KR20170050086A - 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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- C—CHEMISTRY; METALLURGY
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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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- 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
- C08L51/06—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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- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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Abstract
The present invention relates to an ASA-based graft copolymer which improves the stability of a latex by using a substance having both an electrolyte and a buffer, and a thermoplastic resin composition containing the same and having excellent impact strength, heat stability and surface gloss without deteriorating mechanical properties And a molded article in which no protrusion is generated during the extrusion processing.
Description
The present invention relates to an ASA-based graft copolymer, a thermoplastic resin composition and a molded article, and more particularly, to an ASA-based graft copolymer which improves the stability of a latex by using a substance having a role of an electrolyte and a buffer Which is excellent in impact strength, thermal stability and surface gloss without deteriorating the existing mechanical properties, and a molded article in which no protrusion is generated in the extrusion processing of the thermoplastic resin composition.
In the case of an automobile exterior material or a cellular phone housing, it is frequently exposed to a low temperature environment in use and is likely to be exposed to a light source such as ultraviolet rays. In addition, these materials require high heat-resistant temperatures to withstand hot sunlight and require high tensile strength.
Examples of the rubber-reinforced thermoplastic resin include ABS (acrylonitrile-butadiene-styrene) resin, ASA (acrylonitrile-styrene-acrylonitrile) resin, MBS (methylmethacrylate-butadiene-styrene) resin and AIM Is formed through graft copolymerization using a rubbery polymer having a core temperature of 0 DEG C or less as a core and considering the compatibility with the matrix resin.
Generally, ABS resin, which is produced by graft copolymerizing styrene and acrylonitrile monomer to a butadiene rubber polymer, has impact resistance, processability, beautiful appearance, excellent mechanical strength, and high heat distortion temperature, , And construction materials.
However, because of the presence of the ethylenically unsaturated polymer in the butadiene rubber used as an impact modifier, the ABS resin is easily oxidized by ultraviolet rays, light, and heat in the presence of oxygen, resulting in changes in the appearance and color of the resin, There is a problem that it is not suitable as an outdoor material.
Therefore, in order to obtain a thermoplastic resin excellent in physical properties and excellent in weather resistance and aging resistance, an ASA resin which is an acrylate-styrene-acrylonitrile ternary copolymer using an acrylic rubber in which an ethylenically unsaturated polymer is not present instead of butadiene rubber as an impact modifier is used have. These ASA resins are used in various fields such as electronic and electric parts used for outdoor use, construction materials, automobiles, ships, leisure goods, gardening.
For reference, a method of producing an ASA resin excellent in weatherability and aging resistance is disclosed in German Patent No. 1,260,135, US Patent No. 3,426,101, Japanese Patent Application Laid-Open Nos. 4-180949, 5-202264, 7-316243, Patent No. 5,932,655 and the like.
However, the thermoplastic ASA resin including the thermoplastic ASA resin is excellent due to the electrolyte injected during the emulsion polymerization of these ASA resins, but when the sheet is produced by extrusion processing, there is a problem that surface gloss is not sufficient and stone surface is generated on the surface of the sheet. Therefore, there is a need to develop a technique for an ASA-based graft copolymer which does not cause surface projection of a sheet during extrusion processing, further improves surface gloss, and improves impact strength and thermal stability.
The object of the present invention is to provide an ASA-based graft copolymer which improves the stability of latex and a process for producing the same.
Another object of the present invention is to provide a thermoplastic resin composition containing the ASA-based graft copolymer and excellent in impact strength, thermal stability and surface gloss without deteriorating existing mechanical properties, and a molded article in which no projection is generated during its extrusion processing have.
The above object of the present invention can be achieved by all the present invention described below.
The present invention relates to an ASA-based graft copolymer comprising a seed, a core and a shell, wherein the seed or the seed and the core
The present invention also relates to a process for producing an ASA-based graft copolymer comprising a seed, a core and a shell
Also, the present invention provides a thermoplastic resin composition comprising 10 to 70 parts by weight of an ASA-based graft copolymer produced by the above method and 30 to 90 parts by weight of a hard matrix resin.
