KR102023986B1 - Asa based graft copolymer, thermoplastic resin composition and molded products - Google Patents
Asa based graft copolymer, thermoplastic resin composition and molded products Download PDFInfo
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- 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
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
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- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/06—Vinyl aromatic monomers and methacrylates as the only monomers
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- 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
- C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
The present invention provides an ASA-based graft copolymer which improves the stability of latex by using a material having a role of an electrolyte and a buffer, and a thermoplastic resin composition having excellent impact strength, thermal stability, and surface gloss without deterioration of existing mechanical properties. And to provide a molded article that does not generate projections during the extrusion processing thereof.
Description
The present disclosure relates to an ASA-based graft copolymer, a thermoplastic resin composition, and a molded article, and more particularly, to an ASA-based graft copolymer having improved stability of latex by using a material that serves as a buffer and an electrolyte, and the same. The present invention relates to a thermoplastic resin composition having excellent impact strength, thermal stability, and surface gloss without deterioration of existing mechanical properties, and to a molded article in which protrusions are not generated during extrusion processing thereof.
In the case of automotive exterior materials and cell phone housings, they are frequently exposed to low temperature when used, and are easily exposed to light sources such as ultraviolet rays. In addition, these materials require high heat resistance temperatures that can withstand hot sun and high tensile strength.
Typical rubber-reinforced thermoplastics include acrylonitrile-butadiene-styrene (ABS) resins, acrylonitrile-styrene-acrylonitrile (ASA) resins, methylmethacrylate-butadiene-styrene (MBS) resins, and acrylic impact modifier (AIM) resins. The selected shell layer is formed through graft copolymerization in consideration of compatibility with the matrix resin and the rubbery polymer of 0 ° C. or less as a core.
Generally, ABS resin manufactured by graft copolymerization of styrene and acrylonitrile monomer on butadiene-based rubber polymer has impact resistance, processability, beautiful appearance, excellent mechanical strength, and high heat deformation temperature. It is used for various purposes such as construction materials.
However, because ABS resin has ethylenically unsaturated polymer in butadiene rubber used as impact modifier, it is easily oxidized by ultraviolet rays, light and heat in the presence of oxygen, so the resin's appearance and color change and its mechanical properties are weak. There is a problem that it is not suitable as an outdoor material.
Therefore, in order to obtain a thermoplastic resin having excellent physical properties and excellent weatherability and aging resistance, an ASA resin, which is an acrylate-styrene-acrylonitrile terpolymer using an acrylic rubber having no ethylenically unsaturated polymer instead of butadiene rubber, is used as an impact modifier. have. Such ASA resin is used in various fields such as electronic and electrical parts, building materials, automobiles, ships, leisure goods, horticulture, etc. which are used outdoors.
For reference, the manufacturing method of ASA resin excellent in weatherability and aging resistance is German Patent No. 1,260,135, US Patent No. 3,426,101, Japanese Patent Application Laid-Open No. Hei 4-180949, Hei 5-202264, Hei 7-316243, USA Patent No. 5,932,655 and the like.
However, the mechanical properties of the thermoplastic ASA resin including the same due to the electrolyte introduced during the emulsion polymerization of these ASA resins, but when the sheet is manufactured by extrusion processing, there is a problem that the surface gloss is not enough and the projections on the surface of the sheet. Therefore, there is a need to develop a technology for the ASA-based graft copolymer that does not generate surface projections during extrusion and further improves surface gloss and improves impact strength and thermal stability.
It is an object of the present disclosure to provide an ASA-based graft copolymer having improved stability of a latex and a method of manufacturing the same.
Another object of the present disclosure is to provide a thermoplastic resin composition including the ASA graft copolymer and having excellent impact strength, thermal stability, and surface gloss without deterioration of existing mechanical properties, and a molded article having no protrusions during extrusion. have.
The above objects of the present disclosure can all be achieved by the present disclosure described below.
The present substrate is an ASA-based graft copolymer composed of a seed, a core and a shell, wherein the seed or the seed and the core
In addition, the present invention is prepared when the ASA-based graft copolymer composed of a seed, a core and a shell
In addition, the present invention provides a thermoplastic resin composition comprising 10 to 70 parts by weight of the ASA graft copolymer prepared by the above method and 30 to 90 parts by weight of the hard matrix resin.
