts by weight of aryl acrylate was added, and a thermoplastic resin specimen including the same was prepared in the same manner as in Example 1.
Comparative example 2
In preparing the acrylic rubber polymer of Example 1, 0.1 part by weight of triethylene glycol dimethacrylate and 0.1 part by weight of aryl acrylate were added in the first step, and 0.5 weight of triethylene glycol dimethacrylate in the second step. A graft copolymer was prepared in the same manner as in Example 1, except that 0.5 parts by weight of aryl acrylate was added, and a thermoplastic resin specimen including the same was prepared in the same manner as in Example 1.
Comparative example 3
In the preparation of the acrylic rubber polymer of Example 1, the graph is the same as in Example 1 except that 0.2 parts by weight of aryl acrylate is added in the first step, and 0.75 parts by weight of aryl acrylate in the second step. The copolymer was prepared, and the thermoplastic resin specimen including the same was prepared in the same manner as in Example 1.
Comparative example 4
In the preparation of the acrylic rubber polymer of Example 1, the graph is the same as in Example 1 except that 0.01 parts by weight of aryl acrylate is added in the first step, and 0.05 parts by weight of aryl acrylate in the second step The copolymer was prepared, and the thermoplastic resin specimen including the same was prepared in the same manner as in Example 1.
The (co) polymers parameters prepared in Examples 1 to 6 and Comparative Examples 1 to 4 are summarized in Table 1 below.
/ Church
(%)
Assessment Methods
1) impact strength
In order to compare and analyze the impact strength of the graft copolymer, the impact strength analysis of each specimen was performed, and the analysis was performed according to ASTM D256 (1/4, notched at 23 ° C, kgf · cm / cm 2 ).
2) bulk density
In order to compare and analyze the bulk density of the graft copolymer, the bulk density of each specimen was measured, and the bulk density was calculated as follows.
Bulk density = [mass of graft copolymer powder (g)] / [volume of graft copolymer filled in 100 ml container (ml)]
3) Wet powder moisture content
In order to compare and analyze the wet powder moisture content of the graft copolymer, the wet powder water content of each specimen was measured, and the wet powder water content was calculated as follows.
Wet powder moisture content (%) = [{(wet powder mass (g))-(dry powder mass (g))} / {wet powder mass (g)}] * 100
4) Thermal stability
The thermal stability of the pellet prepared by using an extrusion kneader in the injection molding machine at a molding temperature of 260 ℃ for 5 minutes, and then showed the discoloration degree (E) as the following equation 1 for the molded specimen (calculated by measuring equipment Obtained here), where E is the arithmetic mean value of the Hunter Lab values before and after the stay, and the closer to 0, the better the thermal stability.
[Equation 1]
E: discoloration degree
5) Retention glossiness ( % )
After pellets prepared by using an extrusion kneader were held in an injection molding machine at a molding temperature of 260 for 5 minutes, the glossiness of each specimen was measured to compare and analyze surface gloss characteristics of the graft copolymer. Glossiness was measured using a gloss meter at 45 ° according to ASTM D523.
The results of measuring the physical properties of the thermoplastic resin specimens of Examples 1 to 6 and Comparative Examples 1 to 4 based on the above items are shown in Table 2 below.
Moisture content (%)
(kgfcm / cm 2 )
(E)
(%)
Referring to Table 2, in the case of Comparative Example 1 where the ratio of the swelling index to the degree of crosslinking is 0.12 and the Graft rate is low as 30 and Comparative Example 4, which has a molecular weight of 160,000, all the physical properties are inferior to the resin specimens of the examples. It can be confirmed that, in the case of Comparative Example 2 where the ratio of the swelling index to the degree of crosslinking is 0.03, and the Comparative Example 3, the graft ratio is high as 70 and the molecular weight is 80,000, which is low, the impact strength is significantly decreased. On the other hand, in the case of the resin specimens in Examples 1 to 6 it can be confirmed that the excellent evaluation in all five physical properties.
Through this, it can be seen that the typical physical properties of the graft copolymer may depend on the swelling index, crosslinking degree, ratio of swelling index to crosslinking degree, graft rate and molecular weight of the graft copolymer. Thus, by controlling the above parameters, it was confirmed that the acrylate-styrene-acrylonitrile-based graft copolymer with improved physical properties can be provided.
Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.
Claims (18)
A core containing an acrylic rubber polymer; And
A grafting shell located on the surface of the core and containing a styrene-acrylonitrile (SAN) -based copolymer;
The acrylic rubber polymer has a crosslinking degree of 93 to 99, a swelling index of 4 to 10,
The graft shell is a graft copolymer having a graft ratio of 32 to 60%.
The acrylic rubber polymer is a graft copolymer having a ratio of swelling index to the degree of crosslinking of 0.04 to 0.1.
The core is a graft copolymer of 50 to 600 nm in diameter.
The graft shell is a graft copolymer having a thickness of 6 to 200 nm.
Graft copolymer of the styrene-acrylonitrile-based copolymer contained in the graft shell is 90,000 to 150,000.
The acrylate-styrene-acrylonitrile-based graft copolymer is a graft copolymer having a bulk density of 0.4 or more.
The acrylate-styrene-acrylonitrile-based graft copolymer is a graft copolymer having a wet powder moisture content of 35% or less.
The composition for copolymerization of the acrylate-styrene-acrylonitrile graft copolymer of claim 1 having a graft ratio of 32 to 60%.