Furthermore, the present invention provides a molded article which is produced by including the thermoplastic resin composition.
According to the present invention, there is provided an ASA-based graft copolymer which improves the stability of a latex by using a substance which plays a role of an electrolyte and a buffer, and a thermoplastic resin composition containing the same and having excellent impact strength, heat stability and surface gloss There is an effect of providing a resin composition and a molded article in which no projection is generated during its extrusion processing.
Hereinafter, the present invention will be described in detail.
In the ASA-based graft copolymer composed of the ASA-based graft copolymer seed, the core and the shell of the present invention, the seed or the seed and the core
In addition, the process for producing an ASA-based graft copolymer according to the present invention is a process for producing an ASA-based graft copolymer comprising a seed, a core and a shell
The ASA-based graft copolymer of the present invention means an acrylate compound-aromatic vinyl compound-vinyl cyanide copolymer.
The carboxylic acid metal salt may be included in a seed, a seed and a core, and in this case, it has an effect of imparting stability to the latex.
The carboxylic acid metal salt may be emulsion-polymerized, for example, in the preparation of a seed or a seed and a core.
The carboxylic acid metal salt may have a molecular weight of 100 to 750 g / mol, 120 to 700 g / mol, or 130 to 650 g / mol, for example, and has excellent mechanical properties within this range.
The M of the carboxylic acid metal salt is, for example, an alkali metal or an alkaline earth metal, and specific examples thereof may be sodium or potassium.
The carboxylic acid metal salt is another example
As a specific example, the carboxylic acid metal salt may be selected from the group consisting of disodium oxalate, disodium malonate, disodium succinate, disodium phthalate, disodium malate, malate, disodium fumarate, trisodium citrate, trisodium nitrilotriacetate, tetrasodium ethylene diamine tetraacetate, and pentasodium diethylene tri And Pentasodium diethylenetriaminepentaacetate.
The carboxylic acid metal salt may be included in 0.01 to 2 parts by weight of the seed alone, 0.005 to 1 part 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 of the monomers constituting the seed, core and shell Within this range, excellent latex stability can be provided without deteriorating the existing mechanical properties.
The ASA-based graft copolymer includes, for example, a polymerized seed comprising 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 surrounding the seed and polymerized comprising alkyl acrylate; And a shell polymerizing at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate compound to surround the core.
The aromatic vinyl compound may be at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, and vinyltoluene. Specifically, styrene is used, but the present invention is not limited thereto.
The vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. Specifically, acrylonitrile may be used, but the present invention is not limited thereto.
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-vinyl aromatic compound-vinyl cyanide copolymer may be, for example, butyl acrylate-styrene-acrylonitrile.
As another example, the alkyl (meth) acrylate-vinyl aromatic compound-vinyl cyanide copolymer may be butyl acrylate-styrene-acrylonitrile-methyl methacrylate.
The ASA-based graft copolymer includes 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 includes, for example, a seed; Or may be a polymerized copolymer further comprising a crosslinking agent in the seed and core.
In the present description, the crosslinking agent is referred to as a monomer.
Examples of the crosslinking agent include divinylbenzene, trivinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6- Hexanediol diacrylate, 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, trimethylol methane triacrylate, trimethylpropaneethoxylate triacrylate, trimethylpropane propoxylate triacrylate , Pentaerythritol ethoxylate triacrylate, pentaerythritol 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 production of the ASA-based graft copolymer is not particularly limited, but preferably a radical initiator can be used. Examples of the radical initiator include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium persulfate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthol hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxides, 3,5,5-trimethylhexanol peroxide, t-butyl peroxyisobutyrate; At least one selected from the group consisting of azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyl acid) methyl, Lt; / RTI > is an inorganic peroxide, and most preferably persulfate.
An activator may be used to promote the initiation reaction of the peroxide with the polymerization initiator, and the activator may be selected from the group consisting of sodium formaldehyde, sulfoxylate, sodium ethylenediamine, tetraacetate, ferrous sulfate, dextrose, Sodium and sodium sulfite, and the like.