Furthermore, the present invention provides a molded article characterized in that it is produced including the thermoplastic resin composition.
According to the present disclosure, an ASA-based graft copolymer which improves the stability of latex by using a material that serves as a buffer and an electrolyte, and a thermoplastic having excellent impact strength, thermal stability and surface gloss without deterioration of existing mechanical properties It is effective in providing a resin composition and a molded article which does not generate | occur | produce a protrusion at the time of its extrusion process.
Hereinafter, the present description will be described in detail.
In the ASA graft copolymer composed of the ASA graft copolymer seed, the core and the shell of the present invention, the seed or the seed and the core
In addition, the manufacturing method of the ASA-based graft copolymer of the present disclosure is used to prepare an ASA-based graft copolymer composed of a seed, a core, and a shell.
The ASA graft copolymer of the present description means an acrylate compound-aromatic vinyl compound-vinylcyan compound copolymer.
The carboxylic acid metal salt may be included in the seed, or the seed and the core, for example, and in this case, there is an effect of imparting stability to the latex.
The carboxylic acid metal salt may be included in the production of seeds or cores, for example, and may be emulsion polymerized.
The carboxylic acid metal salt may have, for example, a molecular weight of 100 to 750 g / mol, 120 to 700 g / mol, or 130 to 650 g / mol and has excellent mechanical properties within this range.
M of the carboxylic acid metal salt is, for example, an alkali metal or an alkaline earth metal, and specifically, sodium or potassium.
The carboxylic acid metal salt is another example
As a specific example, the carboxylic acid metal salt is disodium oxalate, disodium malonate, disodium succinate, disodium phthalate, disodium maleate malate, Disodium fumarate, Trisodium Citrate, Trisodium nitrilotriacetate, Tetrasodium ethylene diamine tetraacetate, and Pentasodium diethylenetriethylene It may be at least one selected from the group consisting of amine pentaacetate (Pentasodium diethylenetriaminepentaacetate).
The carboxylic acid metal salt may be included as 0.01 to 2 parts by weight only in the seed or 0.005 to 1 parts by weight in the seed and 0.005 to 1 part by weight in the core based on 100 parts by weight of the total monomers constituting the seed, core and shell, for example. Within this range, it is possible to provide excellent latex stability without deteriorating existing mechanical properties.
The ASA graft copolymer may include, for example, a polymerized seed including at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate compound; A rubber core that wraps around the seed and comprises an alkyl acrylate; And a shell surrounding the core and including one or more compounds selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate compound.
The aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, and vinyltoluene. Specifically, styrene is used, but is not limited thereto.
The vinyl cyan compound may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, and specifically, acrylonitrile is used, but is not limited thereto.
In addition, the alkyl (meth) acrylate may include, for example, an alkyl group having 2 to 8 carbon atoms, but is not limited thereto.
The alkyl (meth) acrylate-vinylaromatic compound-vinyl cyan compound copolymer may be, for example, butyl acrylate-styrene-acrylonitrile.
As another example, the alkyl (meth) acrylate-vinylaromatic compound-vinylcyan compound copolymer may be butylacrylate-styrene-acrylonitrile-methyl methacrylate.
The ASA graft copolymer includes, for example, 4 to 30% by weight of the seed, 20 to 76% by weight of the core, and 20 to 76% by weight of the shell, and has an excellent balance of physical properties within this range.
The ASA-based graft copolymer is a seed; Or a copolymer copolymerized with a seed and a core; further comprising a crosslinking agent.
In the present description, the crosslinking agent is referred to separately from the monomer.
The crosslinking agent is, for example, divinylbenzene, trivinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6- Hexanediol dimethacrylate, ethylene glycol diacrylate, hexanediol ethoxylate diacrylate, hexanediol ethoxylate diacrylate, hexanediol propoxylate diacrylate, neopentyl glycol dimethacrylate, neopentyl Glycol ethoxylate diacrylate, neopentyl glycol propoxylate diacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, trimethylpropaneethoxylate triacrylate, trimethylpropane propoxylate triacrylate , Pentaerythritol ethoxylate triacrylate, pentaerythro Propoxy triacrylate, vinyl trimethoxysilane, allyl methacrylate, triallyl isocyanurate may be at least one member selected from the cyanurate, triallyl amine, and di the group consisting of allyl amine.