The aromatic vinyl compound and the vinyl cyan compound is a composition for copolymerization is contained in the ratio of 97: 3 to 60:40 weight ratio.
The aromatic vinyl compound is a composition for copolymerization comprising any one selected from the group consisting of styrene, α-methylstyrene, p-styrene and vinyl toluene and combinations thereof.
The vinyl cyan compound is a copolymer composition comprising any one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and combinations thereof.
The composition for copolymerization is a composition for copolymerization further containing alkyl methacrylate having 1 to 4 carbon atoms of alkyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160030752A KR102049869B1 (en) | 2016-03-15 | 2016-03-15 | Graft copolymers based on acrylonitrile-styrene-acrylate and thermoplastic resin composition comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160030752A KR102049869B1 (en) | 2016-03-15 | 2016-03-15 | Graft copolymers based on acrylonitrile-styrene-acrylate and thermoplastic resin composition comprising the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170107171A KR20170107171A (en) | 2017-09-25 |
| KR102049869B1 true KR102049869B1 (en) | 2019-11-28 |
Family
ID=60035101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020160030752A KR102049869B1 (en) | 2016-03-15 | 2016-03-15 | Graft copolymers based on acrylonitrile-styrene-acrylate and thermoplastic resin composition comprising the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102049869B1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014516104A (en) | 2012-02-03 | 2014-07-07 | エルジー・ケム・リミテッド | ASA-based graft copolymer composition |
| JP2014214259A (en) | 2013-04-26 | 2014-11-17 | ユーエムジー・エービーエス株式会社 | Crosslinked methacrylic resin and scratch-resistant resin composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69027976T2 (en) * | 1989-11-27 | 1997-03-06 | Mitsubishi Rayon Co | High impact graft copolymers and resin compositions |
| KR101478027B1 (en) * | 2013-01-29 | 2014-12-31 | 제일모직주식회사 | Acrylate-Styrene-Acrylonitrile Graft Copolymer Having Excellent Impact-resistance and Dyeability Property, and Method for Preparing Same |
-
2016
- 2016-03-15 KR KR1020160030752A patent/KR102049869B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014516104A (en) | 2012-02-03 | 2014-07-07 | エルジー・ケム・リミテッド | ASA-based graft copolymer composition |
| JP2014214259A (en) | 2013-04-26 | 2014-11-17 | ユーエムジー・エービーエス株式会社 | Crosslinked methacrylic resin and scratch-resistant resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170107171A (en) | 2017-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101692106B1 (en) | Acrylic impact modifier with core-shell structure and composition of acrylic resin comprising thereof | |
| KR102074489B1 (en) | Graft Copolymer, Thermoplastic Resin Composition And Thermoplastic Resin Molded Article Comprising Thereof | |
| CN113166521B (en) | Thermoplastic resin composition comprising (meth) acrylate graft copolymer and method for preparing thermoplastic resin composition | |
| JP7195444B2 (en) | ACRYLIC GRAFT COPOLYMER, METHOD FOR PRODUCING SAME, AND THERMOPLASTIC RESIN COMPOSITION CONTAINING THE SAME | |
| KR20200017161A (en) | Method for preparing graft copolymer, graft copolymer and thermoplastic resin products | |
| KR102068650B1 (en) | Graft copolymer, method for preparing the graft copolymer, thermoplastic resin composition and molding product | |
| KR20110079011A (en) | Thermoplastic resin composition having excellent impact strength and weather resistance | |
| CN113412290B (en) | Alkyl acrylate compound-vinyl cyanide compound-aromatic vinyl compound graft copolymer | |
| JP7098121B2 (en) | Method for Producing Graft Copolymer and Graft Copolymer | |
| KR100998413B1 (en) | Transparent acrylic resin and method of preparing the same | |
| KR102653406B1 (en) | Thermoplastic resin composition and method for preparing the same | |
| KR102165690B1 (en) | Thermoplastic resin composition, method for preparing the resin composition and molded product comprising the same | |
| KR20070035779A (en) | Acrylate-styrene-acrylonitrile graft copolymer and method for preparing the same and thermoplastic resin composition containing the same | |
| KR102354837B1 (en) | Method for preparing graft copolymer powder | |
| KR101072037B1 (en) | Low-gloss thermoplastic resin composition having excellent impact resistance and heat resistance | |
| KR102049869B1 (en) | Graft copolymers based on acrylonitrile-styrene-acrylate and thermoplastic resin composition comprising the same | |
| KR102244956B1 (en) | Method for preparing graft copolymer | |
| KR102642821B1 (en) | Thermoplastic resin composition and method for preparing the same | |
| KR20190043404A (en) | Thermoplastic resin composition and thermoplastic resin molded article prepared by using the same | |
| KR102435333B1 (en) | Method for preparing graft copolymer, graft copolymer and thermoplastic resin products | |
| KR102465134B1 (en) | Method for preparing graft copolymer | |
| KR100507336B1 (en) | Method of Preparing Thermoplastic Resin Composition with Good Heat Resistance and Good Transparence | |
| KR102173493B1 (en) | Transparent thermoplastic resin composition and method for preparing the same | |
| KR20220048111A (en) | Thermoplastic transparent resin composition, and molded product | |
| KR20230172109A (en) | Thermoplastic resin composition, method for preparing the same and article prepared therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right |