The emulsifier of the ASA-based 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 and may be, for example, an alkenyl succinate metal salt, an alkylbenzenesulfonate salt, an aliphatic sulfonate salt, a sulfuric acid ester salt of a higher alcohol, an -olefin sulfonic acid salt, and an alkyl ether sulfuric acid ester salt And the like.
The ASA-based graft copolymer may be, for example, a seed, a core or a shell; The composition may further comprise a mercaptan-based compound as a molecular weight modifier, and preferably the shell may contain a molecular weight modifier.
The ASA-based graft copolymer of the present invention may include, for example, a seed having an average particle diameter of 0.03 to 0.3 탆, 0.05 to 0.2 탆, or 0.1 to 0.2 탆, and an average particle diameter including the seed of 0.05 to 0.5 탆, 0.1 To 0.4 占 퐉, or 0.2 to 0.3 占 퐉.
The ASA-based graft copolymer of the present invention has an average particle diameter larger than the average particle diameter of the core, for example, 0.1 to 0.7 탆, or 0.2 to 0.6 탆, and has an excellent balance of mechanical properties and physical properties within this range .
The copolymer may further contain additives such as dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, plasticizers or matting agents which are conventionally used depending on the application.
The ASA-based graft copolymer composed of the seed, the core and the shell according to the present invention can be provided as a specific example as follows.
The seed may be, for example, at least one seed-forming monomer 4 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 total monomers contained in the ASA-based graft copolymer And 0.01 to 1.0 part by weight of the carboxylic acid metal salt, 0.01 to 1.0 part by weight of the crosslinking agent, 0.1 to 2 parts by weight of the emulsifier and 0.01 to 2 parts by weight of the polymerization initiator. Within this range, Heat stability and surface gloss are excellent.
The core may comprise, for example, from 20 to 80 parts by weight of an alkyl acrylate monomer, from 0 to 1.0 part by weight of a carboxylic acid metal salt, from 0.03 to 2.0 parts by weight of a crosslinking agent, from 0.1 to 0.1 part by weight of an emulsifier To 2 parts by weight of a polymerization initiator and 0.01 to 2 parts by weight of a polymerization initiator. In this range, impact strength, thermal stability and surface gloss are excellent.
The graft shell may be a graft shell selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate compound based on 100 parts by weight of the total monomers contained in the ASA-based graft copolymer. From 20 to 80 parts by weight of an emulsifier, from 0.1 to 2 parts by weight of an emulsifier, from 0 to 1.0 part by weight of a molecular weight modifier and from 0.01 to 2 parts by weight of a polymerization initiator, and has excellent mechanical properties within this range.
As a more specific example, an ASA-based graft copolymer composed of a seed, a core and a shell according to the present invention can be produced as follows.
The seed may be at least one 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 in the production of the ASA-based graft copolymer 4 to 30 parts by weight, 0.01 to 1.0 part by weight of the carboxylic acid metal salt, 0.01 to 1.0 part by weight of a crosslinking agent, 0.1 to 2 parts by weight of an emulsifier and 0.01 to 2 parts by weight of a polymerization initiator, Followed by emulsion polymerization to produce polymer seed latex.
Based on 100 parts by weight of the total monomers used in the production of the ASA-based graft copolymer, 20 to 80 parts by weight of the alkyl acrylate monomer, 0 to 1.0 part by weight of the carboxylic acid metal salt, 0.03 to 2.0 parts by weight of an emulsifier, 0.1 to 2 parts by weight of an emulsifier, and 0.01 to 2 parts by weight of a polymerization initiator are continuously charged or continuously charged, preferably continuously charged and emulsion polymerized to prepare a core as a crosslinked alkyl acrylate rubber polymer .
The shell may be formed from at least one member selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate compound in the presence of the core in an amount of 100 parts by weight based on 100 parts by weight of the total monomers used for producing the ASA- 20 to 80 parts by weight of a graft shell-forming monomer to be selected, 0.1 to 2 parts by weight of an emulsifier, 0 to 1.0 part by weight of a molecular weight modifier and 0.01 to 2 parts by weight of a polymerization initiator are added or continuously charged, To prepare a graft shell.