The initiator used in the preparation of the ASA-based graft copolymer is not particularly limited, but preferably a radical initiator may be used. Examples of the radical initiator include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-mentanehydro peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxides, 3,5,5-trimethylhexanol peroxide and t-butyl peroxy isobutylate; At least one selected from the group consisting of azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobis isobutyric acid (butyl acid) methyl may be used, and is preferable. Preferably inorganic peroxide, most preferably persulfate.
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, pyrroline acid It may be at least one selected from the group consisting of sodium, sodium sulfite and the like.
The emulsifier of the ASA graft copolymer is not particularly limited, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. The emulsifier may preferably be an anionic surfactant, for example alkenyl succinate metal salts, alkylbenzene sulfonates, aliphatic sulfonates, sulfate ester salts of higher alcohols, α-olefin sulfonates, and alkyl ether sulfate ester salts It may be one or more selected from the group consisting of.
The ASA graft copolymer may include, for example, a seed, a core or a shell; It may further comprise a mercaptan compound as the molecular weight regulator in the preparation, and preferably may include a molecular weight regulator only in the shell.
The ASA graft copolymer of the present disclosure may include, for example, a seed having an average particle diameter of 0.03 to 0.3 µm, 0.05 to 0.2 µm, or 0.1 to 0.2 µm, and an average particle diameter including the seed of 0.05 to 0.5 µm and 0.1. To 0.4 μm, or 0.2 to 0.3 μm.
The ASA graft copolymer of the present disclosure has, for example, an average particle diameter larger than the average particle diameter of the core, and may be 0.1 to 0.7 μm, or 0.2 to 0.6 μm, and excellent mechanical and physical property balance within this range. .
The copolymer may further include additives such as dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, thermal stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, plasticizers or matting agents that are commonly used according to the use.
ASA-based graft copolymer composed of a seed, a core and a shell according to the present disclosure may be provided as a specific example.
The seed may include, for example, at least one seed-forming monomer selected from the group consisting of alkyl (meth) acrylate monomers, aromatic vinyl compounds, and vinyl cyan compounds based on 100 parts by weight of the total monomers included in the ASA graft copolymer. To 30 parts by weight, the carboxylic acid metal salt 0.01 to 1.0 parts by weight, crosslinking agent 0.01 to 1.0 parts by weight, emulsification polymerization including the emulsifier 0.1 to 2 parts by weight and 0.01 to 2 parts by weight of the polymerization initiator, the impact strength within this range, The thermal stability and the surface gloss are excellent.
The core is, for example, based on 100 parts by weight of the total monomers included in the ASA graft copolymer, 20 to 80 parts by weight of alkyl acrylate monomers, 0 to 1.0 parts by weight of carboxylic acid metal salts, 0.03 to 2.0 parts by weight of crosslinking agents, and emulsifier 0.1. It is emulsified and polymerized including 2 to 2 parts by weight and 0.01 to 2 parts by weight of a polymerization initiator, and within this range, impact strength, thermal stability and surface gloss are excellent.
The graft shell may be, for example, a graft shell selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, and alkyl (meth) acrylate compounds based on 100 parts by weight of the total monomers included in the ASA graft copolymer. 20 to 80 parts by weight of the forming monomer, 0.1 to 2 parts by weight of an emulsifier, 0 to 1.0 parts by weight of a molecular weight modifier and 0.01 to 2 parts by weight of a polymerization initiator are emulsified and polymerized within this range.
More specifically, the ASA graft copolymer composed of the seed, the core and the shell according to the present disclosure may be prepared as follows.
The seed may be, for example, at least one seed-forming monomer selected from the group consisting of an alkyl (meth) acrylate monomer, an aromatic vinyl compound, and a vinyl cyan compound based on 100 parts by weight of the total monomers used to prepare the ASA graft copolymer. 4 to 30 parts by weight, the metal carboxylate 0.01 to 1.0 parts by weight, the cross-linking agent 0.01 to 1.0 parts by weight, 0.1 to 2 parts by weight of the emulsifier and 0.01 to 2 parts by weight of the polymerization initiator are added in a batch or continuous, preferably a batch And then emulsion polymerized to produce a polymer seed latex.
The core is 20 to 80 parts by weight of the alkyl acrylate monomer under the polymer seed latex, 0 to 1.0 parts by weight of the carboxylic acid metal salt, a crosslinking agent, based on 100 parts by weight of the total monomers used to prepare the ASA graft copolymer, for example. The core may be prepared as a crosslinked alkyl acrylate rubber polymer by adding 0.03 to 2.0 parts by weight, 0.1 to 2 parts by weight of an emulsifier and 0.01 to 2 parts by weight of a polymerization initiator in a batch or continuously, preferably continuously and emulsion polymerization. .
The shell may be, for example, at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, and alkyl (meth) acrylate compounds in the presence of the core based on 100 parts by weight of the total monomers used for preparing the ASA graft copolymer. 20 to 80 parts by weight of the selected graft shell forming monomer, 0.1 to 2 parts by weight of an emulsifier, 0 to 1.0 parts by weight of a molecular weight regulator and 0.01 to 2 parts by weight of a polymerization initiator are added in a batch or in a continuous manner, preferably emulsion polymerization while continuously To produce a graft shell.
The polymerization temperature during the emulsion polymerization is not particularly limited, but may be, for example, 50 to 85 ° C, preferably 60 to 80 ° C.
The ASA graft copolymer provided in accordance with the present disclosure can maintain a stable state of the latex even at a solid content of 40% by weight or more of the latex.
The ASA-based graft copolymers provided in accordance with the present disclosure can be provided as powder particles by coagulation with a flocculant, followed by aging, dehydration and washing.
As the coagulant, 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 coagulant such as sulfuric acid or hydrochloric acid may be used.
The present disclosure provides a thermoplastic resin composition comprising the ASA-based graft copolymer, and also provides a molded article, especially a molded article provided as an extruded sheet, comprising the thermoplastic resin composition.
The thermoplastic resin composition may include, for example, 10 to 70 wt% of the ASA graft copolymer powder and 30 to 90 wt% of the hard matrix resin.
The hard matrix resin may have, for example, a glass transition temperature of 60 ° C. or more, and in another example, at least one compound of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate compound, a polycarbonate polymer, or a mixture thereof. It may be, specifically, may be a styrene-acrylonitrile resin.
The thermoplastic resin composition may be one or more selected from dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, and plasticizers, which are commonly used as needed, without affecting physical properties. You can include more within.
Hereinafter, preferred examples are provided to help the understanding of the present disclosure. However, the following examples are merely illustrative of the present disclosure, and it is apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present disclosure. It goes without saying that changes and modifications belong to the appended claims.
EXAMPLE
Example One
<Production of ASA Graft Copolymer Latex>
Seed Manufacturing Steps
50 parts by weight of distilled water, 5 parts by weight of butyl acrylate, 0.2 parts by weight of trisodium nitrilotriacetate, 0.05 parts by weight of allyl methacrylate, and 0.1 parts by weight of sodium lauryl sulfate were added to a nitrogen-substituted polymerization reactor. After the temperature was raised to 70 ° C., 0.1 parts by weight of potassium persulfate was added to initiate the reaction, and reacted for 1 hour while maintaining 70 ° C. to prepare a seed latex having an average particle diameter of 0.1 μm.
For reference, the average particle diameter in the present disclosure was measured using an intensity Gaussian distribution (Nicomp 380) by dynamic laser light scattering.
Core manufacturing steps
In the presence of the seed latex, a mixture of 60 parts by weight of distilled water, 50 parts by weight of butyl acrylate, 0.5 part by weight of allyl methacrylate, 0.5 part by weight of sodium lauryl sulfate and 0.1 part by weight of potassium persulfate was mixed at 70 ° C. for 2 hours. Continuous injection was carried out, and polymerization was further performed for 1 hour after the completion of charge, and a core having an average particle diameter of 0.23 μm was prepared as an acrylate rubber polymer.