The polymerization temperature in the emulsion polymerization is not particularly limited, but may be, for example, 50 to 85 ° C, preferably 60 to 80 ° C.
The ASA-based graft copolymer provided according to the present invention can maintain a stable state of the latex even when the solid content of the latex is 40% by weight or more.
The ASA-based graft copolymer provided according to the present invention can be provided as powder particles by agglomeration with a flocculant, followed by aging, dewatering and washing.
Examples of the flocculant include an aqueous solution of an inorganic salt such as aluminum chloride, sodium sulfate, sodium nitrate, calcium chloride, magnesium sulfate, and aluminum sulfate, or an aqueous solution of a flocculant such as sulfuric acid or hydrochloric acid.
The present invention provides a thermoplastic resin composition comprising the above ASA-based graft copolymer, and further provides a molded article, particularly a molded article provided with an extruded sheet, comprising the thermoplastic resin composition.
The thermoplastic resin composition may include 10 to 70% by weight of the ASA-based graft copolymer powder and 30 to 90% by weight of the hard matrix resin.
For example, the hard matrix resin may have a glass transition temperature of 60 ° C or higher. As another example, at least one compound selected from an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate compound, a polycarbonate polymer, And may specifically be a styrene-acrylonitrile resin.
The thermoplastic resin composition may contain at least one selected from dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents and plasticizers which are conventionally used as needed, ≪ / RTI >
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined by the appended claims. Changes and modifications may fall within the scope of the appended claims.
[Example]
Example One
≪ Preparation of ASA-based graft copolymer latex >
Seed preparation step
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 part by weight of sodium lauryl sulfate were collectively administered to a polymerization reactor purged with nitrogen, After the temperature was raised to 70 캜, 0.1 part by weight of potassium persulfate was added to initiate the reaction, and the reaction was carried out for 1 hour while maintaining the temperature at 70 캜 to prepare a seed latex having an average particle diameter of 0.1 탆.
For reference, the average particle size was measured using an intensity Gaussian distribution (Nicomp 380) by a dynamic laser light scattering method.
Core fabrication step
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 in the presence of the seed latex at 70 DEG C for 2 hours The polymerization was further carried out for 1 hour after completion of the addition, and a core having an average particle diameter of 0.23 탆 was prepared as an acrylate rubber polymer.
Graft Shell manufacturing step
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 part by weight of potassium persulfate was continuously added to the mixture in the presence of the acrylate rubber polymer at 70 DEG C for 2 hours Reaction was carried out. After completion of the addition, the mixture was further reacted at 70 DEG C for 1 hour and cooled to 60 DEG C to complete the polymerization reaction to prepare the final ASA-based graft copolymer latex.
The polymerized latex had an average particle diameter of 0.29 탆 and a polymerization conversion of 99%. The solid content of the obtained latex was 40% by weight.
<Preparation of ASA-based graft copolymer powder>
The obtained ASA-based graft copolymer latex was agglomerated at 80 ° C using an aqueous solution of calcium chloride, aged at 95 ° C, dehydrated and washed, and then dried with hot air at 90 ° C for 30 minutes to obtain an ASA-based graft copolymer powder .
≪ Preparation of thermoplastic resin composition >
40 parts by weight of the ASA-based graft copolymer powder and 60 parts by weight of a styrene-acrylonitrile copolymer (LG Chem, product name: 92HR) as a hard matrix resin were mixed with 1 part by weight of a lubricant, 0.5 part by weight of an antioxidant, Parts by weight were added and mixed. This was prepared in the form of pellets using a 40 psi extrusion kneader at a cylinder temperature of 220 캜, and the pellets were injected to prepare physical specimens.
Example 2
The same procedure as in Example 1 was repeated except that disodium oxalate was used in the seed preparation step of Example 1 to replace the trisodium nitrilotriacetate with disodium oxalate.
Example 3
The same procedure 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. The procedure of Example 1 was repeated except that tetrasodium ethylene diamine tetraacetate was used instead of trisodium nitrilotriacetate.
Example 4
The same procedure as in Example 1 was carried out 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, And repeated.