Graft Shell manufacturing steps
In the presence of the acrylate rubber polymer, a mixture of 40 parts by weight of distilled water, 34 parts by weight of styrene, 11 parts by weight of acrylonitrile, 0.5 parts by weight of an emulsifier and 0.1 parts by weight of potassium persulfate was polymerized while continuously introduced at 70 ° C. for 2 hours. The reaction was carried out. In addition, in order to increase the polymerization conversion rate, the reaction was completed for 1 hour at 70 ° C. after completion of the addition, and cooled to 60 ° C. to terminate the polymerization reaction to prepare a final ASA graft copolymer latex.
The average particle diameter of the polymerized latex was 0.29 µm, the polymerization conversion was 99%, and the solid content of the obtained latex was 40 wt%.
<ASA Graft Copolymer Powder Preparation>
The obtained ASA graft copolymer latex was agglomerated at 80 ° C. using an aqueous calcium chloride solution, then aged at 95 ° C., and dried for 30 minutes with 90 ° C. hot air after dehydration and washing to obtain ASA graft copolymer powder. Prepared.
<Thermoplastic resin composition preparation>
40 parts by weight of the ASA graft copolymer powder and 60 parts by weight of a styrene-acrylonitrile copolymer (LG Chemical, product name: 92HR) as a hard matrix resin, 1 part by weight of lubricant, 0.5 part by weight of antioxidant, and UV stabilizer 0.5 Parts by weight were added and mixed. This was prepared in pellet form using a 40 pie extrusion kneader at a cylinder temperature of 220 ° C., and injected into the pellet to prepare a physical specimen.
Example 2
The same process as in Example 1 was repeated except that trisodium nitrilotriacetate was replaced with disodium oxalate in the seed preparation step of Example 1.
Example 3
The same process as in Example 1 was repeated except that trisodium nitrilotriacetate was replaced with tetrasodium ethylene diamine tetraacetate in the seed preparation step of Example 1.
Example 4
The same process as in Example 1 was performed except that 0.2 part by weight of trisodium nitrilotriacetate was replaced with 0.5 part by weight of pentasodium diethylenetriaminepentaacetate in the seed preparation step of Example 1. Repeated.
Example 5
The same process as in Example 1 was repeated except that butyl acrylate was replaced with styrene in the seed preparation step of Example 1.
Example 6
The same process as in Example 1 was repeated except that 5 parts by weight of butyl acrylate was replaced with 4 parts by weight of methyl methacrylate and 1 part by weight of acrylonitrile in the seed preparation step of Example 1.
Example 7
The same process as in Example 1 was repeated except that 0.1 part by weight of trisodium nitrilotriacetate was additionally added in the core manufacturing step of Example 1.
Example 8
Except for replacing the 34 parts by weight of styrene, 11 parts by weight of acrylonitrile, 30 parts by weight of styrene, 9 parts by weight of acrylonitrile and 6 parts by weight of methyl methacrylate in the shell manufacturing step of Example 1 and The same process was repeated.
Example 9
The same process as in Example 1 was repeated except that 0.1 parts by weight of tertiary dodecyl mercaptan was added in the shell preparation step of Example 1.
Comparative example One
The same process as in Example 1 was repeated except that trisodium nitrilotriacetate was not used in the seed preparation step of Example 1.
Comparative example 2
The same process as in Example 1 was repeated except that trisodium nitrilotriacetate was replaced with sodium acetate in the seed preparation step of Example 1.
Comparative example 3
The same process as in Example 1 was repeated except that trisodium nitrilotriacetate was replaced with potassium chloride in the seed preparation step of Example 1.
Comparative example 4
The same process as in Example 1 was repeated except that trisodium nitrilotriacetate was replaced with sodium bicarbonate in the seed preparation step of Example 1.
Comparative example 5
The same process as in Example 1 was repeated except that trisodium nitrilotriacetate was replaced with sodium bisulfate in the seed preparation step of Example 1.
Comparative example 6
The same process as in Example 1 was repeated except that trisodium nitrilotriacetate was replaced with potassium phosphate in the seed preparation step of Example 1.
The physical properties of the ASA graft copolymers prepared in Examples and Comparative Examples and the thermoplastic resin composition specimens including the copolymers were measured by the following methods, and the results are shown in Tables 1 and 2 below.
* Average particle size: measured using an intensity Gaussian distribution (Nicomp 380) by dynamic laser light scattering method.
* Polymerization conversion rate (%): Polymerization conversion rate is measured by weighing 1.5 g of the latex prepared in a 150 ℃ hot air dryer after drying for 15 minutes to obtain the total solid content (TSC), and calculate the polymerization conversion rate by It was.
[Equation 1]
* Coagulant content (% by weight): The ASA graft copolymer latex was filtered through a 200 mesh wire mesh to dry the coagulant that did not pass through the mesh at 100 ° C. for 7 hours and then weighed to determine the content of the coagulant to solids. Was calculated. Higher coagulant content indicates less latex stability.
* Protrusion score: The extrusion sheet was manufactured to quantify the degree of protrusion, and the closer to 5 to 1 to 5, the higher the frequency of protrusion.
Izod impact strength (1/4 notched at 23 ° C., kgf · cm / cm): Measured according to ASTM D256.
* Surface gloss (45 °): measured according to ASTM D2457.
* Thermal Stability: After pellets prepared using an extruder kneader for 10 minutes in an injection molding machine having a molding temperature of 260 ℃, the molded specimens exhibited a discoloration degree ( ΔE ) as shown in Equation 2 below, where ΔE is It is the arithmetic mean value of Hunter Lab values before and after stay, and the closer to 0, the better the thermal stability.
[Equation 2]
Through Tables 1 and 2 above, the thermoplastic resin compositions of Examples 1 to 9 including the ASA-based graft copolymers prepared using the carboxylic acid metal salts according to the present disclosure do not use carboxylic acid metal salts or use conventional electrolytes. Compared with the thermoplastic resin composition of Comparative Examples 1 to 6 containing the ASA-based graft copolymer prepared by using the conventional mechanical properties while maintaining excellent impact strength, thermal stability and surface gloss at the same time no protrusions during extrusion Could confirm.
Claims (18)
On the seed or on the seed and core
The carboxylic acid metal salt is an ASA graft copolymer, characterized in that the molecular weight of 100 to 750 g / mol.
The carboxylic acid metal salt is
The carboxylic acid metal salt is disodium oxalate, disodium malonate, disodium succinate, disodium phthalate, disodium malate, Disodium fumarate, Trisodium Citrate, Trisodium nitrilotriacetate, Tetrasodium ethylene diamine tetraacetate, and pentasodium diethylenetriaminepentaacetate (Pentasodium diethylenetriaminepentaacetate) ASA graft copolymer, characterized in that at least one member selected from the group consisting of.
The carboxylic acid metal salt comprises 0.01 to 2 parts by weight only in the seed or 0.005 to 1 parts by weight in the seed and 0.005 to 1 parts by weight in the core based on a total of 100 parts by weight of the monomer constituting the seed, core and shell ASA graft copolymer.
The aromatic vinyl compound is an ASA graft copolymer, characterized in that at least one member selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene and vinyltoluene.
The vinyl cyan compound is an ASA graft copolymer, characterized in that at least one member selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile.
The alkyl of the alkyl (meth) acrylate is an ASA-based graft copolymer, characterized in that 2 to 8 carbon atoms.
The ASA graft copolymer is a seed; Or seed and core; ASA-based graft copolymer, characterized in that it further comprises a crosslinking agent.
The hard matrix resin is a thermoplastic resin composition, characterized in that the glass transition temperature is 60 ℃ or more.
The thermoplastic resin composition further comprises at least one selected from the group consisting of a lubricant, a heat stabilizer, an antioxidant, a light stabilizer, an anti drip agent, a pigment, and an inorganic filler.
The thermoplastic resin composition is a thermoplastic resin composition, characterized in that the surface glossiness measured in accordance with ASTM D2457 or more than 85.
The thermoplastic resin composition The thermoplastic resin composition characterized in that a 4.0 or less thermally stable (Δ E).
The molded article is a molded article, characterized in that the extrusion sheet does not occur projections.
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| JPH0873535A (en) * | 1994-04-27 | 1996-03-19 | Nippon Shokubai Co Ltd | Production of thermoplastic resin |
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| KR101425754B1 (en) * | 2012-08-27 | 2014-08-05 | 주식회사 엘지화학 | Graft copolymer and thermoplastic resin composition comprising thereof |
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