Example 5
The same procedure as in Example 1 was repeated except that butyl acrylate was replaced with styrene in the seed preparation step of Example 1 above.
Example 6
The same procedure 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 procedure as in Example 1 was repeated except that 0.1 part by weight of trisodium nitrilotriacetate was further added in the core preparation step of Example 1.
Example 8
Example 1 was repeated except that 34 parts by weight of styrene and 11 parts by weight of acrylonitrile were replaced with 30 parts by weight of styrene, 9 parts by weight of acrylonitrile and 6 parts by weight of methyl methacrylate in the shell preparation step of Example 1, The same process was repeated.
Example 9
The same procedure as in Example 1 was repeated except that 0.1 part by weight of tertiary dodecyl mercaptan was further added in the shell preparation step of Example 1 above.
Comparative Example One
The same procedure as in Example 1 was repeated except that trisodium nitrilotriacetate was not used in the seed preparation step of Example 1 above.
Comparative Example 2
The same procedure as in Example 1 was repeated except that sodium acetate was used instead of trisodium nitrilotriacetate in the seed preparation step of Example 1. The procedure of Example 1 was repeated except that sodium acetate was used instead of trisodium nitrilotriacetate.
Comparative Example 3
The same procedure as in Example 1 was repeated except that in the seed preparation step of Example 1, potassium chloride was used instead of trisodium nitrilotriacetate.
Comparative Example 4
The same procedure as in Example 1 was repeated except that sodium bicarbonate was used instead of trisodium nitrilotriacetate in the seed preparation step of Example 1. [
Comparative Example 5
The same procedure as in Example 1 was repeated except that sodium bisulfate was used instead of trisodium nitrilotriacetate in the seed preparation step of Example 1 above.
Comparative Example 6
The same procedure as in Example 1 was repeated except that trisodium nitrilotriacetate was replaced with potassium phosphate in the seed preparation step of Example 1 above.
The properties of the ASA-based graft copolymer and the thermoplastic resin composition specimen including the copolymer prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 1 and 2 below.
* Average Particle Diameter: Measured using an intensity Gaussian distribution (Nicomp 380) using a dynamic laser light scattering method.
Polymerization Conversion Rate (%): The polymerization conversion rate was measured by measuring the weight of the prepared latex (1.5 g) after drying in a 150 ° C hot air dryer for 15 minutes to determine the total solid content (TSC) Respectively.
[Equation 1]
* Coagulated water content (wt%): The produced ASA-based graft copolymer latex was filtered with a 200-mesh wire mesh to dry the coagulated product that did not pass through the mesh at 100 ° C for 7 hours and then the weight was measured to determine the content of coagulated product Respectively. The higher the solidification water content, the lower the stability of latex.
* Projection score: The degree of protrusion was quantified by manufacturing an extruded sheet. The closer to 5 points from 1 to 5, the higher the occurrence rate of protrusions.
* Izod impact strength (1/4 notched at 23 占 폚, kgf 占 / m / cm): measured according to ASTM D256.
Surface gloss (45 DEG): Measured according to ASTM D2457.
Thermal Stability: The pellets produced by using an extrusion kneader were held in an injection molding machine at a molding temperature of 260 DEG C for 10 minutes, and then the degree of discoloration ( DELTA E ) was shown by the following equation (2) Is an arithmetic average value of Hunter Lab values before and after stay, and the value closer to 0 indicates excellent thermal stability.
&Quot; (2) "
Through the Tables 1 and 2, the thermoplastic resin compositions of Examples 1 to 9 including the ASA-based graft copolymer prepared by using the carboxylic acid metal salt according to the present invention can be produced by using the carboxylic acid metal salt or using a conventional electrolyte Compared with the thermoplastic resin compositions of Comparative Examples 1 to 6 including the ASA-based graft copolymer prepared by using the thermoplastic resin composition of the present invention, excellent impact strength, thermal stability and surface gloss were obtained, and no protrusion was generated at the time of extrusion .
Claims (18)
Wherein the carboxylic acid metal salt has a molecular weight of 100 to 750 g / mol.
The carboxylic acid metal salt
The carboxylic acid metal salt may be selected from the group consisting of disodium oxalate, disodium malonate, disodium succinate, disodium phthalate, disodium malate, Disodium fumarate, trisodium citrate, trisodium nitrilotriacetate, tetrasodium ethylene diamine tetraacetate, and pentasodium diethylene triamine pentaacetate (Pentasodium diethylenetriaminepentaacetate). ≪ / RTI >
The carboxylic acid metal salt includes 0.01 to 2 parts by weight or 0.005 to 1 part by weight based on 100 parts by weight of the total of the monomers constituting the seed, core and shell, and 0.005 to 1 part by weight to the core. ASA-based graft copolymer.
The ASA-based graft copolymer includes a polymerized seed comprising 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 surrounding the seed and polymerized comprising alkyl acrylate; And a shell polymerized with at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate compound to surround the core, and an ASA-based graft copolymer .
Wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, and vinyltoluene.
Wherein the vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.
Wherein the alkyl of the alkyl (meth) acrylate has 2 to 8 carbon atoms.
Wherein the ASA-based graft copolymer comprises 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.
Wherein the ASA-based graft copolymer comprises a seed; Or a seed and a core; and a cross-linking agent.
Wherein the hard matrix resin has a glass transition temperature of 60 DEG C or more.
Wherein the thermoplastic resin composition further comprises at least one member selected from the group consisting of a lubricant, a heat stabilizer, an antioxidant, a light stabilizer, an antistatic agent, a pigment and an inorganic filler.
Wherein the thermoplastic resin composition has a surface gloss of 85 or more as measured according to ASTM D2457.
The thermoplastic resin composition The thermoplastic resin composition characterized in that a 4.0 or less thermally stable (Δ E).
Wherein the molded article is an extruded sheet from which protrusions have not occurred.
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| US3627741A (en) * | 1967-08-22 | 1971-12-14 | Monsanto Co | Polymerization process for producing uniform acrylonitrile polymers using chlorate/sulfoxy redox initiators and amino polyacids or salts thereof |
| JPH0873535A (en) * | 1994-04-27 | 1996-03-19 | Nippon Shokubai Co Ltd | Production of thermoplastic resin |
| KR20000000784A (en) * | 1998-06-03 | 2000-01-15 | 성재갑 | Resin composition excellent in impact resistance and surface glossiness, and process for producing the same |
| KR20140027872A (en) * | 2012-08-27 | 2014-03-07 | 주식회사 엘지화학 | Graft copolymer and thermoplastic resin composition comprising thereof |
| KR20150010921A (en) * | 2013-07-19 | 2015-01-29 | 주식회사 엘지화학 | Core-Shell Nano Particle for Formation of Transparent Conductive Film, and Manufacturing Method of Transparent Conductive Film Using the Same |
| KR20150038975A (en) * | 2013-10-01 | 2015-04-09 | 주식회사 엘지화학 | Thermoplastic resin composition |
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2015
- 2015-10-29 KR KR1020150151151A patent/KR102023986B1/en active IP Right Grant
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3627741A (en) * | 1967-08-22 | 1971-12-14 | Monsanto Co | Polymerization process for producing uniform acrylonitrile polymers using chlorate/sulfoxy redox initiators and amino polyacids or salts thereof |
| JPH0873535A (en) * | 1994-04-27 | 1996-03-19 | Nippon Shokubai Co Ltd | Production of thermoplastic resin |
| KR20000000784A (en) * | 1998-06-03 | 2000-01-15 | 성재갑 | Resin composition excellent in impact resistance and surface glossiness, and process for producing the same |
| KR20140027872A (en) * | 2012-08-27 | 2014-03-07 | 주식회사 엘지화학 | Graft copolymer and thermoplastic resin composition comprising thereof |
| KR20150010921A (en) * | 2013-07-19 | 2015-01-29 | 주식회사 엘지화학 | Core-Shell Nano Particle for Formation of Transparent Conductive Film, and Manufacturing Method of Transparent Conductive Film Using the Same |
| KR20150038975A (en) * | 2013-10-01 | 2015-04-09 | 주식회사 엘지화학 | Thermoplastic resin composition |
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